CN115216342B - Preparation method of polyester-grade coal-based ethylene glycol - Google Patents
Preparation method of polyester-grade coal-based ethylene glycol Download PDFInfo
- Publication number
- CN115216342B CN115216342B CN202110399174.XA CN202110399174A CN115216342B CN 115216342 B CN115216342 B CN 115216342B CN 202110399174 A CN202110399174 A CN 202110399174A CN 115216342 B CN115216342 B CN 115216342B
- Authority
- CN
- China
- Prior art keywords
- impurities
- ethylene glycol
- glycol
- coal
- raw material
- Prior art date
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 239000003245 coal Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 49
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 40
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003463 adsorbent Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 80
- 239000003054 catalyst Substances 0.000 claims description 29
- 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
- 150000001299 aldehydes Chemical class 0.000 claims description 20
- 239000003085 diluting agent Substances 0.000 claims description 19
- -1 n-amyl Chemical group 0.000 claims description 16
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 239000003607 modifier Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 150000002148 esters Chemical class 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 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
- 150000002576 ketones Chemical class 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- BSABBBMNWQWLLU-UHFFFAOYSA-N hydroxypropionaldehyde Natural products CC(O)C=O BSABBBMNWQWLLU-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 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
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-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
- 125000004432 carbon atom Chemical group C* 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 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
- 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
- 102000007590 Calpain Human genes 0.000 claims description 2
- 108010032088 Calpain Proteins 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 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
- 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
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 4
- 229910017052 cobalt Inorganic materials 0.000 claims 2
- 239000010941 cobalt Substances 0.000 claims 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 2
- 229910052697 platinum Inorganic materials 0.000 claims 2
- 238000002834 transmittance Methods 0.000 abstract description 23
- 238000004821 distillation Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 41
- 238000010438 heat treatment Methods 0.000 description 25
- 238000011068 loading method Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 23
- 239000011248 coating agent Substances 0.000 description 22
- 238000000576 coating method Methods 0.000 description 22
- 238000002156 mixing Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 18
- 239000012467 final product Substances 0.000 description 13
- 238000005086 pumping Methods 0.000 description 13
- 238000007670 refining Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 229910003023 Mg-Al Inorganic materials 0.000 description 6
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 229920000555 poly(dimethylsilanediyl) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000001228 spectrum 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
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 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
- 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
- 238000004040 coloring Methods 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
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002170 ethers Chemical class 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
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 238000005292 vacuum distillation Methods 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
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) The high-purity inferior coal-based glycol raw material passes through an adsorption bed, fully contacts with an adsorbent in the bed to carry out adsorption reaction, and an effluent obtained by the adsorption reaction is named as AD-EG; (2) The AD-EG obtained in the step (1) enters a fixed bed reactor to carry out hydrofining reaction, and effluent obtained after the reaction is recorded 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 glycol product. According to the method, through the accurate and efficient removal of different types of micro/trace impurities in the high-purity inferior raw material, the light transmittance of the obtained polyester-grade ethylene glycol product meets the GB/T4694-2018 rule, and compared with the raw material, the light transmittance at 220nm, 275nm and 350nm is greatly improved.
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 taking 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 mostly used for producing polyester fiber, antifreeze, nonionic surfactant and other products. China is one of countries with the largest glycol import amount, and has higher external dependence degree. At present, two technical routes of ethylene glycol industry exist, one is to prepare ethylene glycol by using crude oil and natural gas as raw materials, and the method has high energy consumption in the production process and large influence of raw material price on cost. The other oxalate method using coal as raw material can effectively save petroleum resources, accords with the energy status quo of 'more coal, less oil and gas' in China, and has been developed faster in recent years. However, a certain amount of impurities are easy to introduce in the process of preparing the ethylene glycol by a coal-based method, wherein a small part of impurities can cause serious reduction of ultraviolet light