CN110981697A - Method for synthesizing 3-methyl-3-butene-1-ol - Google Patents
Method for synthesizing 3-methyl-3-butene-1-ol Download PDFInfo
- Publication number
- CN110981697A CN110981697A CN201911311345.8A CN201911311345A CN110981697A CN 110981697 A CN110981697 A CN 110981697A CN 201911311345 A CN201911311345 A CN 201911311345A CN 110981697 A CN110981697 A CN 110981697A
- Authority
- CN
- China
- Prior art keywords
- oxide
- catalyst
- methyl
- isobutene
- nitrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- CPJRRXSHAYUTGL-UHFFFAOYSA-N isopentenyl alcohol Chemical compound CC(=C)CCO CPJRRXSHAYUTGL-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 23
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 109
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- AWBIJARKDOFDAN-UHFFFAOYSA-N 2,5-dimethyl-1,4-dioxane Chemical compound CC1COC(C)CO1 AWBIJARKDOFDAN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 46
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000002131 composite material Substances 0.000 claims description 31
- -1 nitrogen-containing compound Chemical class 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims description 21
- 150000004706 metal oxides Chemical class 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 19
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 12
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 10
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000395 magnesium oxide Substances 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000005751 Copper oxide Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 238000011068 loading method Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000011787 zinc oxide Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 3
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 2
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 claims description 2
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 claims description 2
- OXAMBMYXAGPEHI-UHFFFAOYSA-N CN(C)CCCO.O Chemical compound CN(C)CCCO.O OXAMBMYXAGPEHI-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 2
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000003927 aminopyridines Chemical class 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011964 heteropoly acid Substances 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- SFBHPFQSSDCYSL-UHFFFAOYSA-N n,n-dimethyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)C SFBHPFQSSDCYSL-UHFFFAOYSA-N 0.000 claims description 2
- GMTCPFCMAHMEMT-UHFFFAOYSA-N n-decyldecan-1-amine Chemical compound CCCCCCCCCCNCCCCCCCCCC GMTCPFCMAHMEMT-UHFFFAOYSA-N 0.000 claims description 2
- VQJOPRHZJAIGEW-UHFFFAOYSA-N n-ethyl-n-methylcyclopropanamine Chemical compound CCN(C)C1CC1 VQJOPRHZJAIGEW-UHFFFAOYSA-N 0.000 claims description 2
- 239000010412 oxide-supported catalyst Substances 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011973 solid acid Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- IGKMCNVRIIQDEB-UHFFFAOYSA-N N,N-dimethylpentacosan-13-amine Chemical compound CCCCCCCCCCCCC(CCCCCCCCCCCC)N(C)C IGKMCNVRIIQDEB-UHFFFAOYSA-N 0.000 claims 1
- MNFORVFSTILPAW-UHFFFAOYSA-N azetidin-2-one Chemical compound O=C1CCN1 MNFORVFSTILPAW-UHFFFAOYSA-N 0.000 claims 1
- 125000005521 carbonamide group Chemical group 0.000 claims 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 claims 1
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 40
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000011949 solid catalyst Substances 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 239000011259 mixed solution Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 239000001099 ammonium carbonate Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000012545 processing Methods 0.000 description 7
- 229930040373 Paraformaldehyde Natural products 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 229920002866 paraformaldehyde Polymers 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical group CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- REHUGJYJIZPQAV-UHFFFAOYSA-N formaldehyde;methanol Chemical compound OC.O=C REHUGJYJIZPQAV-UHFFFAOYSA-N 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- VBPSVYDSYVJIPX-UHFFFAOYSA-N methylbutenol Natural products CCC=C(C)O VBPSVYDSYVJIPX-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- MXVSJNLRVLKAOG-UHFFFAOYSA-N 1-chloro-3-methylbut-1-ene Chemical compound CC(C)C=CCl MXVSJNLRVLKAOG-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000003857 carboxamides Chemical class 0.000 description 1
- 235000021466 carotenoid Nutrition 0.000 description 1
- 150000001747 carotenoids Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229930002839 ionone Natural products 0.000 description 1
- 150000002499 ionone derivatives Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- QVDTXNVYSHVCGW-ONEGZZNKSA-N isopentenol Chemical compound CC(C)\C=C\O QVDTXNVYSHVCGW-ONEGZZNKSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229940041616 menthol Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical compound C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000005543 phthalimide group Chemical class 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
-
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Abstract
The invention provides a method for synthesizing 3-methyl-3-butene-1-ol. The invention takes isobutene and dimethyl dioxane as raw materials, and the raw materials react in a fixed bed filled with a catalyst to obtain 3-methyl-3-butylene-1-alcohol, wherein the conversion rate of the dimethyl dioxane reaches more than 99 percent, and the selectivity reaches more than 98 percent. The method takes the dimethyl dioxane as the raw material to synthesize the 3-methyl-3-butene-1-ol, reduces the production cost and the energy consumption, greatly reduces the discharge amount of three wastes, simplifies the separation process, has stronger continuous operability and is very suitable for amplification and industrialization.
