CN102452906B - Preparation method of 2,6-diphenyl phenol - Google Patents
Preparation method of 2,6-diphenyl phenol Download PDFInfo
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- CN102452906B CN102452906B CN2010105234271A CN201010523427A CN102452906B CN 102452906 B CN102452906 B CN 102452906B CN 2010105234271 A CN2010105234271 A CN 2010105234271A CN 201010523427 A CN201010523427 A CN 201010523427A CN 102452906 B CN102452906 B CN 102452906B
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- ATGFTMUSEPZNJD-UHFFFAOYSA-N 2,6-diphenylphenol Chemical compound OC1=C(C=2C=CC=CC=2)C=CC=C1C1=CC=CC=C1 ATGFTMUSEPZNJD-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000006482 condensation reaction Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 4
- 229920001470 polyketone Polymers 0.000 claims description 40
- 239000000376 reactant Substances 0.000 claims description 34
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 238000001953 recrystallisation Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 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 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 15
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000007795 chemical reaction product Substances 0.000 abstract description 6
- 230000007547 defect Effects 0.000 abstract description 2
- 150000002576 ketones Chemical class 0.000 abstract 3
- 239000000571 coke Substances 0.000 abstract 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 238000006356 dehydrogenation reaction Methods 0.000 description 13
- 239000013078 crystal Substances 0.000 description 12
- 238000004128 high performance liquid chromatography Methods 0.000 description 11
- 238000004458 analytical method Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 238000010812 external standard method Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 5
- AUEZNTKYSSUTGZ-UHFFFAOYSA-N 2,6-dicyclohexylphenol Chemical compound OC1=C(C2CCCCC2)C=CC=C1C1CCCCC1 AUEZNTKYSSUTGZ-UHFFFAOYSA-N 0.000 description 5
- IORDYLSDCDNDFU-UHFFFAOYSA-N 2-cyclohexyl-6-phenylphenol Chemical compound OC1=C(C2CCCCC2)C=CC=C1C1=CC=CC=C1 IORDYLSDCDNDFU-UHFFFAOYSA-N 0.000 description 5
- HXMZLDUBSSPQIB-UHFFFAOYSA-N 2-phenyl-1-benzofuran Chemical class O1C2=CC=CC=C2C=C1C1=CC=CC=C1 HXMZLDUBSSPQIB-UHFFFAOYSA-N 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical compound OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- -1 sterilant Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical compound C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000004081 narcotic agent Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of 2,6-diphenyl phenol. The preparation method is characterized in that 2,6-diphenyl phenol is prepared in a tubular fixed bed reactor aiming at overcoming the defects that operating conditions are difficult to control, continuity is poor, mechanical strength of a catalyst is low, the catalyst is easy to coke and products and the catalyst are difficult to separate in the prior art; the catalyst is loaded, temperature is controlled to be 250-300 DEG C, shielding gas is introduced to realize gas shielding, trimeric ketone obtained through cyclohexanone self-condensation reaction is added into the tubular fixed bed reactor, liquid hourly space velocity is 0.1-10/h, the trimeric ketone flows out from the tubular fixed bed reactor after reaction is carried out in the presence of the catalyst, reaction product flowed out is collected, the reaction product is recrystallized in solvent, and vacuum filtering and drying are carried out, thus 2,6-diphenyl phenol is obtained. The preparation method provided by the invention has the advantages that raw materials are economic, continuous operation can be realized, the preparation method is convenient to control, the mechanical strength of the catalyst is high, the catalyst is difficult to coke and can be completely separated from the product, per-pass conversion of the trimeric ketone is high, and yield of the target product is high.
Description
Technical field
The present invention relates to a kind of preparation method of 2,6-diphenylphenol, specifically, relate to a kind of preparation method of take the 2,6-diphenylphenol that three polyketone that pimelinketone makes from condensation are raw material.
Background technology
2,6-phenylbenzene phenol (2,6-diphenylphenol, be called for short DPP) be a kind of important industrial chemicals, outward appearance is white crystalline powder, fusing point is 101 ℃～103 ℃, is slightly soluble in water, is soluble in organic solvent and the alkaline solutions such as methyl alcohol, ethanol, acetone, benzene, dichlorobenzene and trieline.It is widely used in the fields such as dyestuff, sterilant, narcotics, sorbing material, special engineering plastics, insulating material and antioxidant.Along with the continuous expansion of 2,6-diphenylphenol purposes in recent years, demand increases sharply, and development prospect is very wide.