transmittance of an ethylene glycol product, and the requirement of a polyester-grade product is difficult to reach. In GB/T4694-2018, it is specified that the transmittance of the polyester grade glycol should not be less than 75%, 92% and 99% at wavelengths of 220nm, 275nm and 350 nm. Ethylene glycol products with unacceptable ultraviolet light transmittance are used for producing polymers, and the properties of the polymers, such as chromaticity, glossiness, strength, coloring performance and the like, are seriously affected. Impurities that affect ultraviolet transmittance are generally considered to be aldehyde, ketone, or ester impurities containing a carbonyl structure. In addition, the research shows that certain olefine acid and olefine acid ester substances have very obvious influence on the ultraviolet light transmittance at 220nm, and the substances are often low in the coal-based glycol and are difficult to remove. Therefore, the impurities in the coal-based ethylene glycol are removed, and the polyester-grade coal-based ethylene glycol product is prepared, so that the method 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 above background, many researchers have conducted a series of research efforts around coal-based ethylene glycol impurity removal and the preparation of polyester-grade ethylene glycol. For example, CN105085175 a discloses a method for absorbing impurities in coal-based ethylene glycol by acid leaching pretreatment modified activated carbon, the method is designed according to a coal-based ethylene glycol process route, the impurities in the coal-based ethylene glycol can be effectively absorbed, the UV value at 220nm is improved from 50% to 84%, and finally the product reaches the polyester grade. CN102911013 a discloses a bifunctional solid acid catalyst and a solid base catalyst, and by reduction and catalysis of the catalyst, aldehyde impurities in the petroleum route and impurities such as esters, cyclic diketones and conjugated aldehydes in the coal chemical route can be removed at the same time, so that UV values of coal-based ethylene glycol and petroleum-based ethylene 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 performance of coconut carbon and the hydrogenation reduction capability of a composite hydrogenation catalyst are utilized to improve the ultraviolet light transmittance of ethylene glycol, so that the light transmittance at 220nm is improved 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 ethylene glycol is selected as a raw material, and UV values at 220nm and 275nm are respectively improved from 93% and 96% to 96% and 97% through aldehyde removal. The impurities in the ethylene glycol are removed through different methods, so that the light transmittance of the ethylene glycol is obviously improved, the requirement of a polyester-grade product is finally met, and a good foundation is provided for the deep development of related work.
However, the above researches are carried out by taking ethylene glycol with relatively high light transmittance, relatively few impurity types and low content as raw materials, and the researches on preparing polyester-grade ethylene glycol by taking ethylene glycol with high purity (more than or equal to 99.0%) of raw materials, a plurality of impurity types and extremely low light transmittance of each wave band as raw materials are few, and the related researches are still further needed.
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 the accurate and efficient removal of different types of micro/trace impurities in the high-purity inferior raw material, the light transmittance of the obtained polyester-grade ethylene glycol product meets the GB/T4694-2018 rule, and compared with the raw material, the light transmittance at 220nm, 275nm and 350nm is greatly improved.
The preparation method of the polyester-grade coal-based glycol comprises the following steps:
(1) The high-purity inferior coal-based glycol raw material passes through an adsorption bed, fully contacts with an adsorbent in the bed to carry out adsorption reaction, and an effluent obtained by the adsorption reaction is named as AD-EG;
(2) The AD-EG obtained in the step (1) enters a fixed bed reactor to carry out hydrofining reaction, and effluent obtained after the reaction is recorded as HY-EG;
(3) And (3) carrying out vacuum distillation on the HY-EG obtained in the step (2), and collecting middle and rear section fractions/bottom fractions at the top of the tower to obtain a polyester-grade ethylene glycol product which is marked as VC-EG.
In the method of the invention, the high-purity inferior coal-based ethylene glycol raw material in the step (1) has the following properties: the purity of the glycol is more than or equal to 99.0 percent, the total impurity content is less than 400ppm, wherein the aldehyde impurity content is more than 200mg/kg, and the 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 chromaticity (platinum-cobalt) is 0 to 30 percent.
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, diethyl ether, ethylene glycol ethyl ether, 1, 4-dioxane and the like; the ketone impurity is one or more of 2, 3-butanedione, dihydroxyacetone, 3-methyl-1, 2-cyclopentanedione, etc.; the alcohol 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 and the like; 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 of the invention, the adsorbent in the step (1) is polysilane modified activated carbon, and the polysilane has the following structure:
wherein R is 1 Is one of alkyl, alkoxy and alkoxyalkyl, preferably alkyl, and has 1 to 8 carbon atoms; r is R 2 Is one of alkyl, alkoxy and 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 one of methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, n-pentyloxy and 2-ethylhexyloxy; the alkoxyl alkyl is one of methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl and pentoxymethyl. m is an integer of 5 to 25, preferably 10 to 20.
