CN101952233B - Method of making benzylated phenols - Google Patents
Method of making benzylated phenols Download PDFInfo
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- CN101952233B CN101952233B CN2006800319241A CN200680031924A CN101952233B CN 101952233 B CN101952233 B CN 101952233B CN 2006800319241 A CN2006800319241 A CN 2006800319241A CN 200680031924 A CN200680031924 A CN 200680031924A CN 101952233 B CN101952233 B CN 101952233B
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- China
- Prior art keywords
- phenol
- metal oxide
- benzylalcohol
- alkaline metal
- equal
- Prior art date
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- 150000002989 phenols Chemical class 0.000 title claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 59
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 49
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 36
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 claims description 21
- 239000011148 porous material Substances 0.000 claims description 21
- -1 naphthyl alcohol Chemical compound 0.000 claims description 18
- 229960004217 benzyl alcohol Drugs 0.000 claims description 16
- 239000012702 metal oxide precursor Substances 0.000 claims description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 239000011800 void material Substances 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 8
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- NGPGYVQZGRJHFJ-UHFFFAOYSA-N chembl1604790 Chemical compound OC1=CC(O)=CC=C1N=NC1=CC=C([N+]([O-])=O)C=C1 NGPGYVQZGRJHFJ-UHFFFAOYSA-N 0.000 claims description 6
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- ZBJWWKFMHOAPNS-UHFFFAOYSA-N loretin Chemical compound C1=CN=C2C(O)=C(I)C=C(S(O)(=O)=O)C2=C1 ZBJWWKFMHOAPNS-UHFFFAOYSA-N 0.000 claims description 5
- 229950010248 loretin Drugs 0.000 claims description 5
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000002902 bimodal effect Effects 0.000 claims description 4
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- SBUIQTMDIOLKAL-UHFFFAOYSA-N (2-ethylphenyl)methanol Chemical compound CCC1=CC=CC=C1CO SBUIQTMDIOLKAL-UHFFFAOYSA-N 0.000 claims description 2
- PTHGDVCPCZKZKR-UHFFFAOYSA-N (4-chlorophenyl)methanol Chemical compound OCC1=CC=C(Cl)C=C1 PTHGDVCPCZKZKR-UHFFFAOYSA-N 0.000 claims description 2
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 2
- KWXSTAUVUZAMGW-UHFFFAOYSA-N 3-methyl-1-phenylbutan-1-ol Chemical compound CC(C)CC(O)C1=CC=CC=C1 KWXSTAUVUZAMGW-UHFFFAOYSA-N 0.000 claims description 2
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical group COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 claims description 2
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229960004698 dichlorobenzyl alcohol Drugs 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
- 239000003054 catalyst Substances 0.000 abstract description 18
- 229910001038 basic metal oxide Inorganic materials 0.000 abstract 1
- 239000012808 vapor phase Substances 0.000 abstract 1
- 239000008188 pellet Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 238000001354 calcination Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000001993 wax Substances 0.000 description 5
- DUCSXVAAPCQAEP-UHFFFAOYSA-N 2,6-dibenzylphenol Chemical compound C1=CC=C(CC=2C=CC=CC=2)C(O)=C1CC1=CC=CC=C1 DUCSXVAAPCQAEP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000001095 magnesium carbonate Substances 0.000 description 4
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 4
- 235000014380 magnesium carbonate Nutrition 0.000 description 4
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 4
- 229960001708 magnesium carbonate Drugs 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N 2-butylphenol Chemical compound CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 150000004676 glycans Chemical class 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- LRFAAOQURBBZRF-UHFFFAOYSA-N 2,3-dibenzyl-4-methylphenol Chemical compound C=1C=CC=CC=1CC=1C(C)=CC=C(O)C=1CC1=CC=CC=C1 LRFAAOQURBBZRF-UHFFFAOYSA-N 0.000 description 1
- YZKPJAZHLHPYBZ-UHFFFAOYSA-N 2,4-dibenzylphenol Chemical compound C1=C(CC=2C=CC=CC=2)C(O)=CC=C1CC1=CC=CC=C1 YZKPJAZHLHPYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007049 Juglans regia Species 0.000 description 1
- 235000009496 Juglans regia Nutrition 0.000 description 1
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 description 1
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 description 1
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 235000019808 microcrystalline wax Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/68—Purification; separation; Use of additives, e.g. for stabilisation
- C07C37/88—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/24—Halogenated derivatives
- C07C39/367—Halogenated derivatives polycyclic non-condensed, containing only six-membered aromatic rings as cyclic parts, e.g. halogenated poly-hydroxyphenylalkanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A method of making benzylated phenols comprises contacting a phenol and a benzyl alcohol with a basic metal oxide catalyst at a temperature sufficient to maintain each of the phenol and the benzyl alcohol in a vapor phase. The phenol has at least one hydrogen ortho to its phenolic hydroxyl group.
