CN106495991A - A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol - Google Patents

A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol Download PDF

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CN106495991A
CN106495991A CN201610783626.3A CN201610783626A CN106495991A CN 106495991 A CN106495991 A CN 106495991A CN 201610783626 A CN201610783626 A CN 201610783626A CN 106495991 A CN106495991 A CN 106495991A
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dibenzofuran
phenyl phenol
industrial
biphenyl
catalyst
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CN106495991B (en
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梁长海
李闯
齐骥
张洁
邸鑫
殷东东
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Dalian University of Technology
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Dalian University of Technology
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    • 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
    • C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
    • C07C37/055—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis the substituted group being bound to oxygen, e.g. ether group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a kind of method of industrial dibenzofuran hydrofinishing biphenyl and o-phenyl phenol, belongs to catalyst preparation field.Industrial dibenzofuran is dissolved in dissolution kettle with solvent, solution temperature is 80～100 DEG C, industrial dibenzofuran organic solution injection after dissolving carries out hydrofining reaction in the fixed bed reactors equipped with selection Hydrobon catalyst, after hydrofining reaction, product directly enters rectifying column rectifying, tower top goes out hexamethylene and benzene, will produce solvent according to boiling point and beat the circulation industrial dibenzofuran of dissolving again, and extraction biphenyl is directly granulated as product, extraction o-phenyl phenol is directly granulated as product, the refined dibenzofuran of bottom of towe extraction；Refined dibenzofuran is used for producing o-phenyl phenol as raw material.The present invention produces the high biphenyl of added value and o-phenyl phenol with industrial dibenzofuran；The catalyst for being used has very high selectivity and higher hydrogenation activity.The method has good economic benefit and prospects for commercial application.