Description
Technical Field
The invention relates to a method for synthesizing a raw material 3-methyl-3-butene-1-ol of a polycarboxylic acid high-efficiency water reducing agent, belonging to the technical field of organic chemical synthesis.
Background
3-methyl-3-butylene-1-alcohol is an initiator for synthesizing the side chain TPEG polyether of the polycarboxylic acid high-efficiency water reducing agent, and plays a decisive role in the quality and performance of the polycarboxylic acid high-efficiency water reducing agent. In addition, 3-methyl-3-butylene-1-alcohol can also be used for synthesizing methyl carpicidate which is an intermediate of a pyrethroid pesticide with high efficiency and low toxicity, and is also a main raw material for artificially synthesizing citral, and further synthesizing menthol and derivatives thereof, ionone, carotenoid and vitamin A, essences and fragrances, medical supplies and the like. Therefore, the research on synthesizing the 3-methyl-3-butene-1-ol has wide prospect and great economic and social benefits.
The synthetic route is mainly divided into three major categories according to the difference of raw materials for synthesizing 3-methyl-3-buten-1-ol, wherein the first category is an isoprene method, the second category is a methylbutenol isomerization method, and the third category is a Prins method, also called an isobutene method.
Patent 105541544A discloses a method for synthesizing chloroisopentene by using isoprene and hydrogen chloride as catalysts, hydrolyzing to obtain methylbutenol and isopentenol, and then isomerizing to obtain 3-methyl-3-buten-1-ol, wherein the method is complex in operation, large in equipment investment and high in investment, and hydrogen chloride has great corrosion to equipment.
Patent 103787834B discloses that acetone and formaldehyde are added to obtain 4-hydroxy-2-butanone, the intermediate 1 reacts with isobutene under the action of an acid catalyst to obtain an intermediate 2, the intermediate 1 reacts with a methyleneating reagent to obtain an intermediate 2, and deprotection reaction is carried out to obtain 3-methyl-3-butene-1-ol.
Patent CN102557876A discloses a method for preparing 3-methyl-3-buten-1-ol by Prins condensation by using paraformaldehyde and isobutene as raw materials, chloroform as a solvent and 1.25mol of SnCl4 immobilized on each gram of molecular sieve as a catalyst.
The patent CN105439823A discloses a method for generating 3-methyl-3-butene-1-ol by heating a formaldehyde methanol solution as a raw material to a supercritical state, then feeding the heated formaldehyde methanol solution into a reactor in a spray form, and condensing with isobutene, wherein the conversion rate of isobutene is 99% and the selectivity of 3-methyl-3-butene-1-ol is 96% under the reaction pressure of 15-22 MPa and the reaction temperature of 220-300 ℃.
Patent CN104130107A discloses a method for synthesizing 3-methyl-3-buten-1-ol by using formaldehyde hemiacetal as a raw material, wherein an alcohol-aldehyde condensation compound is synthesized by using alcohol with 1-5 carbon atoms and formaldehyde, and the alcohol-aldehyde condensation compound is reacted under the conditions of reaction pressure of 12-18 MPa and reaction temperature of 280-350 ℃.
In a word, the Prins method in the prior art can efficiently prepare the 3-methyl-3-buten-1-ol, but the raw materials mostly adopt formaldehyde or paraformaldehyde, which has the advantages of low formaldehyde conversion rate and difficulty in separating and removing the formaldehyde, so that the formaldehyde can be remained in the product, the product quality is reduced, and the downstream application of the 3-methyl-3-buten-1-ol is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides the preparation method of the 3-methyl-3-butene-1-ol, which has the advantages of simple process, environmental protection and high yield, and particularly, the 3-methyl-3-butene-1-ol is prepared by the reaction of isobutene and dimethyl dioxane.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of synthesizing 3-methyl-3-buten-1-ol, the method comprising: in the presence of a catalyst, isobutene and dimethyldioxane are reacted to form 3-methyl-3-buten-1-ol.
Dimethyldioxane as a starting material can be prepared from formaldehyde and isobutylene under the condition of an acidic catalyst; the acidic catalyst can be one or more of sulfuric acid, phosphoric acid, hydrochloric acid, solid acid and heteropoly acid.
In the preparation of the dimethyl dioxane, the mass ratio of the formaldehyde to the isobutene can be 2: 1-8: 1.