Description
Background of invention
The present invention relates to prepare the method for benzyl phenol.
Benzyl phenol, particularly ortho position benzyl phenol are valuable inhibitor and chemical intermediate.
Usually, benzylphenol is to prepare with benzyl chloride or benzylalcohol processing phenol through existing at strong acid (for example, aluminum chloride, zinc chloride and sulfuric acid) down.In other method, through heating phenol and sodium hydroxide in toluene and make it and benzyl chloride reacts and to prepare 2-benzylphenol, 2,4-dibenzyl phenol and 2,6-dibenzyl phenol.Perhaps, benzylalcohol can use aluminum chloride catalyst and p-cresol prepared in reaction dibenzyl-p-cresol.Have the adjacent of replacement phenol and benzylalcohol and contact with the active oxidation Al catalysts that to carry out the vapour phase benzylization also be known.
Yet, some in these aforesaid methods obtain a great deal of between the position and the benzylphenol of para-orientation.The other problem that these methods face comprises batch process, corrosion and harsh operational condition.
Therefore, this area constantly need prepare the method for benzyl phenol, and this method optionally prepares ortho position phenol and 2, and 6-dibenzyl phenol and operational condition are not too strict.
The invention summary
The invention discloses the method for preparing benzyl phenol.
According to a kind of embodiment, the method for preparing benzyl phenol comprises: phenol is being enough to that with the alkaline metal oxide catalyzer phenol is contacted with the temperature that the benzylalcohol class all remains in vapour phase with the benzylalcohol class.This phenol has at least one and is positioned at phenolic hydroxyl group adjacent hydrogen.
Detailed Description Of The Invention
In following specification sheets of the present invention and claims, will be with reference to a large amount of terms, these terms have following implication through definition.
Singulative " one, a kind of and should (a, an, the) " comprise a plurality of things that refer to, only if this paper has clearly explanation in addition.
" optional " or " randomly " is meant that incident or the situation described subsequently possibly take place or possibly not take place, and this description comprises situation that said incident takes place and the situation that does not take place.
" combination " used among this paper comprises mixture, multipolymer, reaction product, blend, mixture, or the like.
The end points of quoting all scopes of same characteristic features as proof can combine and comprise the end points of being quoted as proof independently.The numerical value that is expressed as " greater than approximately " or " less than approximately " comprises said end points, and for example, " greater than about 3.5 " comprise numerical value 3.5.
This paper is disclosed to be the method for preparing benzyl phenol, particularly prepares the method for ortho position phenol (for example, 2,6-dibenzyl phenol).As following more detailed description; Have been found that; Through with phenol and benzylalcohol class in the presence of the alkaline metal oxide catalyzer, the ortho position benzyl phenol that can obtain highly selective in the thermotonus that is enough to make reactant remain in vapour phase is (for example, 80%-90%).For example, 300 ℃ to 600 ℃ temperature can be adopted, perhaps, more specifically, 350 ℃ to 450 ℃ temperature can be adopted.The selectivity definition of using among this paper is 100 * (all ortho position benzyl products)/(gross product).