In recent decades, people are research 2 constantly, Friedel-Crafts reaction, sodium phenide generation substitution reaction, can occur by aromatic series halides and phenol in the synthetic method of 6-phenylbenzene phenol at present, 2,6-bicyclohexane base phenol, 2,6-phenylbenzene cyclonene generation dehydrogenation reaction, dehydrogenation after green reagent generation substitution reaction, after pimelinketone generation self-condensation reaction, the multiple synthesis technique such as dehydrogenation makes 2,6-diphenylphenol.But, because the phenyl volume is larger, the steric hindrance of carrying out substitution reaction on phenyl ring is larger, cause substitution reaction condition harshness, it is not very high carrying out 2,6 replacement selectivity simultaneously, causes substitution product numerous.Therefore the common feature of these techniques is severe reaction conditions, need under the condition of high temperature or catalyzer existence, could react, and by product separation of a great variety and difficult, the principal product productive rate is lower.
Wherein, after existing pimelinketone generation self-condensation reaction in dehydrogenating technology, Plesek J be take pimelinketone as raw material, through from condensation, dehydrogenation two-step reaction, making 2,6-phenylbenzene phenol (Plesek J.Selfcondensation ofcyclopentane[J] .Chem Listy.1956, Vol 50:246-251.); Kapner R S of GE etc. has carried out method improvement (Kapner R S to it afterwards, Kippax D L, Murphy K E, et al.Process for the formation of 2,6-diphenylphenol[P] .US:3972951,1976-8-3.).The advantage of this technique is raw material pimelinketone economy, and low in the pollution of the environment, processing step is few, the suitable large-scale commercial production of carrying out; Weak point be the first step pimelinketone under catalyst action after condensation obtains three polyketone, second step adds the Pd/C catalyzer in three polyketone containers, carry out dehydrogenation reaction under 260～290 ℃ and prepare 2, the operational condition of 6-phenylbenzene phenol is wayward, poor continuity, the physical strength of catalyzer is low, easily coking, and product is difficult to separate with catalyzer.
Summary of the invention
For Oxidative Dehydrogenation after existing pimelinketone generation self-condensation reaction standby 2, the defect that in the technique of 6-phenylbenzene phenol, the second step method exists, the object of the present invention is to provide a kind of 2, the preparation method of 6-phenylbenzene phenol, specifically, relate to and a kind ofly take pimelinketone and prepare the method for 2,6-diphenylphenol from condensation product three polyketone as raw material through dehydrogenation reaction.Described method raw material economics, but operate continuously, be convenient to control, and the catalyzer physical strength is high, is difficult for coking, can be complete with product separation, and three polyketone per pass conversion are high, and target product yield is high.
The objective of the invention is to be achieved through the following technical solutions.
A kind of preparation method of 2,6-diphenylphenol, step is as follows:
The described reaction for preparing 2,6-diphenylphenol is carried out in tubular fixed-bed reactor; The catalyzer of packing in described tubular fixed-bed reactor, temperature is controlled at 250～300 ℃, the protection of logical protection gas, three polyketone that will obtain through cyclohexanone self-condensation reaction add in tubular fixed-bed reactor, and liquid hourly space velocity is 0.1～10h
-1, three polyketone flow out from tubular fixed-bed reactor after catalyst reaction, collect the reactant flowed out, and by reactant recrystallization in solvent, after vacuum filtration, drying, obtain 2,6-diphenylphenol of the present invention.
Wherein, the length-to-diameter ratio of described tubular fixed-bed reactor is 5: 1～20: 1, and preferably the length-to-diameter ratio of tubular fixed-bed reactor is 10: 1.
Described protection gas is wherein one or more mixed gas of nitrogen, hydrogen or argon gas, and preferably protecting gas is nitrogen; Described shielding gas act as dehydrogenation reaction the time oxidized for preventing catalyzer.
Described catalyzer is the palladium (Pd) loaded on aluminum oxide, gac or HZSM-5 molecular sieve carrier, and the oeverall quality of described catalyzer of wherein take is 100%, and the mass content of palladium is 1～10%.