The reaction temperature in the preparation of the dimethyl dioxane is preferably 60-100 ℃, and the reaction time is preferably 4-8 h.
Preferably, the reaction temperature of the isobutene and the dimethyl dioxane is 150-220 ℃, and further preferably 160-200 ℃; the reaction pressure is 4MPa to 15MPa, and more preferably 6MPa to 10 MPa.
Preferably, the reaction time of isobutylene and dimethyldioxane is from 10min to 60min, more preferably from 15min to 30 min.
Preferably, the molar ratio of the isobutene to the dimethyldioxane is 3-10: 1 to 5, and preferably 5 to 8: 2 to 4.
Further, the reaction is carried out under an inert atmosphere such as a nitrogen atmosphere. The reaction is preferably carried out in a fixed bed reactor packed with a catalyst.
The catalyst comprises a main catalyst and an auxiliary catalyst, wherein the main catalyst is a metal oxide, and the auxiliary catalyst is a nitrogen-containing compound. The mass ratio of the main catalyst to the auxiliary catalyst is preferably 6: 1 to 3.
The catalyst of the invention can be formed by mixing a main catalyst and a cocatalyst.
Preferably, the loading of the metal oxide of the main catalyst is preferably 3 to 40 wt%, more preferably 5 to 20 wt%, based on the mass of the carrier; the loading amount of the nitrogen-containing compound in the cocatalyst is preferably 1-15 wt%, and more preferably 2-5 wt%.
The main catalyst of the catalyst according to the present invention is preferably a metal oxide including, but not limited to, two or more of magnesium oxide, calcium oxide, manganese oxide, barium oxide, iron oxide, copper oxide, zinc oxide, tin oxide, strontium oxide, such as manganese oxide and barium oxide, calcium oxide and iron oxide, copper oxide and zinc oxide, strontium oxide and magnesium oxide, preferably including at least one alkaline earth metal oxide and at least one oxide selected from iron, copper, tin, manganese, strontium, and the metal oxide is added as the main catalyst, which can effectively promote the cracking of dimethyldioxane, accelerate the reaction with isobutylene, lower the reaction temperature and pressure, reduce the reaction time, and make the reaction conditions milder.
Preferably, the co-catalyst is selected from one or more of the group consisting of imides, carboxamides, fatty amines, aromatic amines, nitrogen-containing heterocycles, quaternary ammonium bases, including but not limited to one or more of phthalimides, propiolactams, caprolactam, dimethylaniline, p-toluidine, methylethylcyclopropylamine, p-chloroaniline, tetradecyldimethylamine, dodecyldimethyl tertiary amine, decaalkyldimethyl tertiary amine, didodecyltriethyl tertiary amine, dioctadecyldecyl tertiary amine, octadecylamine, dioctylamine, didecylamine, dodecylamine, diisooctylamine, isooctylamine, N-pentylamine, N-hexylamine, aminopyridine, pyridine, imidazole, pyrrole, dimethylformamide, triethylamine, N-phenylbenzyamine, tetraisopropylamine iodide, and (2-hydroxyethyl) trimethylamine hydroxide. Adding a nitrogen-containing compound to promote the reaction of the dimethyl dioxane and the isobutene and improve the selectivity of the dimethyl dioxane; on the other hand, the stability of the product 3-methyl-3-butene-1-ol is enhanced, and preferably, the loading amount of the nitrogen-containing compound can be 1 to 15 wt%, preferably 2 to 5 wt%, based on the mass of the carrier.
The carrier of the catalyst according to the present invention, preferably, comprises one or more of alumina, silica and molecular sieve, and has the characteristics of high temperature resistance and high pressure resistance.
The procatalyst may be loaded onto the support using conventional methods. For example, the main catalyst of the present invention can be supported on the carrier by the following method:
firstly, weighing one or more of alumina, silicon oxide and molecular sieve as carriers in a certain mass, adding the two or more of metal oxides in a flask, dissolving the metal oxides by dilute nitric acid, adding the dissolved metal oxides into the flask, placing the mixed solution into an ultrasonic container for mixing, performing ultrasonic treatment on the mixed solution for 1-4 h, standing the mixed solution for 10h, adding a weakly alkaline substance, adjusting the pH value of the solution to 10, completely solidifying the solution on the carriers, filtering the solidified solution after 5h, washing the solution for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 125 ℃, roasting the dried solid catalyst at 540 ℃ for 4.5h, and finally obtaining the composite metal catalyst with uniform particle size and good dispersibility.
