CN1285553C - Process for producing alkylene glycol - Google Patents
Process for producing alkylene glycol Download PDFInfo
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- CN1285553C CN1285553C CNB2004100527181A CN200410052718A CN1285553C CN 1285553 C CN1285553 C CN 1285553C CN B2004100527181 A CNB2004100527181 A CN B2004100527181A CN 200410052718 A CN200410052718 A CN 200410052718A CN 1285553 C CN1285553 C CN 1285553C
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- Prior art keywords
- dihydric alcohol
- nano
- reaction
- alkylene dihydric
- described method
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 40
- -1 alkylene glycol Chemical compound 0.000 title claims abstract description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims description 88
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 title claims description 8
- 230000008569 process Effects 0.000 title description 3
- 239000007788 liquid Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000004593 Epoxy Substances 0.000 claims abstract description 13
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 239000000805 composite resin Substances 0.000 claims abstract description 10
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000011347 resin Substances 0.000 claims description 34
- 229920005989 resin Polymers 0.000 claims description 34
- 125000002947 alkylene group Chemical group 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 22
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000002041 carbon nanotube Substances 0.000 claims description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 14
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 13
- 239000002086 nanomaterial Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- 108010010803 Gelatin Proteins 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 3
- ONJMNXFNTYIEEA-UHFFFAOYSA-N benzene ethene Chemical compound C1=CC=CC=C1.C=C.C=C.C=C ONJMNXFNTYIEEA-UHFFFAOYSA-N 0.000 claims description 3
- ZCZDJNBPZPSQPZ-UHFFFAOYSA-N benzene;prop-1-ene Chemical compound CC=C.C1=CC=CC=C1 ZCZDJNBPZPSQPZ-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- 229920000159 gelatin Polymers 0.000 claims description 3
- 239000008273 gelatin Substances 0.000 claims description 3
- 235000019322 gelatine Nutrition 0.000 claims description 3
- 235000011852 gelatine desserts Nutrition 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- DBSDMAPJGHBWAL-UHFFFAOYSA-N penta-1,4-dien-3-ylbenzene Chemical compound C=CC(C=C)C1=CC=CC=C1 DBSDMAPJGHBWAL-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 238000006703 hydration reaction Methods 0.000 abstract description 13
- 230000036571 hydration Effects 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 125000001118 alkylidene group Chemical group 0.000 abstract 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000012153 distilled water Substances 0.000 description 28
- 238000005406 washing Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 230000007935 neutral effect Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000009466 transformation Effects 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 238000004445 quantitative analysis Methods 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 238000012856 packing Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 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 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000005815 base catalysis Methods 0.000 description 2
- HRQGCQVOJVTVLU-UHFFFAOYSA-N bis(chloromethyl) ether Chemical compound ClCOCCl HRQGCQVOJVTVLU-UHFFFAOYSA-N 0.000 description 2
- 230000037396 body weight Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- SZYJELPVAFJOGJ-UHFFFAOYSA-N trimethylamine hydrochloride Chemical compound Cl.CN(C)C SZYJELPVAFJOGJ-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical class CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 239000005703 Trimethylamine hydrochloride Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000005838 radical anions Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method for preparing alkylidene dibasic alcohol, which mainly solves the problems of short service life and poor heat tolerance of catalyst under the conditions of high conversion rate and high selectivity of the catalyst in the prior art. The present invention adopts epoxy alkane and water as raw material. Under the conditions that the reaction temperature is from 60 to 150 DEG C, the reaction pressure is from 0.5 to 2.0 megapascal, the mol ratio of the water to epoxy alkane is from 5 to 15: 1, and the liquid space velocity is from 3 to 6 hours <-1>, the raw material contacts composite resin catalyst to prepare alkylidene dibasic alcohol. The composite resin catalyst comprises monomer, co-monomer, nanometer material, initiator and auxiliary agent component, and the composite resin utilizes the treatment of OH<->, Cl<->, HSO4<->, HCO3<-> or HCOO<-> anion compounds to solve the problems. The present invention is used in industrial production that ethylene oxide has catalytic hydration to prepare alkylidene dibasic alcohol.