Description

A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol
Technical field
The invention belongs to catalyst preparation field, is related to a kind of industrial dibenzofuran hydrofinishing and prepares biphenyl and adjacent benzene The method of base phenol.
Background technology
Biphenyl (BP) is important Organic Ingredients, is widely used in the fields such as medicine, agricultural chemicals, dyestuff, liquid crystal material.Can use To synthesize plasticizer, preservative, can be also used for manufacturing fuel, engineering plastics and high-energy fuel etc..Biphenyl be present in coal tar, In former oil and gas.The preparation method of biphenyl to be had be pyrolyzed the chemical synthesis of biphenyl processed etc. by benzene and pass through various coal tar The separation and Extraction method of cut biphenyl.Mass fraction of the biphenyl in coal tar be 0.20%-0.40%, current coal tar oil extract Method and chemical synthesis are simultaneously deposited.O-phenyl phenol (OPP) is used as a kind of important new fine chemical product and organic synthesis Intermediate, is widely used in sterilization and anticorrosion, printing and dyeing assistant and surfactant, synthesizing new plastics, resin and macromolecule material The aspects such as the stabilizer and fire retardant of material, and have extremely vast potential for future development.With o-phenyl phenol synthesis technique continuous To cleaning, low cost, in high yield direction develop, demand cumulative year after year of the domestic and international market to o-phenyl phenol, sale Market is had an optimistic view of, and is that the development of OPP industries brings opportunity.Dibenzofuran main source is by the washing oil produced during coal tar distillation Isolated.Mass fraction of the dibenzofuran in washing oil is about 10%, mass fraction up to more than 30% in heavy wash oil.Closely several Year, for the concern that dibenzofuran has also obtained people for the method that raw material prepares o-phenyl phenol, this route is by dibenzofuran and gold Category sodium reaction, then with acid acidifying product, obtains o-phenyl phenol.But as technology is not yet ripe, this process route is not yet Realize industrialization.At present, as global consumption demand amount increases year by year, OPP prices are also further improved.Washing using low value Oil extract composition-dibenzofuran processing OPP has fabulous economic benefit.Can utilize industrial dibenzofuran hydrofinishing biphenyl with O-phenyl phenol.But industrial dibenzofuran is because containing the impurity such as dibenzothiophenes, carbazole, fluorenes, acenaphthene, its dibenzofuran content 95% or so, oxygen Fluorenes can direct hydrogenation deoxidation biphenyl, it is also possible to which catalytic hydrogenation open loop prepares o-phenyl phenol, but dibenzofuran catalytic hydrogenation open loop system O-phenyl phenol needs to use noble metal catalyst.Noble metal catalyst use condition is harsh, and sulphur and nitrogen content need to be down to several Individual ppm level.Therefore OPP directly catalytic hydrogenation open loop can not be produced as raw material with industrial dibenzofuran, raw material must be refined.Pin To industrial dibenzofuran property, Hydrobon catalyst, the industrial dibenzofuran hydrofinishing biphenyl of exploitation and o-phenyl phenol technique is developed Technology.With being continuously increased for biphenyl and o-phenyl phenol consumption, develop with dibenzofuran as raw material hydrogenation deoxidation prepare biphenyl or plus Hydrogen open loop is directly prepared in OPP reactions, and the hydrogenation open loop of catalyst is active, selective most important.Adjacent as raw material system with dibenzofuran Phenylphenol is it has been reported that but be really rarely reported with dibenzofuran as the direct deoxidation biphenyl of raw material.Following known technologies, is all present Some shortcomings：
Chinese patent, publication number：CN 103319313A, introduce a kind of method that dibenzofuran open loop prepares o-phenyl phenol, with Dibenzofuran is raw material, uses glycol dimethyl ether or diethylene glycol dimethyl ether as solvent, adds metallic sodium, under nitrogen protection Reacted, reactant mixture is cooled down, added ethanol stirring, then distillating recovering solvent is added water in residue, cold But to room temperature, unreacting material is recovered by filtration, adds water concentrated hydrochloric acid to adjust pH less than 3, separate out brown oil, use acetic acid second Ester is extracted, anhydrous sodium sulfate drying, and solvent is sloughed in decompression, recrystallizes to obtain o-phenyl phenol with petroleum ether.Active metal sodium makes With technique process is more, comparatively laborious, there is certain risk.
Content of the invention
The invention provides a kind of method of industrial dibenzofuran hydrofinishing biphenyl and o-phenyl phenol.Rationally sharp with resource For the purpose of with dibenzofuran, for dibenzofuran hydroconverted products many drawbacks of, develop dibenzofuran hydrofinishing special-purpose catalyst, converted Biphenyl and o-phenyl phenol for high added value.
Technical scheme：
A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol, step are as follows：
Industrial dibenzofuran is dissolved in dissolution of raw material kettle with organic solvent, solution temperature is 80～100 DEG C, and obtaining concentration is The organic solution of 5～20% industrial dibenzofuran；By the organic solution injection of industrial dibenzofuran equipped with selection Hydrobon catalyst Carry out hydrofining reaction in hydrofining reaction tower, 300～380 DEG C of hydrofining reaction temperature, 1～4MPa of Hydrogen Vapor Pressure, 0.2～1.5h of reaction velocity-1；Product after hydrofining reaction directly enters rectifying column rectifying, and rectifying column is packed tower, and tower pressure is 5-40kPa, bottom temperature are 280 DEG C, and reflux ratio is more than 0.8, and tower top goes out hexamethylene and benzene, organic molten by produced according to boiling point Agent is circulated for dissolving industrial dibenzofuran, and the biphenyl of extraction is directly granulated as product, and the o-phenyl phenol of extraction directly granulates work For product, the refined dibenzofuran of bottom of towe extraction；Refined dibenzofuran is used for producing o-phenyl phenol as raw material.