The cocatalyst in the present invention can be loaded on the metal oxide-supported catalyst support by the following method:
firstly, weighing carrier particles (such as the composite metal catalyst particles prepared above) carrying a main catalyst metal oxide, heating the carrier particles (such as in an oil bath) to 50-100 ℃, weighing a nitrogen-containing compound, adding the nitrogen-containing compound into the heated carrier particles, dissolving and mixing the nitrogen-containing compound with an organic solvent (such as stirring or ultrasonic treatment for 1-5 hours), then removing the solvent, washing (such as washing with ethanol), drying the obtained composite metal catalyst carrying the nitrogen-containing compound (such as drying the composite metal catalyst at 120 ℃), and further roasting (such as roasting the composite metal catalyst at 250 ℃) to obtain the composite metal catalyst carrying the nitrogen-containing compound.
According to the preparation method of the catalyst, a carrier and a metal oxide are mixed in an ultrasonic container, the mixed solution is subjected to ultrasonic treatment for 1-4 hours and then is kept stand for 10 hours, the added weak alkaline substances include one or more of ammonia water, ammonium bicarbonate and ammonium carbonate, the pH of the solution is adjusted to 10, and the metal oxide can be solidified and completely attached to the carrier. Preferably, the nitrogen-containing compound is blended with the composite metal catalyst particles, the blending organic solvent includes but is not limited to one or more of toluene, xylene, chlorobenzene, dichlorobenzene and ethylbenzene, in a preferred scheme, the blending process of the nitrogen compound and the composite metal catalyst particles is carried out in a nitrogen atmosphere, and in particular, the subsequent process comprises solvent washing and drying.
Preferably, the catalyst is mechanically ground, and a proper amount of polyvinyl alcohol and sesbania powder are added, and then the mixture is dried, baked, ground, sieved and separated to obtain the solid catalyst with the particle size of 30-100 meshes, preferably 50-80 meshes.
Because the stability of the dimethyl dioxane is higher than that of formaldehyde and formaldehyde hemiacetal, and various structures such as monomers, dimers, polymers and the like do not exist, no formaldehyde is generated in the reaction process, so that the reaction is more stable, and higher conversion rate and selectivity can be obtained by adding a catalyst and adjusting the temperature and the pressure. Because no formaldehyde residue and high polymer are generated in the reaction liquid, formaldehyde does not need to be removed in the subsequent separation treatment process, and because no components such as solvent and the like are generated, the separation process is more efficient, and finally the separation yield of the 3-methyl-3-butene-1-ol is improved.
According to a more specific embodiment of the present invention, a method for synthesizing 3-methyl-3-buten-1-ol comprises:
(1) firstly, nitrogen or inert gas is used for purging the reactor, and air in the reactor is completely replaced;
(2) heating isobutene to the required temperature of 100-300 ℃ through a preheater, preferably 150-220 ℃, and preheating dimethyl dioxane through the preheater to the required temperature of 60-140 ℃, and further preferably 80-120 ℃;
(3) mixing the two materials through a mixer, continuously feeding the mixed materials into a fixed bed reactor, and reacting under the action of a catalyst to generate 3-methyl-3-butene-1-ol;
(4) and (3) cooling the reaction liquid, then performing pressure rectification separation, separating unreacted isobutene, introducing the residual reaction liquid into a de-heavy rectifying tower, and extracting the 3-methyl-3-butene-1-ol from a lateral line to obtain the high-purity 3-methyl-3-butene-1-ol.
In the preparation step (3), the reaction pressure is preferably 6MPa to 10MPa, the reaction temperature is preferably 160 ℃ to 200 ℃, and the reaction time is preferably 15min to 30 min.
The molar ratio of the isobutylene and the dimethyldioxane fed in the above production step (3) is preferably 5 to 8: 2 to 4.
Compared with the prior art, the method for preparing the 3-methyl-3-butene-1-ol has the following beneficial effects:
(1) dimethyl dioxane is used for replacing formaldehyde, reaction raw materials are easy to obtain, byproducts are few, no formaldehyde residue is generated, the problems of low formaldehyde conversion rate and difficulty in separation and removal are solved, and the product quality is improved;
(2) the reaction condition is milder and more reliable, the side reaction is reduced, the preparation is simple, the fixed bed operation is adopted, the continuous production is realized, the production efficiency is improved, and the operation risk is reduced;
(3) the conversion rate of the raw material dimethyl dioxane is more than 99 percent, and the selectivity of isobutene is more than 98 percent.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. The detection method used in the examples is explained below:
a gas chromatograph is adopted to detect the conversion rate and selectivity of the dimethyl dioxane, and the specific analysis conditions are as follows:
the chromatograph was an Agilent 7890A, a chromatographic column model HP-5, an inner diameter of 320.00 μm, a length of 30.0m, and a maximum temperature of 325.0 ℃. And (3) a temperature raising program, namely firstly keeping the temperature at 40 ℃ for 1 minute, raising the temperature to 140 ℃ at 10 ℃/min for 2 minutes, raising the temperature to 280 ℃ at 20 ℃/min for 6 minutes, and keeping the total running time at 30 minutes.