Described recrystallization solvent be ethanol, normal hexane or octane-iso one of them, preferably recrystallization solvent is ethanol or normal hexane.
Described three polyketone are the mixture that 2,6-bis-(1-cyclohexenyl) pimelinketone, 2-hexamethylene alkylidene group-6-(1-cyclohexenyl) pimelinketone and 2,6-, bis-hexamethylene alkylidene group pimelinketone form, and main component is 2,6-bis-(1-cyclohexenyl) pimelinketone.
Beneficial effect
1. raw material pimelinketone economy, low in the pollution of the environment;
2., but the tubular fixed-bed reactor operate continuously is reacted, be convenient to control;
3. catalyzer is efficient, and the catalytic dehydrogenation productive rate reaches as high as 65.37%, and physical strength is high, is difficult for coking, can with reaction product, separate fully;
4. three polyketone per pass conversion are high, are up to 93.63%;
5. reaction product 2,6-diphenylphenol yield is high, and selectivity reaches as high as 70.63%, and reaction product is separated automatically with catalyzer, and after recrystallization, purity surpasses 98%.
Embodiment
In order to absolutely prove characteristic of the present invention and to implement mode of the present invention, below provide embodiment.
Embodiment 1
With reference to being permitted East Sea Deng<< naval vessel chemical defence " method described in the article " 2,6-diphenylphenol intermediate study on the synthesis " delivered on 30th～34 pages of the 1st phases in 2009, take pimelinketone as synthetic three polyketone of raw material.Connect prolong on the 250mL there-necked flask, add the 98.2g pimelinketone, 40mL toluene, be heated to 150 ℃, add 0.28g potassium hydroxide as catalyzer, 150 ℃ of lower back flow reaction 2.5 hours, after reaction stops, reaction product is neutralized with 10% hydrochloric acid soln, separate water layer, drying, vacuum distilling, collect cut under differing temps, the pimelinketone that the massfraction that obtains product is 12.6%, 35.6% two polyketone, 50.6% three polyketone, 1.2% high boiling product.
Embodiment 2
The tubular fixed-bed reactor that is 10: 1 by length-to-diameter ratio is placed in process furnace, the Pd/Al of the content 5% of packing in tubular fixed-bed reactor
2o
3catalyzer, temperature of reaction is controlled at 290 ℃, and logical nitrogen protection, after temperature-stable, is inputted three polyketone that prepare in embodiment 1 with pump from the tubular fixed-bed reactor end opening, and liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, analytical results is as follows: the quality of described reactant of take is 100%, wherein three polyketone are that 6.9%, 2-cyclohexyl-6-phenylphenol is 20.4%, 2,6-dicyclohexyl phenol is 6.9%, 2,6-diphenylphenol is 64.3%, and phenyl benzofurans is 0.4%, meta-terphenyl is 0.6%, and other products are 0.5%; Three polyketone per pass conversion reach 93.1%, and the selectivity of 2,6-diphenylphenol reaches 70%, and the catalytic dehydrogenation productive rate reaches 65.2%.
Embodiment 3
The tubular fixed-bed reactor that is 5: 1 by length-to-diameter ratio is placed in process furnace; the aluminum oxide of packing in tubular fixed-bed reactor is the catalyzer that carrier palladium content is 5%; temperature of reaction is controlled at 290 ℃; logical nitrogen protection; after temperature-stable; with pump, three polyketone that prepare in embodiment 1 are inputted from the tubular fixed-bed reactor end opening, liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, analytical results is as follows: the quality of described reactant of take is 100%, wherein, three polyketone are that 7.4%, 2-cyclohexyl-6-phenylphenol is 29.4%, 2,6-dicyclohexyl phenol is 11.1%, 2,6-phenylbenzene phenol is 42.5%, phenyl benzofurans is 3.3%, and meta-terphenyl is 2.7%, and other products are 3.6%; Three polyketone per pass conversion reach 92.4%, and the selectivity of 2,6-diphenylphenol reaches 47%, and the catalytic dehydrogenation productive rate reaches 43.4%.