Description
Technical field
The present invention relates to prepare the method for alkylene dihydric alcohol, particularly about prepare the method for alkylene dihydric alcohol by the epoxy alkane catalytic hydration.
Background technology
Ethylene glycol, propylene glycol are important aliphatic dihydroxy alcohols, and wherein the ethylene glycol purposes is the most extensive, and main application is to produce vibrin, comprises fiber, film and engineering plastics.Also can directly be used as refrigerant and frostproofer, also be simultaneously to produce the indispensable materials of product such as Synolac, softening agent, paint, tackiness agent, tensio-active agent, explosive and capacitor electrolyte.
In ethylene glycol compounds, the range of application of glycol ether, triglycol or senior polyoxyethylene glycol is narrower than the range of application of ethylene glycol.Therefore, in order to improve the selectivity that oxyethane is converted into ethylene glycol, industrial often is with excessive water, and promptly 20~25 times to the molar weight of oxyethane, is used for above-mentioned hydration reaction.At this moment, reaction does not need catalyzer, and the oxyethane transformation efficiency generates the selectivity 88~91% of ethylene glycol near 100%.Therefore, the glycol concentration of gained mostly was about 10~20% most after reaction finished.In the recovery and purification step of ethylene glycol, must from the mixture of ethylene glycol and water, remove excessive water by still-process, this needs lot of energy.For example, when the mol ratio of water and oxyethane is 20, removes the required heat energy consumption of no water that is approximately 19 times of ethylene glycol by evaporation and need 170 kilocalories for every mole of ethylene glycol.This means that producing 1 ton of ethylene glycol will expend about 5.5 tons of steam.For this reason, various countries research institution has carried out deep research to the catalyzing epoxyethane hydration preparing ethylene glycol one after another, and reducing the mol ratio of water and oxyethane, raising selectivity and yield reach and cut down the consumption of energy and the purpose of material consumption.
Preparing ethandiol by catalyzing epoxyethane hydration is divided into two kinds of methods, and a kind of is direct hydration method, i.e. oxyethane direct and water effect generation monoethylene glycol under catalyst action; Another kind is the ethylene carbonate method, promptly oxyethane under catalyst action, elder generation and CO
2Reaction generates ethylene carbonate, and ethylene carbonate is hydrolyzed into monoethylene glycol in the presence of catalyzer then.
Once adopting liquid acid in early days is catalyzer, and as sulfuric acid, the ethylene glycol yield is 88~90%, and shortcoming is an etching apparatus.Had for the shortcoming that overcomes liquid acid once proposes to use--SO
3H,--PO (OH)
2The storng-acid cation exchange resin of active group.Hydration can operate continuously under low temperature, low pressure, and resin is through regeneration, the repeated use of washing back.Industrial do not have widely used reason to be: if want to improve the yield of ethylene glycol, water and ethylene glycol proportioning are big, and product concentration is low, puies forward dense difficulty; Ion exchange resin is after using for some time in addition, and tradable volume descends more, can not restore fully after the regeneration.The base catalysis hydration is used industrial failing, mainly be oxyethane can be in large quantities with ethylene glycol and the condensed ethandiol continuation effect that generates by ethylene glycol, generate the product that contracts of ethylene glycol more, reduced the yield of ethylene glycol.Because all there are some shortcomings in acid, base catalysis hydration, thereby the hydration of present industrial employing on-catalytic.In order to improve speed of reaction, industrial temperature of reaction is generally 150~200 ℃, pressure 0.8~2.0MPa.
Can obtain higher transformation efficiency, good selectivity and low water/epoxy alkane ratio with the EP-A-156449 disclosed method.According to the document, epoxy alkane is hydrolyzed in the presence of the anionic material of containing metal thing improving optionally, and preferably having has the positive polarity of affinity to cooperate the solid material at center to metalate anion.Described solid material is anionite-exchange resin preferably, and metalate anion is molybdate, wolframate radical, metavanadic acid root, pyrovanadic acid hydrogen root and pyrovanadium acid radical anion.The trouble of this method is that the product stream of alkylene glycol containing also contains a large amount of metalate anion that displace from the positive polarity cooperation center of the anionic solid material of containing metal thing.Proposed to simplify method for product recovery with water-insoluble vanadate and molybdate.But when using these metalate anion salt, resulting selectivity is starkly lower than the selectivity when using the water-soluble metal thing.