The dimethyldioxanes used in the examples were prepared from formaldehyde and isobutene by the following method: firstly, 500g of Cu-Al-MCM-41 molecular sieve is selected as a catalyst, the catalyst is filled in a reactor, the temperature is raised to 96 ℃ after nitrogen replacement, then an isobutylene replacement reaction system is used, the pressure in the reactor is regulated to 2MPa by controlling a back pressure valve at the outlet of the reactor, isobutylene is preheated to 100 ℃, the feeding speed is 30g/h, a 37% formaldehyde solution is preheated to 95 ℃, the feeding speed is 150g/h, the mixed temperature of the two is 96 ℃, the reaction time is 5.8h, and the dimethyl dioxane with the purity close to 100% can be obtained by simple separation after the reaction liquid is cooled. The conversion rate of isobutene reaches more than 96 percent, and the selectivity of dimethyl dioxane is 100 percent.
Example 1
Preparation of the catalyst
Weighing 500g of molecular sieve, adding into a flask, taking 25g of manganese oxide and 25g of barium oxide, adding dilute nitric acid to dissolve metal oxides, adding into the flask, placing into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 3.5h, standing for 10h, adding ammonia water, adjusting the pH value of the solution to 10, solidifying for 5h, filtering, cleaning for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 125 ℃, and roasting for 4.5h at 540 ℃ to obtain the composite metal catalyst. Weighing 12g of tetradecyl dimethyl tertiary amine, adding toluene to dissolve, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating to 80 ℃, stirring or performing ultrasonic treatment for 2 hours, removing the solvent, washing with ethanol, drying at 120 ℃, roasting at 250 ℃ for 3 hours, and finally processing to obtain the 60-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
1) Adding 200g of the catalyst into a fixed bed, and replacing air in the fixed bed with nitrogen;
2) preheating isobutene to 190 ℃, introducing the isobutene into a mixer and a fixed bed at a flow of 16g/min, setting the temperature of the fixed bed at 180 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 8MPa, preheating dimethyldioxane to 120 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at a flow rate of 7.5g/min to be mixed with the isobutene, and introducing the mixture into the reactor for reaction for 12 hours continuously;
3) the reaction liquid is cooled and decompressed to 0.5MPa, after isobutene is separated, the reaction liquid is rectified and separated to obtain a product of 3-methyl-3-butene-1-ol, the content of the 3-methyl-3-butene-1-ol is analyzed by gas chromatography, and the yield is calculated to be 97.5%.
Example 2
Preparation of the catalyst
Weighing 500g of alumina, adding the alumina into a flask, taking 30g of calcium oxide and 20g of iron oxide, adding dilute nitric acid to dissolve metal oxides, adding the calcium oxide and the iron oxide into the flask, placing the mixture into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 3.5h, standing the mixed solution for 10h, adding ammonium bicarbonate, adjusting the pH value of the solution to 11, filtering the mixed solution after curing the mixed solution for 4.5h, washing the mixed solution for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 125 ℃, and roasting the solid catalyst at 540 ℃ for 5h to obtain the composite metal catalyst. Weighing 15g of phthalimide, adding toluene to dissolve the phthalimide, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating the mixture to 100 ℃, stirring or ultrasonically treating the mixture for 2 hours, removing the solvent, washing the mixture by using ethanol, drying the mixture at 120 ℃, roasting the mixture for 3.5 hours at 250 ℃, and finally processing the mixture to obtain the 70-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
The synthesis of example 1 was used with the following exceptions: preheating isobutene to 170 ℃, introducing the isobutene into a mixer and a fixed bed at the flow rate of 18g/min, setting the temperature of the fixed bed at 200 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 10MPa, preheating dimethyldioxane to 100 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at the flow rate of 5g/min to be mixed with the isobutene, introducing the mixture into the reactor to perform reaction for 12 hours continuously, and finally obtaining the yield of the 3-methyl-3-butene-1-ol by calculation, wherein the yield of the 3-methyl-3-butene-1-ol is 97.8 percent.