In the method of the invention, the preparation method of polysilane modified activated carbon in the step (1) comprises the following steps: spraying active carbon by using a mixture of polysilane and a diluent, and then performing temperature programming roasting treatment in an inert atmosphere, wherein a roasted product is polysilane modified active carbon; wherein the diluent can be one of toluene, ethylbenzene, n-hexane, cyclohexane, n-octane, isooctane and n-heptane; polysiliconeThe volume ratio of the alkane modifier to the diluent is 1:1-1:9. The activated carbon raw material is one of coal-based activated carbon, wood-based activated carbon and shell-based activated carbon, and the specific surface area of the activated carbon raw material is 500-2000 m 2 Preferably 1000 to 1800 m/g 2 And/g. The mass ratio of the polysilane and diluent mixture to the active carbon raw material is 1:2-1:10. The temperature programming roasting conditions are as follows: roasting for 0.5-4 hours at 100-150 ℃, and then roasting for 0.5-4 hours at 200-300 ℃. The inert atmosphere is one or more of nitrogen, helium, neon and argon. In the method of the present invention, the adsorption reaction conditions in step (1) are: the temperature is 20-60 ℃, preferably 30-50 ℃; the liquid hourly space velocity is 0.25-25 h -1 Preferably 2.5 to 12.5 hours -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction pressure is 0.05-0.6 MPa, preferably 0.1-0.4 MPa.
In the method of the present invention, the hydrofining catalyst in the step (2) is a transition metal supported catalyst. The active metal component of the transition metal supported catalyst is one or two of Cu, ni, pd, pt, ru and Rh, preferably Ni and/or Pd; the carrier of the transition metal supported catalyst is any one of alumina, chromia, titania, zirconia, silica, activated carbon and calpain, preferably alumina and/or titania.
In the method of the present invention, the transition metal supported catalyst in step (2) may further include a promoting metal component in addition to the active metal component, where the promoting metal component has the effects of reducing the acting force between the active metal and the carrier, and improving the dispersity and catalytic activity of the active component. The catalytic metal component is any one or any two of W, mo, mg, fe, ce, V, ca, mn and Ba.
In the method of the present invention, the active metal component loading amount of the transition metal supported catalyst in the step (2) is 0.01wt% to 55wt%, preferably 0.1wt% to 40wt%; the load of the auxiliary catalytic metal component of the transition metal supported catalyst is 0.01-30 wt%, preferably 0.1-15 wt%.
In the method of the present invention, the hydrofining reaction conditions in the step (2) are as follows: the reaction temperature is 40-160 ℃, preferably 80-120 DEG CThe pressure is 0.1-5 MPa, preferably 0.2-2.5 MPa, the volume ratio of hydrogen to raw materials (hydrogen-material ratio for short) is 50:1-2500:1, preferably 500:1-2000:1, and the volume space velocity is 0.2-10 h -1 Preferably 0.5 to 5 hours -1 。
In the method of the invention, the vacuum rectification in the step (3) is intermittent common vacuum rectification, and the rectification process does not use entrainer and catalyst, and the specific process conditions are as follows: the theoretical plate number is 10-20, the tower top pressure is 2-20 KPa, the reflux ratio R is 3-12, and the temperature of a tower kettle reboiler is 100-160 ℃. The overhead distillate with the mass accounting for 20 percent of the mass of the raw material, namely the front-end fraction of the overhead product with the enriched impurities, is generally collected and is treated, and the middle-rear-end fraction and the bottom fraction of the rest overhead product are target products.
The polyester-grade glycol product obtained by the method meets the specification of GB/T4694-2018, and has the following specific properties: the purity of the glycol is more than or equal to 99.6%, the aldehyde content is 0-8 mg/kg, and the UV is 75% or less 220nm ≤100%，92%≤UV 275nm ≤100%，99%≤UV 350nm Less than or equal to 100 percent, and the chromaticity (platinum-cobalt) is 0 to 5.
Compared with the prior art, the invention has the following advantages:
(1) The coal-based ethylene glycol raw material in the prior art is generally low in aldehyde content, simple in impurity type and high in self-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) Aiming at the complex micro/trace impurity composition characteristics of the raw materials, the invention adopts a technical route of adsorption, hydrogenation and rectification. The adsorption process is matched with a specific adsorbent (the invention utilizes the reaction of active hydrogen on polysilane and active carbon oxygen-containing groups at high temperature to remove oxygen-containing functional groups and generate water, and ensures that polysilane is uniformly distributed on the surface of the active carbon, thereby obviously improving the adsorption capacity of the active carbon to nonpolar or weakly polar impurities), and the adsorption process effectively adsorbs and removes ether impurities with polarity different from other impurities. After the ether impurities are removed, the aldehyde impurities are removed through milder hydrofining, and then the acid and ester impurities which are difficult to convert in the milder hydrogenation are removed through reduced pressure rectification.
Drawings
FIG. 1 GC-MC spectrum of a poor quality coal-based ethylene glycol feedstock.
FIG. 2 GC-MS spectrum of the polyester-grade ethylene glycol obtained in example 5.
Detailed Description
The method for preparing coal-based polyester-grade ethylene glycol according to the present invention is further described below by way of specific examples, but is not limited thereto.