This method is applicable to the phenol of wide region.The aromatic hydroxy compound that all have at least one hydroxyl that combines with aromatic ring described prevailingly in used term " phenol ".The phenol that in said method, uses has at least one and is positioned at phenolic hydroxyl group adjacent hydrogen.In addition, selecting phenol to make it to be heated to is enough to make it to change the temperature of vapour phase into and do not have too much decomposition.The instance of suitable phenol comprises phenol, ortho-cresol, p-cresol, 4-ethylphenol, 4-phenylphenol, naphthyl alcohol, β-Nai Fen, 4-chlorophenol, 2-chlorophenol, 2; 4-NSC 2879,4-bromophenol, Resorcinol, 4-methoxyphenol, 4-thanatol; Or the like, and the combination that comprises at least a above-mentioned phenol.Specially suitable phenol comprises compound phenol, C
6H
5OH, with and single lower alkyl derived thing such as p-cresol, ortho-cresol, p-ethyl phenol, align butylphenol, or the like.More specifically, in one embodiment, this phenol is compound phenol.
The compounds with formula I structure described widely in term " benzylalcohol class ":
R wherein
1Can or have the alkyl of 1-5 carbon for hydrogen.Ar representes monobasic cyclophane family's group or polynary cyclophane family group, and it can be unsubstituted or replaced by the group of for example alkyl, halogen, alkoxyl group etc.Suitable benzylalcohol class comprises to xylyl alcohol, to ethyl benzylalcohol, o-methyl benzyl alcohol, to isobutyl-benzylalcohol, p-Chlorobenzyl alcohol, 2; 4-Dybenal, adjacent bromobenzyl alcohol, p-methoxybenzyl alcohol, to oxyethyl group benzylalcohol; Or the like, and the combination that comprises at least a aforementioned substances.In one embodiment, the benzylalcohol class comprises compound phenylcarbinol, C
6H
5CH
2OH.
In reaction, can use the benzylalcohol class of different amounts for every moles of phenol.For example, the amount of the benzylalcohol class of every moles of phenol use can be 0.2 mole to 10 moles.In this scope, the amount of benzylalcohol class can for every moles of phenol more than or equal to 1 mole of benzylalcohol class, perhaps, more specifically, for every moles of phenol more than or equal to 2 moles of benzylalcohol classes.In this scope, the amount of benzylalcohol class can be less than or equal to 5 moles of benzylalcohol classes for every moles of phenol equally, perhaps, more specifically, for every moles of phenol is less than or equal to 3 moles of benzylalcohol classes.
For example, in one embodiment, when the needs dibenzyl, the amount of the used benzylalcohol class of every moles of phenol is 1 mole to 3 moles, perhaps, more specifically, is 1.5 moles to 2.5 moles.In another kind of embodiment,, perhaps, more specifically, when being 3 moles to 4 moles, can obtain 2 of high yield (for example), 6-dibenzyl phenol more than or equal to 40% when the amount of the used benzylalcohol class of every moles of phenol is 2 moles to 5 moles.In another embodiment, when the needs monobenzyl, the used benzylalcohol class amount of every moles of phenol is 0.2 mole to 3 moles, perhaps, more specifically, is 0.5 mole to 1 mole.
The catalyzer that in said method, uses comprises that at least a alkaline metal oxide is as main ingredient.The metal that is suitable for this alkaline metal oxide comprises iron, magnesium, calcium, barium and strontium.This alkaline metal oxide can derive from the alkaline metal oxide precursor, comprises azoviolet, ferron, or comprises the combination of at least a aforementioned substances.Can use the magnesian azoviolet of any generation.Equally, can use the ferron of any generation red stone.
Suitable azoviolet includes but not limited to, Natural manganese dioxide, Marinco H, magnesiumcarbonate, magnesium, magnesium basic carbonate, and the mixture that comprises at least a aforementioned substances.Azoviolet is generally the powder form.For example, the mean particle size of azoviolet (passing each particulate full diameter (that is, longest diameter) measures definite) is 5 microns to 50 microns, in particular for 10 microns to 30 microns.
The instance that is used to prepare the ferron of catalyzer includes but not limited to iron nitrate, ferric sulfate, iron(ic)chloride, Iron nitrate, ferrous sulfate and iron protochloride.In one embodiment, ferron comprises iron nitrate.Red stone can be any form.For example, the suitable form of red stone includes but not limited to, FeO, Fe
2O
3, Fe
3O
4, and the mixture that comprises at least a aforementioned substances.