EP-A-226799 discloses the method for preparing ethylene glycol and/or propylene glycol in the presence of a kind of catalytic composition at carboxylic acid and carboxylate salt (both can use by arbitrary combination) by the hydration of corresponding alkylene oxide hydrocarbon.These acid/salt compositions are the solution form, and they must be separated from reaction product.
JP-A-57-139026 discloses a kind of at halogen-type anionite-exchange resin and CO
2Co-exist in down the method for alkylene oxide and water reaction.RU-C-2001901 points out that above-mentioned document invention disclosed has the shortcoming that generates carbonate in reaction mixture, because boiling point is approaching, carbonate is difficult to separate from glycol.
(the USPatent:5 of Shell company of the U.S., 874,653, WO:99/23053), the Shvets V.F. of Mendeleev Chemical Engineering Univ., Russia, (WO:99/12876, RU:2,149,864) etc. have developed a series of anionite-exchange resin that have quaternary ammonium group by vinylbenzene and divinyl benzene crosslinked is catalyzer.Use this catalyst system, the transformation efficiency of oxyethane is near 100%, and the selectivity of ethylene glycol can reach 95%.Yet the remarkable shortcoming of this catalyst system be to use the life-span short, resistance toheat is poor.Simultaneously, even if in lower temperature range (<95 ℃), the expansion of catalyzer is still relatively more serious.Although thereby above-mentioned research work obtained very big progress, but still can't realize industrialization.
Summary of the invention
Technical problem to be solved by this invention is the method that in the past prepared alkylene dihydric alcohol, the catalyzer that uses has higher conversion and optionally under the condition, exist catalyzer short work-ing life, the problem of poor heat resistance provides a kind of new method for preparing alkylene dihydric alcohol.This method is used for having catalyzer transformation efficiency height when the epoxy alkane catalytic hydration prepares the alkylene dihydric alcohol reaction, product alkylene dihydric alcohol selectivity height, while catalyzer long service life, the characteristics that resistance toheat is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing alkylene dihydric alcohol, with epoxy alkane and water is raw material, in temperature of reaction is 60~150 ℃, reaction pressure is 0.5~2.0 MPa, water/epoxy alkane mol ratio is 5~15: 1, and the liquid air speed is 3~6 hours
-1Under the condition, raw material contacts with composite resin catalyst and generates alkylene dihydric alcohol, and use therein composite resin catalyst comprises following component by weight percentage:
(1) monomer 30~90%;
(2) comonomer 5~30%;
(3) nano material 0.1~30%;
(4) initiator 0.1~5%;
(5) auxiliary agent 0.5~5%;
Wherein monomer is selected from least a in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin; Compound resin carries out ion-exchange and makes catalyzer with being selected from the compound that contains hydroxide radical, chlorine root, bisulfate ion, bicarbonate radical or formate anion, and the exchanging equivalent of resin is 2.0~4.5 milligramequivalents/gram compound resin.
The epoxy alkane preferred version is oxyethane or propylene oxide in the technique scheme; The alkylene dihydric alcohol preferred version is ethylene glycol or propylene glycol.The temperature of reaction preferable range is 75~110 ℃, and the reaction pressure preferable range is 1.0~1.5 MPas, and liquid air speed preferable range is 3~4 hours
-1The monomer preferred version is a vinylbenzene; The comonomer preferred version is a divinylbenzene; The nano material preferred version is a CNT (carbon nano-tube); The initiator preferred version is a benzoyl peroxide; The auxiliary agent preferred version is a polyvinyl alcohol; The exchanging equivalent preferable range of resin is 3.0~3.5 milligramequivalents/gram compound resin.
The carbon nanotube that uses in the inventive method is prepared by chemical Vapor deposition process as multi-walled carbon nano-tubes (MWNTs).Matrix material is obtained by situ aggregation method or improvement in-situ compositing by carbon nanotube and monomer.Carbon nanotube also can adopt Single Walled Carbon Nanotube (SWNTs), and composite material and preparation method thereof also can adopt arc process, solid-phase pyrolysis etc.