Example 3
Preparation of the catalyst
Weighing 500g of molecular sieve, adding into a flask, taking 26g of copper oxide and 15g of zinc oxide, adding dilute nitric acid to dissolve metal oxide, adding into the flask, placing into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 3.5h, standing for 10h, adding ammonium bicarbonate, adjusting the pH value of the solution to 11, filtering after curing for 4.5h, cleaning for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 125 ℃, and roasting for 5h at 540 ℃ to obtain the composite metal catalyst. Weighing 8.5g of dioctylamine, adding toluene for dissolving, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating to 100 ℃, stirring or ultrasonically treating for 2 hours, removing the solvent, washing by using ethanol, drying at 120 ℃, roasting at 250 ℃ for 3.5 hours, and finally processing to obtain the 80-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
The synthesis of example 1 was used with the following exceptions: preheating isobutene to 200 ℃, introducing the isobutene into a mixer and a fixed bed at a flow rate of 20g/min, setting the temperature of the fixed bed at 190 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 9MPa, preheating dimethyldioxane to 95 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at a flow rate of 3g/min to be mixed with the isobutene, introducing the mixture into the reactor to perform reaction for 12 hours continuously, and finally calculating to obtain the yield of the 3-methyl-3-butene-1-ol, wherein the yield of the 3-methyl-3-butene-1-ol is 97.4%.
Example 4
Preparation of the catalyst
Weighing 500g of silicon oxide, adding into a flask, taking 40g of strontium oxide and 30g of magnesium oxide, adding dilute nitric acid to dissolve metal oxide, adding into the flask, placing into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 8h, standing for 12h, adding ammonium bicarbonate, adjusting the pH value of the solution to 11, solidifying for 7.5h, filtering, cleaning for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 130 ℃, and roasting at 530 ℃ for 8h to obtain the composite metal catalyst. Weighing 25g of caprolactam, adding toluene to dissolve the caprolactam, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating the mixture to 110 ℃, stirring or ultrasonically treating the mixture for 7 hours, removing the solvent, washing the mixture by using ethanol, drying the mixture at 130 ℃, roasting the mixture for 5 hours at 250 ℃, and finally processing the mixture to obtain the 80-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
The synthesis of example 1 was used with the following exceptions: preheating isobutene to 160 ℃, introducing the isobutene into a mixer and a fixed bed at the flow rate of 30g/min, setting the temperature of the fixed bed at 170 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 9MPa, preheating dimethyldioxane to 110 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at the flow rate of 4g/min to be mixed with the isobutene, introducing the mixture into the reactor to perform reaction for 12 hours continuously, and finally obtaining the yield of the 3-methyl-3-butene-1-ol by calculation, wherein the yield of the 3-methyl-3-butene-1-ol is 97.2%.
Example 5
Preparation of the catalyst
Weighing 500g of molecular sieve, adding into a flask, taking 15g of barium oxide and 25g of magnesium oxide, adding dilute nitric acid to dissolve metal oxide, adding into the flask, placing into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 4h, standing for 6h, adding ammonium bicarbonate, adjusting the pH value of the solution to 11, solidifying for 4.5h, filtering, cleaning for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 130 ℃, and roasting at 530 ℃ for 6h to obtain the composite metal catalyst. Weighing 8g of caprolactam, adding toluene to dissolve the caprolactam, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating the mixture to 110 ℃, stirring or ultrasonically treating the mixture for 5 hours, removing the solvent, washing the mixture with ethanol, drying the mixture at 130 ℃, roasting the mixture for 4 hours at 250 ℃, and finally processing the mixture to obtain the 70-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
The synthesis of example 1 was used with the following exceptions: preheating isobutene to 160 ℃, introducing the isobutene into a mixer and a fixed bed at a flow rate of 80g/min, setting the temperature of the fixed bed at 180 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 10MPa, preheating dimethyldioxane to 120 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at a flow rate of 12g/min to be mixed with the isobutene, introducing the mixture into the reactor to perform reaction for 12 hours continuously, and finally obtaining the yield of the 3-methyl-3-butene-1-ol by calculation, wherein the yield of the 3-methyl-3-butene-1-ol is 97.7%.
Example 6
Preparation of the catalyst
Weighing 500g of molecular sieve, adding into a flask, taking 50g of manganese oxide and 12g of barium oxide, adding dilute nitric acid to dissolve metal oxide, adding into the flask, placing into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 7h, standing for 8h, adding ammonium bicarbonate, adjusting the pH value of the solution to 11, solidifying for 7.5h, filtering, cleaning for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 130 ℃, and roasting at 530 ℃ for 8h to obtain the composite metal catalyst. Weighing 22g of dimethylaniline, adding toluene to dissolve the dimethylaniline, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating the mixture to 110 ℃, stirring or ultrasonically treating the mixture for 8 hours, removing the solvent, washing the mixture by using ethanol, drying the mixture at 130 ℃, roasting the mixture for 5 hours at 250 ℃, and finally processing the mixture to obtain the 65-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
The synthesis of example 1 was used with the following exceptions: preheating isobutene to 190 ℃, introducing the isobutene into a mixer and a fixed bed at a flow of 10g/min, setting the temperature of the fixed bed at 200 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 7MPa, preheating dimethyldioxane to 110 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at a flow rate of 2g/min to be mixed with the isobutene, introducing the mixture into the reactor to perform reaction for 12 hours continuously, and finally obtaining the yield of the 3-methyl-3-butene-1-ol by calculation, wherein the yield of the 3-methyl-3-butene-1-ol is 97.1%.