Catalyzer is through with alkaline metal oxide precursor and at least a filler, and optional pore former (pore former) is done and mixed and form.Like what use among the present invention, term " do mix " refers to routine techniques that single composition is mixed with dryness at first, and by any " wet method " technology as suspension-s blend (suspension blending) or precipitate.Can use the mechanical mixer or the blending machine of any kind, for example belt blending machine.Term " filler " includes but not limited to, lubricant, tackiness agent and filler.
The filler total amount that in catalyst composition, exists can be less than or equal to 20 weight %, based on the gross weight of filler and alkaline metal oxide precursor.In some embodiments, the filler total amount is less than or equal to 10 weight %.The examples of fillers that is used for catalyst composition comprises graphite and ppe (PPE).In some embodiments, the amount that ppe uses is less than or equal to 10 weight %, based on the gross weight of filler and alkaline metal oxide precursor.In some embodiments, used quantity of graphite is less than or equal to 5 weight %.
Optional pore former is the material that can in catalyzer, help to form the hole.For example, suitable pore former includes but not limited to wax and polysaccharide.Wax can comprise paraffin, polyethylene wax, Microcrystalline Wax, montanin wax, or the like, and the combination that comprises at least a aforementioned substances.Polysaccharide can comprise Mierocrystalline cellulose, CMC 99.5, FM, starch, English walnut powder, Hydrocerol A, polyoxyethylene glycol, oxalic acid, Triple Pressed Stearic Acid, or the like, and the combination that comprises at least a aforementioned substances.Same useful is positively charged ion and AS, is generally the long-chain (C that contains neutral acid groups (acid specie) (for example, carboxylic acid, phosphoric acid and sulfonic acid group)
10-28) hydrocarbon.
The mean pore size that the amount that optional pore former uses is enough to after calcining, to provide be 50
to 300
; Perhaps; More specifically, the calcining after mean pore size be 100
to 300
.For example, the amount that pore former exists can be 0.5wt.% to 50wt.%, based on the gross weight of alkaline metal oxide precursor, filler and pore former.In this scope, the amount that pore former exists can be less than or equal to 40wt.%, perhaps, more specifically, is less than or equal to 30wt.%.Equally in this scope, the amount that pore former exists can be more than or equal to 2wt.%, perhaps, more specifically, more than or equal to 5wt.%.
In some embodiments, catalyzer has bimodal void distribution.Be not wishing to be bound by theory, think first and the less void distribution of diameter derive from the alkaline metal oxide precursor of calcination process, that is, these holes and calcining do not contain the measure-alike of those holes that the alkaline metal oxide precursor of pore former obtains.Think second and the bigger void distribution of diameter be that pore former itself adds and the incinerating result, that is, after calcining the alkaline metal oxide precursor that does not contain pore former, can not find these apertures in a large number.
In one embodiment; Bimodal void distribution has first void distribution and second void distribution; Wherein first mean pore size that distribute less than 100
and second mean diameter that distribute more than or equal to 100
and be less than or equal to 500
.
After doing the pore former completion that mixes alkaline metal oxide precursor, filler (or multiple filler) and choose wantonly, be the powder form through blended solid catalyst compsn.The bulk density of this powder is generally 0.1 gram/cubic centimetre (g/cm
3) to 0.5g/cm
3, perhaps, more specifically, be 0.25g/cm
3To 0.5g/cm
3Then, before being configured as the shape of expectation, usually powder is further processed.For example, can powder be screened (to obtain narrower size-grade distribution), grind, suppress, or the like.In most of embodiment, catalyst composition carries out degasification before with other processing after dried mixing.Through removing the gas of carrying secretly in the powder (being mainly air) by the strong hand, degasification has further increased the bulk density of material.
Catalyzer can be shaped as any desired shape.For example, catalyzer can be pressed into pellet or " small pieces ", and this can include but not limited to USP 4,900 through prilling granulator, and the device described in 708 is realized.Then, the catalyst composition of calcining shaping.Calcining is carried out usually as follows: at the temperature heatable catalyst that is enough to the alkaline metal oxide precursor is changed into alkaline metal oxide (it is the active substance in the catalyzer).Calcining has increased the surface-area of catalyzer.Calcining temperature can change according to metal precursor, but is generally 350 ℃ to 600 ℃.Calcination atmosphere can be oxidizing atmosphere, inert atmosphere or reducing atmosphere.Perhaps, can be when the benzyl reaction begins calcined catalyst.In other words, in the presence of raw material (for example phenol and benzylalcohol class), calcine.