The preparation method of the compound resin that uses in the inventive method may further comprise the steps:
(1) auxiliary agent being made into weight percent concentration is 2~5% water solution A;
(2) with monomer, comonomer and initiator, wiring solution-forming B;
(3) solution A and solution B are mixed, reacted 0~8 hour down at 70~90 ℃; Add nano material, reacted 2~8 hours down at 70~90 ℃; Be warming up to 90~100 ℃ of reactions 2~8 hours, after reaction finished, inclining supernatant liquid, washed with water, filtered then, dry compound pearl body, and wherein the nano material in above-mentioned reaction mixture adds wiring solution-forming B in step (2); Perhaps add reaction system after 0~8 hour in solution A and solution B hybrid reaction;
(4) 100~500% of the compound pearl body weight of adding chloromethyl ether and 20~70% zinc chloride catalyzer in compound pearl body, under 30~50 ℃, compound pearl body is carried out Friedel-crafts reaction, reaction times is 8~20 hours, 20~70% of the compound pearl body weight of adding ethylene dichloride after the suction strainer washing, 70~200% trimethylamine hydrochloride and 60~180% sodium hydroxide, 25~40 ℃ of reactions 5~20 hours, reaction finishes back adding sodium hydroxide and makes the transition, be washed to neutrality then, promptly get composite resin material, wherein monomer is selected from methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, at least a in vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin.
The Preparation of catalysts method of using in the inventive method may further comprise the steps:
(1) gets above-mentioned composite resin material and pack in the metal tube, feed distilled water backwash resin bed, feed distilled water then and just washing 20~40 minutes as vector resin;
(2) washed resin bed 20~40 minutes with 500~1500% (weight ratio, as follows) methanol solution, dry up with nitrogen;
(3) be made into 2~10% aqueous solution with 10~40% oxyethane and washed resin bed 20~40 minutes, with distillation washing 20~30 minutes;
(4) be made into the 1 mol aqueous solution with 150~300% hydrochloric acid and washed resin bed 40~60 minutes, be washed till effluent liquid with distilled water and be neutral;
(5) be made into the 1 mol aqueous solution with 150~300% MY and washed resin bed 40~60 minutes, wherein M
+Be selected from Na
+Or K
+, Y
-Be selected from OH
-, Cl
-, HCOO
-, HCO
3 -Or HSO
4 -, being washed till effluent liquid with distilled water and being neutral, nitrogen dries up the back and takes out.
The catalyzer that uses in the inventive method contains OH with compound resin with being selected from then owing to make compound resin with nano material
-, Cl
-, HCOO
-, HCO
3 -Or HSO
4 -Anionic compound carries out ion-exchange and makes catalyzer.This catalyzer is used for the epoxy alkane catalytic hydration and prepares alkylene dihydric alcohol when reaction, and the inventor finds that surprisingly the catalyzer swelling property is less, Heat stability is good, and use temperature has promoted about 40~50 ℃ than general ion exchange resin.The inventive method has following advantage simultaneously:
1, activity of such catalysts height.Compare with existing technology, reaction velocity can be by existing 2 hours
-1Bring up to 3~6 hours
-1Thereby, the throughput of raising device.
2, the mol ratio of water and oxyethane is low.Compare with existing ethylene glycol production technique, catalyzer of the present invention can make water than obviously reducing, can reduce to 10: 1 by 20~25: 1 of existing technology, thus the energy consumption of greatly reducing.
3, alkylene dihydric alcohol selectivity and yield improve.Compare with existing technology, catalyzer of the present invention can make the alkylene dihydric alcohol selectivity improve, and can be increased to 95~97% by 88~91% of existing ethylene glycol production technique, thereby greatly reduce material consumption.
4, the good stability of catalyzer, the life-span is long.But continuous operation is more than half a year, and the transformation efficiency of oxyethane is not seen tangible reduction, and the selectivity of alkylene dihydric alcohol remains unchanged substantially.
5, this catalyzer does not have corrosion to equipment, environmentally safe.
Obtained better technical effect.
The invention will be further elaborated below by embodiment.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.