The raw materials in the examples and comparative examples of the invention are high-purity inferior coal-based ethylene glycol, and the main properties of the inferior 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 indicating the inferior degree of the high purity coal-based ethylene glycol raw material, and does not limit the raw materials selected in the present invention.
TABLE 1 Primary Properties of inferior coal-based ethylene glycol feedstock
As shown in the table, the purity of the inferior 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 inferior raw material is as high as 262mg/kg. The aldehyde impurities are mainly glycolaldehyde and 2-hydroxybutyraldehyde; the inferior raw material contains other various impurities at the same time, wherein the ketone impurities are mainly 2, 3-butanedione and dihydroxyacetone; the ether impurities are mainly methyl ethyl ether and 1, 4-dioxane; the alcohol impurities are mainly 1, 2-propylene glycol, 1, 2-butanediol, 1, 2-pentanediol, 3-ethyl-2-pentanol and diethylene glycol (same genus ethers); the acid and ester impurities are mainly ethyl glycolate, ethylene carbonate and dimethyl oxalate.
The transmittance of the polyester-grade glycol in the examples and comparative examples of the present invention was measured by a Japanese Hitachi U-3900 ultraviolet spectrophotometer, and specific measurement steps and methods were referred to the standard GB/T14571.4-2008.
UV in all of the examples and comparative examples below 220nm 、UV 275nm 、UV 350nm The meaning indicated is the transmittance of ethylene glycol at 220nm, 275nm, 350 nm.
Example 1
Preparing a coating solution by using polymethyl ethyl silane (m=25) as a modifier and toluene as a diluent according to a volume ratio of 1:1, and mixing the coating solution with a specific surface area of 500 m 2 Uniformly mixing per gram of coal-based activated carbon according to the mass ratio of 1:10, then heating and roasting at 100 ℃ for 0.5h and 300 ℃ for 4h in a nitrogen atmosphere, and naturally cooling to obtain the polymethyl ethyl silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 20deg.C for 0.25 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.05MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-1. Pumping AD-EG-1 into a fixed bed reactor, and carrying out hydrogen material ratio of 50:1 and 0.2h at 40 ℃ and 0.1MPa -1 Hydrofining under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt load is 0.01% wt, the Mg load is 0.1% wt, and the product obtained by hydrofining is recorded as HY-EG-1; the HY-EG-1 is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 160 ℃ of a tower kettle reboiler under the conditions of 10 theoretical plates, 2KPa of tower top pressure and reflux ratio R=3, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-1, and the UV value is detected. Detected, final product UV 220nm =76.8，UV 275nm =96.5，UV 350nm =99.2。
Example 2
Adopting polypropylmethoxy silane (m=5) as modifier and n-hexane as diluent to prepare coating liquid according to the volume ratio of 1:9, and mixing the coating liquid with the specific surface area of 2000m 2 Uniformly mixing/g shell-based activated carbon fiber according to a mass ratio of 1:2, heating and roasting in helium atmosphere at 150 ℃, 4h,200 ℃ and 0.5h, and naturally cooling to obtain the polypropylmethoxy silane modified activated carbonAn adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 60deg.C for 25 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.6MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-2. Pumping AD-EG-2 into a fixed bed reactor, and heating at 160 ℃ and 5MPa for 10 hours at a hydrogen-to-feed ratio of 2500:1 -1 Hydrofining under the condition that the hydrofining catalyst is Cu/Mn-TiO 2 Wherein Cu loading is 55% wt, mn loading is 15% wt, and the product obtained by hydrofining is HY-EG-2; the HY-EG-2 is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the ordinary reduced pressure rectification is carried out at the temperature of 100 ℃ of a tower kettle reboiler under the conditions of 20 theoretical plates, 20KPa of tower top pressure and reflux ratio R=12, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-2, and the UV value is detected. Detected, final product UV 220nm =77.2，UV 275nm =97.4，UV 350nm =99.5。
Example 3
Preparing a coating solution by taking polyethoxy-methoxymethyl silane (m=7) as a modifier and cyclohexane as a diluent according to a volume ratio of 1:6, and mixing the coating solution with a specific surface area of 750 m 2 Uniformly mixing/g coal material-based activated carbon according to the mass ratio of 1:5, heating and roasting at 130 ℃ for 3 hours and 220 ℃ for 1.5 hours in an argon atmosphere, and naturally cooling to obtain the polyethoxy-methoxymethyl silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 30deg.C for 2.5 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.1MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-3. Pumping AD-EG-3 into a fixed bed reactor, and carrying out hydrogen material ratio of 500:1 and 0.5h at 80 ℃ and 0.2MPa -1 Hydrofining under the condition that the hydrofining catalyst is Ni-Pt/Fe-ZrO 2 Wherein the Ni-Pt loading is 0.1% wt (Ni: pt=1:1), the Fe loading is 0.01% wt, and the hydrofining product is HY-EG-3; the HY-EG-3 is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the ordinary reduced pressure rectification is carried out at the temperature of 155 ℃ of a tower kettle reboiler under the conditions of 18 theoretical plates, 12KPa of tower top pressure and reflux ratio R=5, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-3, and the UV value is detected. Detected, final product UV 220nm =79.4，UV 275nm =98.5，UV 350nm =99.8。