The surface-area of catalyst pellets can be 50 meters squared per gram (m
2/ g) to 300m
2/ g perhaps, more specifically, is 120 meters squared per gram (m
2/ g) to 200m
2/ g analyzes based on BET (Brunauer, Emmett, and Teller).The pellet density of unsintered pellet (pellet density) is 1.3g/cm
3To 2.1g/cm
3In this scope, the pellet density of this pellet is more than or equal to 1.4g/cm
3, and particularly more than or equal to 1.6g/cm
3In this scope, the pellet density of this pellet is less than or equal to 2.0g/cm equally
3, and be less than or equal to 1.9g/cm particularly
3
In one embodiment, the surface-area of catalyst pellets and volume ratio are 950 metre squared per cubic (m
2/ m
3) to 4000m
2/ m
3In this scope, the surface-area of catalyst pellets and volume ratio are particularly more than or equal to 1100m
2/ m
3, more specifically more than or equal to 1300m
2/ m
3In this scope, the surface-area of catalyst pellets and volume ratio are less than or equal to 3800m particularly equally
2/ m
3, more specifically be less than or equal to 3000m
2/ m
3
In another embodiment, the length-to-diameter ratio of catalyst pellets (aspect ratio) is 0.7 to 1.0.In this scope, length-to-diameter ratio is particularly more than or equal to 0.72, more specifically more than or equal to 0.75.In this scope, length-to-diameter ratio is less than or equal to 0.95 particularly equally, more specifically is less than or equal to 0.90.Length-to-diameter ratio is defined as the ratio of length and diameter or length and width in this article.
The phenol and the benzylalcohol class that in operation, will have at least one the not replacement adjacent with its phenolic hydroxyl group (dehydrogenation is as outside the substituting group) position are introduced (for being easy to discuss, the back is called " catalyst bed ") in the container that contains catalyzer.The temperature maintenance of catalyst bed is being enough to make reactant remain in the temperature (for example, 300 ℃ to 600 ℃ temperature) of vapour phase.Reaction is under atmospheric pressure carried out, but also can adopt normal atmosphere above or below.This reaction also can be carried out in the presence of water vapor.For example, the amount that water vapor exists can be 1wt.% to 35wt.% based on the gross weight of reactant, perhaps, more specifically, is 5wt.% to 25wt.%.
Said method makes the selectivity of ortho position benzyl product (for example, ortho position phenol and 2,6-dibenzyl phenol) more than or equal to 80%, and perhaps, more specifically, selectivity is more than or equal to 85%.In some embodiments, selectivity is more than or equal to 99%.Change kind of a mode and explain, embodiment disclosed herein does not have by product to produce basically.For example, the 1wt.% that is less than or equal to the reaction product gross weight is by product (for example, benzylic ether, a position or a contraposition benzylphenol).Although possibly produce phenyl aldehyde, it can form ortho position benzyl product through reclaiming.When catalyzer comprises red stone, produce ortho position benzylphenol based on reaction product gross weight 15wt.%.
Following examples only supply to explain and represent the instance of preparation benzyl phenol, and should not regard restriction scope of the present invention as.
Embodiment
Embodiment 1
Use high speed shear blending machine that about 10 gram magnesiumcarbonate and 1 gram wax were mixed 10 minutes.Under liquid nitrogen, carry out this mixing process, so that mix.The blend of gained is configured as pellet and under nitrogen, 390 ℃ to 410 ℃ temperature calcinings, the temperature rise rate of employing (ramp rate) be 0.2 degrees celsius/minute (℃/min) to 5 ℃/min.With nitrogen flow remain on 0.06 the gram nitrogen/hour/gram (g/hr/g) catalyzer to the 10g/hr/g catalyzer.The incinerating initial temperature also changes to 200 ℃ from room temperature.Use Micromeritics 2010 analysers that about 300 milligrams of incinerating samples are carried out surface-area and porosity (porosity) measurement.Pore size distribution and surface-area derive from the nitrogen desorption isotherm.The overall average pore diameter of 120
to 180
.Pore volume is that 0.5 cubic centimetre/gram (cc/g) is to 0.7cc/g.Surface-area is 100m
2/ g to 250m
2/ g.