Embodiment
The preparation method of compound resin
[embodiment]
In 250 milliliters of there-necked flasks, add 120 ml distilled waters and 0.6 gram polyvinyl alcohol, start the stirring intensification polyvinyl alcohol is all dissolved.Stop to stir, cold slightly back adds the monomer mixture solution (20.4 gram vinylbenzene, 6.1 gram divinylbenzenes, 3.9 gram carbon nanotubes, 1.4 gram benzoyl peroxides) that contains initiator, starts stirring, is warming up to 85 ℃, reacts 5 hours.Be warming up to 95 ℃ about 2 hours.After reaction finished, inclining supernatant liquid, with 85 ℃ of hot washes several times, more several times, filter then with cold wash, drying, weigh compound pearl body.The functionalization of compound pearl body: in 500 milliliters of there-necked flasks, add the 20.6 compound pearl body A of gram and 80 milliliters of chloromethyl ethers, start to stir and be warmed up to 30 ℃, adding 8 gram zinc chloride is catalyzer, under 39~40 ℃, compound pearl body A is carried out Friedel-crafts reaction, reaction times is 10 hours, and suction strainer is with washings such as acetone.Add 8.5 grams, two oxidative ethanes, 18.5 gram trimethylamine hydrochlorides, 75 milliliters of 20% weight sodium hydroxides, reaction is about 12 hours about 30 ℃.After reaction finishes, progressively thin up when proportion equals 1.O, washing, hydro-oxidation sodium is washed to neutrality after transition, promptly gets composite resin material.
Method for preparing catalyst
Catalyst A
Get 40 milliliters of support of the catalyst resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with methanol solution; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to effluent liquid; Washed 50 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to effluent liquid; Washed flow rate of liquid 10 ml/min 70 minutes with 10% (weight) HCOONa solution; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to effluent liquid; Nitrogen purging took out after 1.5 hours.
Catalyst B
Get 25 milliliters of support of the catalyst resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 ml/min, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with methanol solution; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Washed 50 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to effluent liquid; Washed 100 minutes with the 5% weight NaOH aqueous solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to effluent liquid; With 2% weight CO
2The aqueous solution is at 2.0 MPa CO
2Washed flow rate of liquid 15 ml/min under the atmosphere 100 minutes; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to effluent liquid; Nitrogen purging took out after 1.5 hours.
Catalyzer C
Get 25 milliliters of support of the catalyst resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Washed 50 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to effluent liquid; With 1 mol NaHCO
3Solution was washed 50 minutes, and flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to effluent liquid; With 2% weight CO
2The aqueous solution is at 2.0 MPa CO
2Washed flow rate of liquid 15 ml/min under the atmosphere 100 minutes; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to effluent liquid; Nitrogen purging took out after 1.5 hours.
Catalyzer D
Get 30 milliliters of support of the catalyst resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Washed 100 minutes with 1 mol HCl solution, flow rate of liquid 15 ml/min feed distilled water washing 20 minutes and are neutral to effluent liquid; With 10% weight NaHSO
4Solution was washed 60 minutes, flow rate of liquid 10 ml/min; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to effluent liquid; Nitrogen purging took out after 1.5 hours.
Catalyzer E
Get 25 milliliters of support of the catalyst resins, in the metal tube of packing into, and take turns doing following processing: feed distilled water backwash resin bed, feed distilled water then and just washing 30 minutes, flow rate of liquid 10 ml/min; Washed 30 minutes flow rate of liquid 10 ml/min with methanol solution; Washed 30 minutes flow rate of liquid 10 ml/min with 3% weight aqueous solution of ethylene oxide; Feed distilled water washing 20 minutes, flow rate of liquid 20 ml/min; With 2% weight CO
2The aqueous solution is at 2.0 MPa CO
2Washed flow rate of liquid 15 ml/min under the atmosphere 100 minutes; Feed distilled water washing 20 minutes and be neutral, flow rate of liquid 20 ml/min to effluent liquid; Nitrogen purging took out after 1.5 hours.