Example 7
Preparation of the catalyst
Weighing 500g of molecular sieve, adding into a flask, taking 30g of barium oxide and 6g of tin oxide, adding dilute nitric acid to dissolve metal oxide, adding into the flask, placing into an ultrasonic container for mixing, ultrasonically treating the mixed solution for 5.5h, standing for 7h, adding ammonium bicarbonate, adjusting the pH value of the solution to 11, filtering after curing for 6.5h, cleaning for three times by using pure water to obtain a solid catalyst, drying the solid catalyst at 125 ℃, and roasting for 6.5h at 480 ℃ to obtain the composite metal catalyst. Weighing 24g of N-phenyl benzylamine, adding toluene to dissolve, mixing 300g of the prepared composite metal catalyst, adding the mixture into an oil bath, heating to 115 ℃, stirring or ultrasonically treating for 7.5h, then removing the solvent, washing by using ethanol, drying at 130 ℃, roasting at 280 ℃ for 4.5h, and finally processing to obtain the 70-mesh nitrogen-loaded composite metal catalyst.
Experiment for synthesizing 3-methyl-3-buten-1-ol
The synthesis of example 1 was used with the following exceptions: preheating isobutene to 220 ℃, introducing the isobutene into a mixer and a fixed bed at a flow rate of 20g/min, setting the temperature of the fixed bed at 200 ℃, adjusting a back pressure valve to control the pressure of the reactor to be 10MPa, preheating dimethyldioxane to 85 ℃ after the pressure is stable, introducing the dimethyldioxane into the mixer at a flow rate of 4g/min to be mixed with the isobutene, introducing the mixture into the reactor to perform reaction for 24 hours, and finally obtaining the yield of the 3-methyl-3-butene-1-ol by calculation, wherein the yield of the 3-methyl-3-butene-1-ol is 97.4%.
Comparative example 1
According to the prior art, formaldehyde methanol hemiacetal is used as a raw material to synthesize 3-methyl-3-butene-1-alcohol, the formaldehyde methanol hemiacetal is heated to 290 ℃ and pressurized to 19MPa, isobutene is heated to 290 ℃ and pressurized to 19MPa, the formaldehyde methanol hemiacetal and the isobutene are mixed and then enter a tubular reactor to react for 4min, and after the reaction is finished, methanol is separated by rectification, wherein the conversion rate of the formaldehyde methanol hemiacetal is 98.9 percent, and the selectivity is 98.6 percent.
Comparative example 2
According to the prior art, 3-methyl-3-butene-1-ol is synthesized by taking paraformaldehyde as a raw material, firstly, the paraformaldehyde is depolymerized by methylal in a reaction kettle, the temperature is controlled at 150 ℃, and the reaction is carried out for 3 hours to obtain a transparent solution; adding isobutene into a reaction kettle, wherein the mass ratio of olefine to aldehyde is 10, the reaction temperature is 230 ℃, the reaction pressure is 15-16 MPa, the reaction time is 3 hours, discharging reaction materials, and rectifying to separate isobutene, methanol and methylal, wherein the yield of corresponding paraformaldehyde is up to 93.5%.
As shown in comparative example 1, the synthesis of 3-methyl-3-buten-1-ol from formaldehyde-methanol hemiacetal has high temperature and pressure, high requirements from the viewpoint of reactor design and process safety, and high cost, and although the methanol generated by the reaction can be reused after rectification and separation, the energy consumption and cost are increased.
The comparative example 2 shows that the reaction time of 3h for synthesizing the 3-methyl-3-buten-1-ol by reacting the methylal which is synthesized by taking paraformaldehyde as a raw material with isobutene is 3h, the yield is limited due to the extension of the reaction time, and meanwhile, the reactor is a kettle type reactor, so that the problem of difficult design of the reactor exists in the industrial amplification process, and the methanol and the methylal which are generated by the reaction need to be separated, so that the energy consumption is relatively increased.
The method of the invention can better embody the obvious advantages of the invention in the aspects of raw material selection, process conditions, reactor design and the like by combining the comparative example and the method of the invention, and has more value of industrial application.
Claims (10)
1. A method of synthesizing 3-methyl-3-buten-1-ol, the method comprising: in the presence of a catalyst, isobutene and dimethyldioxane are reacted to form 3-methyl-3-buten-1-ol.