Embodiment 4
The tubular fixed-bed reactor that will be 20: 1 by length-to-diameter ratio is placed in process furnace; the aluminum oxide of packing in tubular fixed-bed reactor is the catalyzer that carrier palladium content is 5%; temperature of reaction is controlled at 290 ℃; logical nitrogen protection; after temperature-stable; with pump, three polyketone that prepare in embodiment 1 are inputted from the tubular fixed-bed reactor end opening, liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, analytical results is as follows: the quality of described reactant of take is 100%, wherein, three polyketone are that 7.3%, 2-cyclohexyl-6-phenylphenol is 23.2%, 2,6-dicyclohexyl phenol is 9.7%, 2,6-phenylbenzene phenol is 40.5%, phenyl benzofurans is 9.7%, and meta-terphenyl is 6.5%, and other products are 3.1%; Three polyketone per pass conversion reach 92.7%, and the selectivity of 2,6-diphenylphenol reaches 44%, and the catalytic dehydrogenation productive rate reaches 40.8%.
Embodiment 5
The tubular fixed-bed reactor that is 10: 1 by length-to-diameter ratio is placed in process furnace; the aluminum oxide of packing in tubular fixed-bed reactor is the catalyzer that carrier palladium content is 5%; temperature of reaction is controlled at 290 ℃; logical hydrogen shield; after temperature-stable; with pump, three polyketone that prepare in embodiment 1 are inputted from the tubular fixed-bed reactor end opening, liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, analytical results is as follows: the quality of described reactant of take is 100%, wherein three polyketone are that 11.6%, 2-cyclohexyl-6-phenylphenol is 28.1%, 2,6-dicyclohexyl phenol is 9.5%, 2,6-diphenylphenol is 46.3%, and phenyl benzofurans is 1.4%, meta-terphenyl is 0.9%, and other products are 2.2%; Three polyketone per pass conversion reach 88.4%, and the selectivity of 2,6-diphenylphenol reaches 52%, and the catalytic dehydrogenation productive rate reaches 45.9%.
Embodiment 6
The tubular fixed-bed reactor that is 10: 1 by length-to-diameter ratio is placed in process furnace; be respectively charged in tubular fixed-bed reactor and take the catalyzer of gac as the different palladium content of carrier; temperature of reaction is controlled at 290 ℃; logical nitrogen protection; after temperature-stable; with pump, three polyketone that prepare in embodiment 1 are inputted from the tubular fixed-bed reactor end opening, liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, and the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, result is as shown in table 1:
Table 1
Embodiment 7
The tubular fixed-bed reactor that is 10: 1 by length-to-diameter ratio is placed in process furnace, the aluminum oxide of packing in tubular fixed-bed reactor is the catalyzer that carrier palladium content is 5%, temperature is controlled at 290 ℃, logical hydrogen shield, after temperature-stable, input three polyketone that prepare in embodiment 1 with pump from the tubular fixed-bed reactor end opening, the flow velocity of regulating pump changes liquid hourly space velocity, rely on the pressure of pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, and the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, result is as shown in table 2:
Table 2
Embodiment 8
The tubular fixed-bed reactor that is 10: 1 by length-to-diameter ratio is placed in process furnace; the aluminum oxide of packing in tubular fixed-bed reactor is the catalyzer that carrier palladium content is 5%; logical nitrogen protection; after temperature of reaction is stable; with pump, three polyketone that prepare in embodiment 1 are inputted from the tubular fixed-bed reactor end opening, liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, and the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, when temperature of reaction is respectively 250 ℃, 270 ℃ or 300 ℃, result is as shown in table 3:
Table 3
Embodiment 9
The tubular fixed-bed reactor that is 5: 1 by length-to-diameter ratio is placed in process furnace; the HZSM-5 molecular sieve of packing in tubular fixed-bed reactor is the catalyzer that carrier palladium content is 5%; temperature of reaction is controlled at 290 ℃; logical nitrogen protection; after temperature-stable; with pump, three polyketone that prepare in embodiment 1 are inputted from the tubular fixed-bed reactor end opening, liquid hourly space velocity is 2.9h
-1, the pressure of dependence pump, three polyketone from tubular fixed-bed reactor outflow suitable for reading, are collected the reactant flowed out after catalyst reaction; Adopt external standard method, with HPLC, described reactant is analyzed, analysis condition is: 30 ℃ of column temperatures, the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, analytical results is as follows: the quality of described reactant of take is 100%, wherein, three polyketone are that 7.7%, 2-cyclohexyl-6-phenylphenol is 29.1%, 2,6-dicyclohexyl phenol is 7.5%, 2,6-phenylbenzene phenol is 50.3%, phenyl benzofurans is 2.4%, and meta-terphenyl is 1.2%, and other products are 1.8%; Three polyketone per pass conversion reach 93.1%, and the selectivity of 2,6-diphenylphenol reaches 55%, and the catalytic dehydrogenation productive rate reaches 51.2%.