Embodiment 2
With 5 cubic centimetres of (cc) mean particle sizes is that 1000 microns to 1400 microns magnesiumcarbonate pellet is packed in the packed bed reactor.With the condition of the speed of 0.2～0.5 ℃/min, 0.06～0.24 (10) g nitrogen/hr/g catalyzer 390 ℃ of original position calcined catalysts 16 to 22 hours.Institute responds and all under atmospheric pressure carries out.In two hours, under nitrogen atmosphere, temperature is risen to 475 ℃ from 390 ℃ after the calcination.Reach after this temperature 15 minutes, incoming mixture is introduced with 0.12cc/min.This charging contains 16.21wt.% phenol, 74.48wt.% phenylcarbinol and 9.31wt.% water (mol ratio of phenylcarbinol and phenol is 4: 1).Under isothermal condition, carry out benzyl reaction 24 hours.Monitoring reaction product such as 2-methane, 2 after 20 hours, the productive rate of 6-dibenzyl phenol, phenyl aldehyde and unreacting phenol and phenylcarbinol.Measured transformation efficiency is based on the area percentage at the peak of gc record.The result is shown in table 1.
Table 1
| Product | Productive rate |
| Phenol | 1.3 |
| The 2-benzylphenol | 20.2 |
| 2,6-dibenzyl phenol | 46.5 |
| Phenyl aldehyde | 13.5 |
| Phenylcarbinol | 18.5 |
Present embodiment shows, when the mol ratio of phenylcarbinol and phenol that adopts 4: 1, the productive rate of ortho position benzyl phenol is greater than 50%, more specifically, and greater than 60%.More particularly, 2, the productive rate of 6-dibenzyl phenol is more than or equal to 40%.This reaction confirms that the selectivity of ortho position benzyl phenol is 83%, and another significant product phenyl aldehyde is only arranged, and it can loop back and obtain other products in the reaction.
In the present embodiment, said method is used basic catalyst such as magnesiumcarbonate cheaply, and it can situ converting be a Natural manganese dioxide.The reaction product of gained comprises the product that minimum is not expected, like a contraposition and a position benzylphenol.For example, use the reaction of catalyzer of the present invention to have 13.5% by product (phenyl aldehyde is only arranged), by contrast, use the same reaction of αYang Hualv to have 50% by product.
Said method allows to use the catalyzer of lower cost, and obtains the ortho position benzyl phenol of highly selective.Therefore, can realize the reduction of separation costs.In addition, this method allows to adopt continuation method, and this can improve turnout than discontinuous method.Said method is not used the acid that can cause corrosion or increase the treatment facility cost.
Though described the present invention with reference to exemplary, it will be appreciated by those skilled in the art that without departing from the scope of the invention, can carry out various variations and can substitute its element with Equivalent.In addition, under the situation that does not break away from base region of the present invention, can carry out many changes, to adapt to concrete situation or material according to instruction of the present invention.Therefore, the optimal mode that the present invention and being not intended to is confined to consider as embodiment of the present invention and disclosed specific embodiments, but the present invention will comprise falling all embodiments within the scope of the appended claims.
Claims (9)
1. method for preparing benzyl phenol, this method comprises:
Phenol is contacted with the temperature of alkaline metal oxide catalyzer at 300 ℃ to 600 ℃ with the benzylalcohol class, and wherein this phenol has at least one and is positioned at phenolic hydroxyl group adjacent hydrogen, and said alkaline metal oxide comprises the oxide compound of iron, magnesium, calcium, barium or strontium.
2. the method for claim 1; Wherein said phenol is selected from phenol, ortho-cresol, p-cresol, 4-ethylphenol, 4-phenylphenol, naphthyl alcohol, β-Nai Fen, 4-chlorophenol, 2-chlorophenol, 2; 4-NSC 2879,4-bromophenol, Resorcinol, 4-methoxyphenol, 4-thanatol and comprise the combination of at least a aforementioned substances.