Described selection Hydrobon catalyst is supported CoMo catalyst, consisting of：Co contents are 3～10%, Mo contents are 10～25%；Described supported CoMo catalyst is prepared using coprecipitation, and its carrier is SiO2、Al2O3、 TiO2、SiO2-Al2O3Or Al2O3-TiO2.
One or two or more kinds mixing of described organic solvent for decane, decahydronaphthalene, D40, D60.
Beneficial effects of the present invention：The present invention produces the high biphenyl of high added value, adjacent phenyl with industrial dibenzofuran as raw material Phenol and cyclohexylbenzene；By the method for the present invention production obtain biphenyl selectivity more than 60%, o-phenyl phenol 10% or so, below 10%, other are cyclohexylbenzene to benzene+hexamethylene yield to yield.The catalyst for being used has superelevation Selective.The method not only have simple to operate, and with good economic benefit and prospects for commercial application.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
In figure：1 dissolution of raw material kettle；2 hydrofining reaction towers；3 rectifying columns.
Specific embodiment
Below in conjunction with the specific embodiment that technical scheme and accompanying drawing describe the present invention in detail.
Embodiment 1：Supported CoMo catalyst is prepared using coprecipitation, and its carrier is SiO2、Al2O3、TiO2、SiO2- Al2O3Or Al2O3-TiO2, concrete preparation process is：Cobalt nitrate and ammonium molybdate are dissolved respectively, then is added in cobalt nitrate solvent Complexing agent, is being slowly added to ammonium molybdate, is making Co and Mo form complex compound, carrier is added in metal complex liquid, and it is heavy to add Shallow lake agent, is settled out solid in 180 DEG C of dryings, dries aftershaping calcining, and Hydrobon catalyst, reducing program are prepared in reduction For：Reduction 50ml catalyst, density of hydrogen is 85%, hydrogen flowing quantity 2000ml/min, and heating rate is 2 DEG C/min, at 420 DEG C Constant temperature 8h, Temperature fall are passivated standby.The catalyst that different loadings can be prepared by the amount for changing carrier and carrier, changes The ratio for becoming metal Co and Mo can prepare the catalyst of different metal ratio.
Embodiment 2：On the basis of embodiment 1,6Co16Mo/SiO is prepared2、6Co16Mo/Al2O3、6Co16Mo/ TiO2、6Co16Mo/SiO2-Al2O3And 6Co16Mo/Al2O3-TiO2Catalyst.
Embodiment 3：On the basis of embodiment 1,6Co16Mo/SiO is prepared2, the loading of metal Co is 6%, metal The loading of Mo is 16%.
Embodiment 4：With the 6Co16Mo/SiO that embodiment 3 is prepared2For fixed bed hydrogenation catalyst for refining.Investigate reaction Impact of the condition to reaction result.Table 1 below is shown in reaction result.
As shown in Table 1 with 6Co16Mo/SiO2For Hydrobon catalyst, when temperature is more than 360 DEG C, product S and N content 5ppm below is reduced to.Biphenyl (BP), o-phenyl phenol (OPP), cyclohexylbenzene (CHB), benzene (B) and hexamethylene (CH). Increase the generation that temperature and air speed are all conducive to biphenyl, increase the generation that pressure is conducive to cyclohexylbenzene, increase light oil to producing Thing selectively affects less.In reaction condition it is：Pressure 1MPa, 380 DEG C of temperature, air speed 1h-1, must join under the conditions of hydrogen-oil ratio 200 Benzene+o-phenyl phenol+cyclohexylbenzene is selectively more than 90%.
Embodiment 5：The catalyst of the different carriers that is prepared with embodiment 2 is as Hydrobon catalyst.Investigate carrier pair The impact of reaction.Table 2 below is shown in reaction result.
As shown in Table 2, this five kinds of carriers remove can S the and N hydrofinishings in dibenzofuran, when support acidity strengthens, The selectivity of CHB+B+CH is substantially increased, and acid increase is conducive to C-O and C-C key scission of links to be thus advantageous to cyclohexylbenzene and benzene Generation with hexamethylene.With dibenzofuran Hydrogenation biphenyl and o-phenyl phenol, preferably with neutral carrier as catalyst carrier.
Embodiment 6：Stability experiment is carried out on the basis of embodiment 4, with 6Co16Mo/SiO2It is catalyzed for hydrofinishing Agent, in reaction condition be：Pressure 1MPa, 380 DEG C of temperature, air speed 1h-1, under the conditions of hydrogen-oil ratio 200, table 3 below is shown in that 500h catalyst is steady Qualitative experiment reaction result.
500h catalyst stabilities experimental result as shown in Table 3, catalyst hydrogenation activity are basically unchanged, but hydrodesulfurization and Denitrification effect is deteriorated, and the catalyst for being primarily due to our metallic state may cure, and the sulfide of generation has acidity, makes The selectivity of benzene and hexamethylene in product increases.
Embodiment 7：Product separating experiment is carried out on the basis of embodiment 6, and rectifying column is packed tower, and tower pressure is 20kPa, Bottom temperature is 280 DEG C, and reflux ratio is 1, and theoretical cam curve is 400, feeds in tower, and feeding temperature is 240 DEG C.The connection that produces The purity of benzene>98.5%, the purity of o-phenyl phenol>99.1%, the purity of bottom of towe dibenzofuran>98%, wherein in dibenzofuran, S and N contain Amount can be sold as smart dibenzofuran all in below 5ppm, after prepare o-phenyl phenol as raw material for being hydrogenated with open loop.