2. The process according to claim 1, wherein dimethyldioxane as a starting material is prepared from formaldehyde and isobutylene under acidic catalyst conditions; the acid catalyst can be one or more of sulfuric acid, phosphoric acid, hydrochloric acid, solid acid and heteropoly acid, and the mass ratio of the formaldehyde to the isobutene is 2: 1-8: 1;
preferably, the reaction temperature in the preparation of the dimethyldioxane is 60-100 ℃, and the reaction time is 4-8 h.
3. A process as claimed in claim 1, wherein the reaction temperature of isobutene and dimethyldioxane is from 150 to 220 ℃, more preferably from 160 to 200 ℃; the reaction pressure is 4MPa to 15MPa, and more preferably 6MPa to 10 MPa.
4. A process as claimed in claim 3, wherein the reaction time of isobutene with dimethyldioxane is from 10min to 60min, more preferably from 15min to 30 min.
5. The process as claimed in any one of claims 1 to 4, wherein the molar ratio of isobutene to dimethyldioxane is from 3 to 10: 1 to 5, and preferably 5 to 8: 2 to 4.
6. The process according to any one of claims 1-5, wherein the reaction is carried out under an inert atmosphere, such as nitrogen, and in a fixed bed reactor filled with a catalyst.
7. The process of any of claims 1-6, wherein the catalyst comprises a procatalyst and a cocatalyst, the procatalyst being a metal oxide and the cocatalyst being a nitrogen-containing compound.
8. The process of claim 7, wherein the procatalyst metal oxide loading is preferably 3 to 40 wt%, more preferably 5 to 20 wt%, based on the mass of the support; preferably, the nitrogen-containing compound loading amount of the cocatalyst is preferably 1 to 15 wt%, more preferably 2 to 5 wt%, based on the mass of the carrier.
9. The method according to claim 7, wherein the metal oxide is selected from two or more of magnesium oxide, calcium oxide, manganese oxide, barium oxide, iron oxide, copper oxide, zinc oxide, tin oxide, strontium oxide, such as manganese oxide and barium oxide, calcium oxide and iron oxide, copper oxide and zinc oxide, strontium oxide and magnesium oxide, preferably including at least one alkaline earth metal oxide and an oxide selected from at least one of iron, copper, tin, manganese, strontium;
the cocatalyst is preferably selected from one or more of imide, carbonamide, fatty amine, aromatic amine, nitrogen-containing heterocycle, quaternary ammonium base, preferably one or more of phthalimide, propiolactam, caprolactam, dimethylaniline, p-toluidine, methylethylcyclopropylamine, p-chloroaniline, tetradecyldimethylamine, dodecyldimethylamine, decaalkyldimethylamine, didodecyltrimethylamine, dioctadecylmethylamine, trioctylalkylamine, octadecylamine, dioctylamine, didecylamine, dodecylamine, diisooctylamine, isooctylamine, N-pentylamine, N-hexylamine, aminopyridine, pyridine, imidazole, pyrrole, dimethylformamide, triethylamine, N-phenylbenzenemethylmethylamine, tetraisopropylamine iodide, and (2-hydroxyethyl) trimethylamine hydroxide;
preferably, the support comprises one or more of alumina, silica, molecular sieves;
preferably, the promoter is loaded onto the metal oxide-supported catalyst support by:
firstly weighing a carrier carrying a main catalyst metal oxide, heating to 50-100 ℃, weighing a nitrogen-containing compound, adding the nitrogen-containing compound into the heated carrier, dissolving and mixing the nitrogen-containing compound and the heated carrier by using an organic solvent, then removing the solvent, washing, drying the obtained nitrogen-containing compound-carrying composite metal catalyst, and further roasting to obtain the nitrogen-containing compound-carrying composite metal catalyst.
10. The method according to any one of claims 1-9, wherein the method comprises the steps of:
(1) firstly, nitrogen or inert gas is used for purging the reactor, and air in the reactor is completely replaced;
(2) heating isobutene to the required temperature of 100-300 ℃ through a preheater, preferably 150-220 ℃, and preheating dimethyl dioxane through the preheater to the required temperature of 60-140 ℃, and further preferably 80-120 ℃;
(3) mixing the two materials through a mixer, continuously feeding the mixed materials into a fixed bed reactor, and reacting under the action of a catalyst to generate 3-methyl-3-butene-1-ol;
(4) and (3) cooling the reaction liquid, then performing pressure rectification separation, separating unreacted isobutene, introducing the residual reaction liquid into a de-heavy rectifying tower, and extracting the 3-methyl-3-butene-1-ol from a lateral line to obtain the high-purity 3-methyl-3-butene-1-ol.
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