Embodiment 10
By the reactants dissolved that obtains in embodiment 2 in alcohol solvent, reactant: the mass ratio of alcohol solvent 2: 1, being heated to 70 ℃ dissolves fully, be placed in recrystallization under room temperature, after filtration, after vacuum-drying, obtain white needle-like crystals, fusing point is 101～102 ℃, is 2,6-diphenylphenol of the present invention; Adopt external standard method, with HPLC, described white needle-like crystals is detected, analysis condition is: 30 ℃ of column temperatures, and the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, the purity that records the 2,6-diphenylphenol crystal is 99%,
Embodiment 11
By the reactants dissolved that obtains in embodiment 2 in the normal hexane solvent, reactant: the mass ratio of normal hexane solvent 1.5: 1, being heated to 60 ℃ dissolves fully, be placed in recrystallization under room temperature, after filtration, after vacuum-drying, obtain white needle-like crystals, fusing point is 101～102 ℃, is 2,6-diphenylphenol of the present invention; Adopt external standard method, with HPLC, described white needle-like crystals is detected, analysis condition is: 30 ℃ of column temperatures, and the methanol aqueous solution that moving phase is 80%, flow rate of mobile phase is 0.5ml/min, the purity that records the 2,6-diphenylphenol crystal is 98%.
Embodiment 12
The reactant obtained in embodiment 3,4,5 and 9 is analyzed by the recrystallization condition in embodiment 10 and HPLC analysis condition respectively, and the 2,6-diphenylphenol crystal obtained is all white needle-like crystals, and fusing point is all between 101～102 ℃; Wherein, the 2,6-diphenylphenol crystal purity that the reactant that embodiment 3 obtains obtains after recrystallization, filtration, vacuum-drying is: 97%; The 2,6-diphenylphenol crystal purity that the reactant that embodiment 4 obtains obtains after recrystallization, filtration, vacuum-drying is: 97%; The 2,6-diphenylphenol crystal purity that the reactant that embodiment 5 obtains obtains after recrystallization, filtration, vacuum-drying is: 97%; The 2,6-diphenylphenol crystal purity that the reactant that embodiment 9 obtains obtains after recrystallization, filtration, vacuum-drying is: 98%.
Claims (3)
1. the preparation method of a 2,6-diphenylphenol, it is characterized in that: described method is carried out in tubular fixed-bed reactor; The catalyzer of packing in tubular fixed-bed reactor, temperature is controlled at 250～300 ℃, the protection of logical protection gas, three polyketone that will obtain through cyclohexanone self-condensation reaction add in tubular fixed-bed reactor, and liquid hourly space velocity is 0.1～10h-1, three polyketone flow out from tubular fixed-bed reactor after catalyst reaction, collect the reactant flowed out, by reactant recrystallization in solvent, after vacuum filtration, drying, obtain 2,6-diphenylphenol of the present invention;
Wherein, the length-to-diameter ratio of described tubular fixed-bed reactor is 5:1～20:1;
Described protection gas is nitrogen;
Described catalyzer is the palladium loaded on aluminum oxide, gac or HZSM-5 molecular sieve carrier, and the oeverall quality of described catalyzer of wherein take is 100%, and the mass content of palladium is 1～10%;
Described recrystallization solvent be ethanol, normal hexane or octane-iso one of them.
2. the preparation method of a kind of 2,6-diphenylphenol according to claim 1, it is characterized in that: the length-to-diameter ratio of described tubular fixed-bed reactor is 10:1.
3. the preparation method of a kind of 2,6-diphenylphenol according to claim 1, it is characterized in that: described recrystallization solvent is ethanol or normal hexane.
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| US3972951A (en) * | 1966-12-14 | 1976-08-03 | General Electric Company | Process for the formation of 2,6-diphenyl-phenol |
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| US3972951A (en) * | 1966-12-14 | 1976-08-03 | General Electric Company | Process for the formation of 2,6-diphenyl-phenol |
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