3. claim 1 or 2 method; Wherein said benzylalcohol class is selected from phenylcarbinol, to xylyl alcohol, to ethyl benzylalcohol, o-methyl benzyl alcohol, to isobutyl-benzylalcohol, p-Chlorobenzyl alcohol, 2; 4-Dybenal, adjacent bromobenzyl alcohol, p-methoxybenzyl alcohol, to oxyethyl group benzylalcohol with comprise the combination of at least a aforementioned substances.
4. each method of claim 1-3, wherein said alkaline metal oxide catalyzer is obtained by the alkaline metal oxide precursor, and this alkaline metal oxide precursor comprises azoviolet, ferron, or comprises the combination of at least a aforementioned substances.
5. each method of claim 1-4, wherein said alkaline metal oxide catalyzer has bimodal void distribution.
6. the method for claim 5, wherein said bimodal void distribution comprise that first void distribution and the mean diameter of mean pore size less than
is more than or equal to
and second void distribution that is less than or equal to
.
7. each method of claim 1-6, the consumption of wherein said benzylalcohol class is 0.2 mole to 10 moles benzylalcohol class of every moles of phenol.
8. each method of claim 1-7, wherein said alkaline metal oxide catalyzer has
mean pore size to
.
9. each method of claim 1-8, wherein the ortho position benzyl product selectivity of this method is more than or equal to 80%.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US21429505A | 2005-08-29 | 2005-08-29 | |
| US11/214,295 | 2005-08-29 | ||
| PCT/US2006/030662 WO2007027375A2 (en) | 2005-08-29 | 2006-08-08 | Method of making benzylated phenols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101952233A CN101952233A (en) | 2011-01-19 |
| CN101952233B true CN101952233B (en) | 2012-12-05 |
Family
ID=37529448
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006800319241A Expired - Fee Related CN101952233B (en) | 2005-08-29 | 2006-08-08 | Method of making benzylated phenols |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1934162A2 (en) |
| JP (1) | JP2009507789A (en) |
| KR (1) | KR20080044891A (en) |
| CN (1) | CN101952233B (en) |
| WO (1) | WO2007027375A2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2981069B1 (en) * | 2011-10-06 | 2013-12-20 | Rhodia Operations | PROCESS FOR PREPARING A VANILLIN DERIVATIVE |
| CN104922096A (en) * | 2015-05-27 | 2015-09-23 | 云南中医学院 | Application of 4-methoxy benzyl alcohol to preparation of antioxidant type drug |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4105699A (en) * | 1977-02-16 | 1978-08-08 | Continental Oil Company | Preparation of o-benzylphenol |
| US4514577A (en) * | 1982-10-15 | 1985-04-30 | Ethyl Corporation | Chemical process for preparing di-ortho benzyl phenols |
| JPS6032740A (en) * | 1983-08-03 | 1985-02-19 | Mitsubishi Chem Ind Ltd | Production of o-benzylphenol |
| CA1234154A (en) * | 1984-12-24 | 1988-03-15 | Allen H. Filbey | Dibenzylphenolic antioxidiants |
| DE3700917A1 (en) * | 1987-01-14 | 1988-07-28 | Bayer Ag | METHOD FOR PRODUCING P-SUBSTITUTED O-BENZYLPHENOLS |
-
2006
- 2006-08-08 JP JP2008529052A patent/JP2009507789A/en not_active Withdrawn
- 2006-08-08 CN CN2006800319241A patent/CN101952233B/en not_active Expired - Fee Related
- 2006-08-08 KR KR1020087007684A patent/KR20080044891A/en not_active Application Discontinuation
- 2006-08-08 WO PCT/US2006/030662 patent/WO2007027375A2/en active Application Filing
- 2006-08-08 EP EP06800851A patent/EP1934162A2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| CN101952233A (en) | 2011-01-19 |
| JP2009507789A (en) | 2009-02-26 |
| WO2007027375A3 (en) | 2010-05-06 |
| EP1934162A2 (en) | 2008-06-25 |
| KR20080044891A (en) | 2008-05-21 |
| WO2007027375A2 (en) | 2007-03-08 |
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