Example 4
Preparing a coating solution by using poly isopropyl-butoxy silane (m=13) as a modifier and n-octane as a diluent according to a volume ratio of 1:8, and mixing the coating solution with a specific surface area of 1800: 1800m 2 Uniformly mixing/g shell-based activated carbon fiber according to the mass ratio of 1:7, heating and roasting at 145 ℃ for 2 hours and 275 ℃ for 3.5 hours in a nitrogen atmosphere, and naturally cooling to obtain the poly isopropyl-butoxy silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 50deg.C for 12.5 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under 0.4MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-4. Pumping AD-EG-4 into a fixed bed reactor, and carrying out hydrogen material ratio of 2000:1 and 5h at 120 ℃ and 2.5MPa -1 Hydrofining is carried out under the condition that the hydrofining catalyst is Ni/Mo-calpain, wherein the Ni loading amount is 40wt percent, the Mo loading amount is 30wt percent, and the product obtained by hydrofining is HY-EG-4; the HY-EG-4 is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the ordinary reduced pressure rectification is carried out at the temperature of 125 ℃ of a tower kettle reboiler under the conditions of 12 theoretical plates, 18KPa of tower top pressure and reflux ratio R=7, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-4, and the UV value is detected. Detected, final product UV 220nm =80.2，UV 275nm =98.9，UV 350nm =99.8。
Example 5
Preparing a coating solution by taking polydimethylsilane (m=22) as a modifier and isooctane as a diluent according to a volume ratio of 1:7, and mixing the coating solution with a specific surface area of 1000 m 2 Uniformly mixing/g of wood-based activated carbon according to the mass ratio of 1:4, then heating and roasting at 115 ℃ for 2.5h and 248 ℃ for 1h in a nitrogen atmosphere, and naturally cooling to obtain the polydimethylsilane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 45deg.C for 10 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.3MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-5. Pumping AD-EG-5 into a fixed bed reactor, and heating at 115 ℃ and 2MPa with hydrogen-to-material ratio of 800:1 for 2h -1 Hydrofining under the condition that the hydrofining catalyst is Ni/W-Ce, wherein the Ni loading is 30% wt, the W loading is 10% wt, and the product obtained by hydrofining is recordedIs HY-EG-5; the HY-EG-5 is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 144 ℃ of a tower kettle reboiler under the conditions of 16 theoretical plates, 5KPa of tower top pressure and reflux ratio R=10, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-5, and the UV value is detected. Detected, final product 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 1:5, and mixing the coating solution with a specific surface area of 850 m 2 Uniformly mixing/g of wood-based activated carbon according to the mass ratio of 1:6, then heating and roasting at 144 ℃ for 1.5h and 289 ℃ for 3h in a nitrogen atmosphere, and naturally cooling to obtain the polybutyl-isobutyl silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 40deg.C for 8 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.35MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-6. Pumping AD-EG-6 into a fixed bed reactor, and heating at 100deg.C under 1.5MPa with hydrogen ratio of 600:1 for 1.5h -1 Hydrofining under the condition that the hydrofining catalyst is Pd/V-Cr 2 O 3 Wherein Pd loading is 0.5% wt, V loading is 3% wt, and the product obtained by hydrofining is HY-EG-6; the HY-EG-6 is filled as a rectifying material to the bottom of a batch rectifying tower, the reflux ratio R=6 is carried out under the conditions of the theoretical plate number of 13, the tower top pressure of 6.5KPa and the tower kettle reboiler temperature of 100 ℃, the ordinary reduced pressure rectification is carried out, the middle and rear section distillate of the tower top is collected and recorded as VC-EG-6, and the UV value is detected. Detected, final product 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 1:4, and mixing the coating solution with a specific surface area of 1280 and 1280 m 2 Uniformly mixing/g of wood-based activated carbon according to the mass ratio of 1:3, then heating and roasting in a nitrogen atmosphere at 131 ℃ for 2.5h and 292 ℃ for 3.5h, and naturally cooling