Claims (4)

1. a kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol, it is characterised in that step is as follows：
Industrial dibenzofuran is dissolved in the dissolution of raw material kettle with organic solvent, solution temperature is 80～100 DEG C, obtain concentration for 5～ The organic solution of 20% industrial dibenzofuran；By the organic solution injection of industrial dibenzofuran equipped with the hydrogenation for selecting Hydrobon catalyst Hydrofining reaction, 300～380 DEG C of hydrofining reaction temperature, 1～4MPa of Hydrogen Vapor Pressure, reaction is carried out in refining reaction tower 0.2～1.5h of air speed-1；Product after hydrofining reaction directly enters rectifying column rectifying, and rectifying column is packed tower, and tower pressure is 5- 40kPa, bottom temperature are 280 DEG C, and reflux ratio is more than 0.8, and tower top goes out hexamethylene and benzene, according to the organic solvent that boiling point will be produced Circulate for dissolving industrial dibenzofuran, the biphenyl of extraction is directly granulated as product, and the o-phenyl phenol of extraction directly granulates conduct Product, the refined dibenzofuran of bottom of towe extraction；Refined dibenzofuran is used for producing o-phenyl phenol as raw material.
2. method according to claim 1, it is characterised in that described selection Hydrobon catalyst is load type Co Mo Catalyst, consisting of：It is 10～25% that Co contents are 3～10%, Mo contents.
3. method according to claim 2, it is characterised in that described supported CoMo catalyst is using co-precipitation legal system Standby, its carrier is SiO2、Al2O3、TiO2、SiO2-Al2O3Or Al2O3-TiO2.
4. according to the arbitrary described method of claim 1-3, it is characterised in that described organic solvent be decane, decahydronaphthalene, One or two or more kinds mixing of D40, D60.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445786A (en) * 2017-09-11 2017-12-08 大连理工大学 A kind of method of dibenzofuran Hydrogenation biphenyl
CN108947775A (en) * 2018-08-07 2018-12-07 斯爱玲 A method of catalysis dibenzofuran open loop prepares o-phenyl phenol
CN108947758A (en) * 2018-08-07 2018-12-07 斯爱玲 A method of catalysis dibenzofurans open loop prepares biphenyl
CN109438154A (en) * 2018-11-05 2019-03-08 大连理工大学 A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989761A (en) * 1975-08-08 1976-11-02 Monsanto Company Production of orthophenylphenols
US4000203A (en) * 1975-08-08 1976-12-28 Monsanto Company Production of orthophenylphenols
US4035428A (en) * 1975-08-08 1977-07-12 Monsanto Company Process for production of orthophenylphenol
CN103319313A (en) * 2013-07-18 2013-09-25 辽宁石化职业技术学院 Method for preparing o-phenyl phenol by ring opening of dibenzofuran

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3989761A (en) * 1975-08-08 1976-11-02 Monsanto Company Production of orthophenylphenols
US4000203A (en) * 1975-08-08 1976-12-28 Monsanto Company Production of orthophenylphenols
US4035428A (en) * 1975-08-08 1977-07-12 Monsanto Company Process for production of orthophenylphenol
CN103319313A (en) * 2013-07-18 2013-09-25 辽宁石化职业技术学院 Method for preparing o-phenyl phenol by ring opening of dibenzofuran

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107445786A (en) * 2017-09-11 2017-12-08 大连理工大学 A kind of method of dibenzofuran Hydrogenation biphenyl
CN107445786B (en) * 2017-09-11 2021-01-19 大连理工大学 Method for preparing biphenyl by hydrogenation of dibenzofuran
CN108947775A (en) * 2018-08-07 2018-12-07 斯爱玲 A method of catalysis dibenzofuran open loop prepares o-phenyl phenol
CN108947758A (en) * 2018-08-07 2018-12-07 斯爱玲 A method of catalysis dibenzofurans open loop prepares biphenyl
CN109438154A (en) * 2018-11-05 2019-03-08 大连理工大学 A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen

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