[embodiment 1~5]
It is 10 millimeters that above-mentioned catalyst A, B, C, D, E each 15 milliliters (granularity 20~40 orders) are filled in a diameter respectively successively, in long 350 millimeters the stainless steel fixed-bed reactor, uses metering pump massage that than charging in 12: 1 raw water and oxyethane.Reacting system pressure is 1.2 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[comparative example 1]
With granularity be 15 milliliters on 20~40 purpose porcelain rings to fill in a diameter be 10 millimeters, in long 350 millimeters the stainless steel fixed-bed reactor, with raw water and oxyethane with the metering pump massage you than charging in 12: 1.Reacting system pressure is 1.5 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 6]
It is 10 millimeters that 15 milliliters of above-mentioned catalyzer C (granularity 20~40 orders) are filled in a diameter, in long 350 millimeters the stainless steel fixed-bed reactor, with raw water and oxyethane your ratio of metering pump massage charging in 22: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 6 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 7]
It is 10 millimeters that 15 milliliters of above-mentioned catalyzer C (granularity 20~40 orders) are filled in a diameter, in long 350 millimeters the stainless steel fixed-bed reactor, with raw water and oxyethane your ratio of metering pump massage charging in 5: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 8]
It is 10 millimeters that 15 milliliters of above-mentioned catalyst B (granularity 20~40 orders) are filled in a diameter, in long 350 millimeters the stainless steel fixed-bed reactor, with raw water and oxyethane your ratio of metering pump massage charging in 10: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
[embodiment 9]
It is 10 millimeters that 15 milliliters of above-mentioned catalyzer C (granularity 20~40 orders) are filled in a diameter, in long 350 millimeters the stainless steel fixed-bed reactor, with raw water and oxyethane your ratio of metering pump massage charging in 15: 1.Reacting system pressure is 1.2 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 1.
The reactivity worth of table 1 different catalysts
Sequence number | Catalyzer | EO transformation efficiency % | EG selectivity % |
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 comparative examples 1 embodiment 6 embodiment 7 embodiment 8 embodiment 9 | A B C D E - C C B C | 99.2 100 99.76 99.65 99.61 10.63 98.3 99.2 99.41 99.49 | 86.68 94.23 96.65 70.23 42.31 92.09 98.0 92.34 94.08 97.1 |
[embodiment 10]
It is 10 millimeters that 17 milliliters of above-mentioned catalyzer C (granularity 20~40 orders) are filled in a diameter, carries out the catalyst stability test in long 400 millimeters the stainless steel fixed-bed reactor, uses metering pump massage that than charging in 12: 1 raw water and oxyethane.Reacting system pressure is 1.2 MPas, and 90 ℃ of temperature of reaction, liquid air speed are 3 hours
-1, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography, and it the results are shown in table 2.
The test of table 2 catalyst stability
Reaction times (hour) | EO transformation efficiency % | EG selectivity % |
200 300 400 500 600 700 800 900 1000 1100 1200 1300 | 99.21 100 99.76 99.65 99.61 99.56 99.2 99.41 99.49 99.45 99.35 99.32 | 96.68 95.91 95.65 96.26 95.41 95.74 96.51 95.89 96.59 96.58 96.25 96.35 |
[embodiment 11]
24 milliliters of above-mentioned catalyzer C are incorporated in one 300 milliliters the stainless steel gap reactor, add 4.9 moles of raw waters and 0.48 mole of propylene oxide.Reacting system pressure is 1.2 MPas, 120 ℃ of temperature of reaction, and the reaction times is 3 hours, product carries out qualitative, quantitative analysis with the HP5890 gas-chromatography.The propylene oxide transformation efficiency is 99.1%, and the propylene glycol selection rate is 95.2%.
[embodiment 12]
According to each condition and the operation steps of embodiment 3, just changing water/oxyethane mol ratio is 15, and temperature of reaction is 110 ℃, and reaction pressure is 1.0 MPas, and the liquid air speed is 4 hours
-1, its result is: the EO transformation efficiency is 100%, the EG selectivity is 96.3%.
[embodiment 13]
According to each condition and the operation steps of embodiment 3, just changing the reaction liquid air speed is 3.5 hours
-1, its result is: the EO transformation efficiency is 99.51%, the EG selectivity is 96.5%.