to obtain the polydidisilane modified activated carbon adsorbent. Loading activated carbon adsorbent toBed layer, at 52 ℃ for 15h -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.5MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-7. Pumping AD-EG-7 into a fixed bed reactor, and pumping the AD-EG-7 into the fixed bed reactor at 88 ℃ and 4MPa with a hydrogen-to-material ratio of 1250:1 for 5.5h -1 Hydrofining under the condition that the hydrofining catalyst is Rh/Ba-SiO 2 Wherein Rh loading is 7% wt, ba loading is 4.5% wt, and the product obtained by hydrofining is HY-EG-7; the HY-EG-7 is filled as a rectifying material to the bottom of a batch rectifying tower, the ordinary reduced pressure rectification is carried out at the temperature of 152 ℃ of a tower kettle reboiler under the conditions of 19 theoretical plates, 11.5KPa of tower top pressure and reflux ratio R=8, the middle and rear section distillate of the tower top is collected and recorded as VC-EG-7, and the UV value is detected. Detected, final product UV 220nm =81.7，UV 275nm =99.0%，UV 350nm =99.7。
Comparative example 1
Preparing a coating solution by using polymethyl ethyl silane (m=25) as a modifier and toluene as a diluent according to a volume ratio of 1:1, and mixing the coating solution with a specific surface area of 500 m 2 Uniformly mixing per gram of coal-based activated carbon according to the mass ratio of 1:10, then heating and roasting at 100 ℃ for 0.5h and 300 ℃ for 4h in a nitrogen atmosphere, and naturally cooling to obtain the polymethyl ethyl silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 20deg.C for 0.25 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.05MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-a. AD-EG-a is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 160 ℃ of a tower kettle reboiler under the conditions of 10 theoretical plates, 2KPa of tower top pressure and reflux ratio R=3, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-a, and the UV value is detected. Detected, final product UV 220nm =36.4，UV 275nm =81.2，UV 350nm =94.2。
Comparative example 2
Preparing a coating solution by using polymethyl ethyl silane (m=25) as a modifier and toluene as a diluent according to a volume ratio of 1:1, and mixing the coating solution with a specific surface area of 500 m 2 Uniformly mixing/g coal-based activated carbon according to a mass ratio of 1:10, and heating in a nitrogen atmosphere at 100 ℃ for 0.5h,300 ℃ for 4hRoasting, and naturally cooling to obtain the polymethyl ethyl silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 20deg.C for 0.25 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.05MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-b. Pumping AD-EG-b into a fixed bed reactor, and carrying out hydrogen material ratio of 50:1 and 0.2h at 40 ℃ and 0.1MPa -1 Hydrofining under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt load is 0.01% wt and the Mg load is 0.1% wt, the product obtained by hydrofining is recorded as HY-EG-b, and the UV value is detected. Detected, final product UV 220nm =33.8，UV 275nm =86.7，UV 350nm =96.6。
Comparative example 3
Pumping inferior coal-based glycol raw material into a fixed bed reactor, and carrying out hydrogen-material ratio of 50:1 and 0.2h at 40 ℃ and 0.1MPa -1 Hydrofining under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt load is 0.01% wt, the Mg load is 0.1% wt, and the product obtained by hydrofining is recorded as HY-EG-c; the HY-EG-c is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 160 ℃ of a tower kettle reboiler under the conditions that the theoretical plate number is 10, the tower top pressure is 2KPa and the reflux ratio R=3, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-c, and the UV value is detected. Detected, final product UV 220nm =35.5，UV 275nm =85.4，UV 350nm =96.2。
Comparative example 4
Pumping inferior coal-based glycol raw material into a fixed bed reactor, and carrying out hydrogen-material ratio of 50:1 and 0.2h at 40 ℃ and 0.1MPa -1 Hydrofining under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt load is 0.01% wt, the Mg load is 0.1% wt, and the product obtained by hydrofining is recorded as HY-EG-d; preparing a coating solution by using polymethyl ethyl silane (m=25) as a modifier and toluene as a diluent according to a volume ratio of 1:1, and mixing the coating solution with a specific surface area of 500 m 2 Uniformly mixing per gram of coal-based activated carbon according to the mass ratio of 1:10, then heating and roasting at 100 ℃ for 0.5h and 300 ℃ for 4h in a nitrogen atmosphere, and naturally cooling to obtain the polymethyl ethyl siliconAn alkane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 20deg.C for 0.25 hr -1 And (3) enabling the HY-EG-d to pass through an adsorption bed under the pressure of 0.05MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-d. AD-EG-d is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 160 ℃ of a tower kettle reboiler under the conditions that the theoretical plate number is 10, the tower top pressure is 2KPa and the reflux ratio is R=3, the middle-rear section fraction of the tower top is collected and recorded as VC-EG-d, and the UV value is detected. Detected final product UV 220nm =37.2，UV 275nm =87.0，UV 350nm =97.1。
Comparative example 5
Preparing a coating solution by using polymethyl ethyl silane (m=25) as a modifier and toluene as a diluent according to a volume ratio of 1:1, and mixing the coating solution with a specific surface area of 500 m 2 Uniformly mixing per gram of coal-based activated carbon according to the mass ratio of 1:10, then heating and roasting at 100 ℃ for 0.5h and 300 ℃ for 4h in a nitrogen atmosphere, and naturally cooling to obtain the polymethyl ethyl silane modified activated carbon adsorbent. Loading activated carbon adsorbent into bed layer, and heating at 20deg.C for 0.25 hr -1 Allowing inferior coal-based glycol to pass through an adsorption bed under the pressure of 0.05MPa, and recording the product obtained by preliminary adsorption refining as AD-EG-e. AD-EG-e is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 160 ℃ of a tower kettle reboiler under the conditions that the theoretical plate number is 10, the tower top pressure is 2KPa and the reflux ratio is R=3, and the middle-rear section fraction at the tower top is collected and recorded as VC-EG-e; pumping the VC-EG-e raw material into a fixed bed reactor, and heating at 40 ℃ and 0.1MPa, and hydrogen-material ratio of 50:1 for 0.2h -1 Hydrofining under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt load is 0.01% wt and the Mg load is 0.1% wt, the product obtained by hydrofining is recorded as HY-EG-e, and the UV value is detected. Detected final product UV 220nm =34.0，UV 275nm =89.2，UV 350nm =97.3。
Comparative example 6
Adopting a specific surface area of 500 m 2 Coal-based activated carbon per gram is used as adsorbent, and is filled into a bed layer at 20 ℃ for 0.25h -1 Passing inferior coal-based glycol through an adsorption bed under 0.05MPa, and recording the product obtained by preliminary adsorption refiningIs AD-EG-f. Pumping AD-EG-f into a fixed bed reactor, and carrying out hydrogen-feed ratio of 50:1 and 0.2h at 40 ℃ and 0.1MPa -1 Hydrofining under the condition that the hydrofining catalyst is Pt/Mg-Al 2 O 3 Wherein the Pt load is 0.01% wt, the Mg load is 0.1% wt, and the product obtained by hydrofining is recorded as HY-EG-f; the HY-EG-f is used as a rectifying material to be filled into the bottom of a batch rectifying tower, the common reduced pressure rectification is carried out at the temperature of 160 ℃ of a tower kettle reboiler under the conditions that the theoretical plate number is 10, the tower top pressure is 2KPa and the reflux ratio is R=3, the middle and rear section fractions at the tower top are collected and recorded as VC-EG-f, and the UV value is detected. Detected, final product UV 220nm =48.5，UV 275nm =90.6，UV 350nm =98.4。
Example 8
The ethylene glycol products obtained in the examples and comparative examples were analyzed and evaluated in terms of various properties according to the methods and standards shown 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 of examples 1-7 were UV 220nm All greater than 75%, UV 270nm Are all greater than 92%, UV 350nm All are more than 99%, the aldehyde content is less than 8mg/kg, and the platinum-cobalt chromaticity is less than 5, which indicates that the high-quality ethylene glycol product with the performance meeting the polyester-grade ethylene glycol standard can be obtained by adopting the methods described in examples 1-7 by taking high-purity inferior coal-based ethylene glycol as a raw material. The samples of comparative examples 1-3 have relatively low light transmittance at 220nm, 275nm and 350nm, and particularly have light transmittance at 220nm which is less than 40%, which indicates that the method described in examples 1-3 is difficult to deeply remove aldehyde and complex impurities, and unsaturated components in ethylene glycol are too much to reach the polyester grade ethylene glycol standard. Comparative examples 4 and 5 were prepared in the same manner as in examples 1 to 7 except that the preparation steps were changed, and the evaluation results showed that the samples of comparative examples 4 and 5 had light transmittance at 220nm, 275nm and 350nm which was only slightly higher than that of the samples of comparative examples 1 to 3 at the above wavelengths, and were distant from the polyesterThere is a large gap in the standard requirements of the grade ethylene glycol. Comparative example 6 was prepared in exactly the same manner as in examples 1-7, except that the adsorbent used in the adsorption treatment was conventional activated carbon not modified with polysilane, and the evaluation result showed that the transmittance at each wavelength was relatively highest in comparative example 6, but still did not meet the standard requirements for polyester grade ethylene glycol, as compared with comparative examples 1-5.