[embodiment 14]
According to each condition and the operation steps of embodiment 3, just changing water/oxyethane mol ratio is 8, and temperature of reaction is 80 ℃, and reaction pressure is 1.5 MPas, and its result is: the EO transformation efficiency is 99.05%, and the EG selectivity is 96.81%.
[embodiment 15]
According to each condition and the operation steps of embodiment 3, just changing water/oxyethane mol ratio is 15, and temperature of reaction is 110 ℃, and its result is: the EO transformation efficiency is 99.2%, and the EG selectivity is 95.87%.
Claims (9)
1, a kind of method for preparing alkylene dihydric alcohol is a raw material with epoxy alkane and water, and 60~150 ℃ of temperature of reaction, reaction pressure is 0.5~2.0 MPa, and water/epoxy alkane mol ratio is 5~15: 1, and the liquid air speed is 3~6 hours
-1Under the condition, raw material contacts with composite resin catalyst and generates alkylene dihydric alcohol, and use therein composite resin catalyst comprises following component by weight percentage:
(1) monomer 30~90%;
(2) comonomer 5~30%;
(3) nano material 0.1~30%;
(4) initiator 0.1~5%;
(5) auxiliary agent 0.5~5%;
Wherein monomer is selected from least a in methyl methacrylate, butyl methacrylate, ethyl propenoate, butyl acrylate, divinyl, vinylbenzene or the vinyl cyanide; Comonomer is selected from least a in the two Methacrylamides of methacrylate glycol ester, hexa-methylene, two propylene benzene, divinyl phenylmethane, divinylbenzene or the triethylene benzene; Nano material is selected from least a in nano aluminium oxide, nano silicon oxide, nano-titanium oxide, CNT (carbon nano-tube), nano magnesia or the nano zine oxide; Initiator is selected from least a in benzoyl peroxide or the Diisopropyl azodicarboxylate; Auxiliary agent is selected from least a in polyvinyl alcohol, wilkinite, lime carbonate or the gelatin; Compound resin carries out ion-exchange and makes catalyzer with being selected from the compound that contains hydroxide radical, chlorine root, bisulfate ion, bicarbonate radical or formate anion, and the exchanging equivalent of resin is 2.0~4.5 milligramequivalents/gram compound resin.
2,, it is characterized in that epoxy alkane is oxyethane or propylene oxide according to the described method for preparing alkylene dihydric alcohol of claim 1; Alkylene dihydric alcohol is ethylene glycol or propylene glycol.
3, according to the described method for preparing alkylene dihydric alcohol of claim 1, it is characterized in that temperature of reaction is 75~110 ℃, reaction pressure is 1.0~1.5 MPas, the liquid air speed is 3~4 hours-1.
4, according to the described method for preparing alkylene dihydric alcohol of claim 1, it is characterized in that monomer is selected from vinylbenzene.
5, according to the described method for preparing alkylene dihydric alcohol of claim 1, it is characterized in that comonomer is selected from divinylbenzene.
6, according to the described method for preparing alkylene dihydric alcohol of claim 1, it is characterized in that nano material is selected from CNT (carbon nano-tube).
7, according to the described method for preparing alkylene dihydric alcohol of claim 1, it is characterized in that initiator is selected from benzoyl peroxide.
8, according to the described method for preparing alkylene dihydric alcohol of claim 1, it is characterized in that auxiliary agent is selected from polyvinyl alcohol.
9,, it is characterized in that the compound resin exchanging equivalent is 3.0~3.5 milligramequivalents/gram compound resin according to the described method for preparing alkylene dihydric alcohol of claim 1.
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CN102219642B (en) * | 2010-04-15 | 2013-12-04 | 中国石油化工股份有限公司 | Method for producing glycol by virtue of hydration of ethylene oxide |
CN109575295B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Method for catalytic hydration of alkylene oxides |
CN109574793B (en) * | 2017-09-29 | 2021-05-28 | 中国石油化工股份有限公司 | Method for preparing glycol by hydrating alkylene oxide |
CN109574807B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol by catalytic hydration of alkylene oxide |
CN109574794B (en) * | 2017-09-29 | 2021-05-11 | 中国石油化工股份有限公司 | Method for producing ethylene glycol by catalytic hydration of alkylene oxide |
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