Claims (13)
1. The preparation method of the polyester-grade coal-based glycol comprises the following steps: (1) The high-purity inferior coal-based glycol raw material passes through an adsorption bed, fully contacts with an adsorbent in the bed to carry out adsorption reaction, and an effluent obtained by the adsorption reaction is named as AD-EG; (2) The AD-EG obtained in the step (1) enters a fixed bed reactor to carry out hydrofining reaction, and effluent obtained after the reaction is recorded as HY-EG; (3) Performing reduced pressure rectification on the HY-EG obtained in the step (2) to obtain a polyester-grade glycol product which is named as VC-EG; the high-purity inferior coal-based ethylene glycol raw material in the step (1) has the following properties: the purity of the glycol is more than or equal to 99.0wt percent, the total impurity content is not higher than 400ppm, wherein the aldehyde impurity content is more than 200mg/kg, and the 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 chromaticity of platinum and cobalt is 0 to 30 percent; the adsorbent in the step (1) is polysilane modified activated carbon, and the polysilane has the following structure:wherein R is 1 Is one of alkyl, alkoxy or alkoxyalkyl; r is R 2 Is one of alkyl, alkoxy or alkoxyalkyl, and m is any integer between 5 and 25.
2. The method according to claim 1, characterized in that: 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, diethyl ether, ethylene glycol ethyl ether and 1, 4-dioxane; the ketone impurities are one or more of 2, 3-butanedione, dihydroxyacetone and 3-methyl-1, 2-cyclopentanedione; the alcohol 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.
3. The method according to claim 1, characterized in that: said R is 1 Alkyl, with carbon number of 1-8; r is R 2 Is alkyl, the number of carbon atoms is 1-8, and m is any integer between 10-20.
4. The method according to claim 1, characterized in that: the alkyl is one of methyl, ethyl, propyl, butyl, n-amyl, isopropyl, isobutyl, cyclohexyl, 2-ethylhexyl, neopentyl and isoamyl; the alkoxy is one of methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, n-pentyloxy and 2-ethylhexyloxy; the alkoxyl alkyl is one of methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl and pentoxymethyl.
5. The method according to claim 1, characterized in that: the preparation method of the polysilane modified activated carbon in the step (1) comprises the following steps: spraying active carbon by using a mixture of polysilane and a diluent, and then performing temperature programming roasting treatment in an inert atmosphere, wherein a roasted product is polysilane modified active 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 1:1-1:9.
6. The method according to claim 5, 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。
7. The method according to claim 5, wherein: the mass ratio of the polysilane and diluent mixture to the active carbon raw material is 1:2-1:10.
8. The method according to claim 5, wherein: the temperature programming roasting conditions are as follows: roasting for 0.5-4 hours at 100-150 ℃, and then roasting for 0.5-4 hours at 200-300 ℃; the inert atmosphere is one or more of nitrogen, helium, neon and argon.
9. The method according to claim 1, characterized in that: the adsorption reaction conditions in the step (1) are as follows: the temperature is 20-60 ℃; the liquid hourly space velocity is 0.25-25 h -1 The method comprises the steps of carrying out a first treatment on the surface of the The reaction pressure is 0.05-0.6 MPa.
10. The method according to claim 1, characterized in that: the hydrofining catalyst in the step (2) is a transition metal supported catalyst; the active metal component of the transition metal supported catalyst is 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, chromia, titania, zirconia, silica, activated carbon and calpain.
11. The method according to claim 1, characterized in that: the hydrofining reaction conditions in the step (2) are as follows: the reaction temperature is 40-160 ℃, the reaction pressure is 0.1-5 MPa, the volume ratio of hydrogen to raw materials is 50:1-2500:1, and the volume airspeed is 0.2-10 h -1 。
12. The method according to claim 1, characterized in that: the vacuum rectification in the step (3) is batch vacuum rectification, and the rectification process does not use entrainer and catalyst, and the specific process conditions are as follows: the theoretical plate number is 10-20, the tower top pressure is 2-20 KPa, the reflux ratio is 3-12, and the temperature of a tower kettle reboiler is 100-160 ℃.
13. The polyester-grade ethylene glycol obtained by the method according to any one of claims 1 to 12, characterized by the following properties: ethylene glycol purity is 99.9-100%, aldehyde content is 0-8 mg/kg, and UV is 75% or less 220nm ≤100%，92%≤UV 275nm ≤100%，99%≤UV 350nm Less than or equal to 100 percent, and the chromaticity of platinum and cobalt is 0 to 5.
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| CN107285997B (en) * | 2016-03-30 | 2022-04-22 | 长春美禾科技发展有限公司 | Method for improving ultraviolet transmittance of ethylene glycol |
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| 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 |
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