CN109438154A - A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen - Google Patents
A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen Download PDFInfo
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- CN109438154A CN109438154A CN201811305302.4A CN201811305302A CN109438154A CN 109438154 A CN109438154 A CN 109438154A CN 201811305302 A CN201811305302 A CN 201811305302A CN 109438154 A CN109438154 A CN 109438154A
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- 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
- C07C1/247—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by splitting of cyclic ethers
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/56—Platinum group metals
- C07C2523/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tatalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/652—Chromium, molybdenum or tungsten
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/882—Molybdenum and cobalt
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
- C07C2523/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- C07C2523/85—Chromium, molybdenum or tungsten
- C07C2523/88—Molybdenum
- C07C2523/883—Molybdenum and nickel
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/24—Nitrogen compounds
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- 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
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The method of industrial dibenzofuran hydrofinishing biphenyl, belongs to catalyst preparation technical field under a kind of atmospheric hydrogen.Used catalyst adds hydrogen highly selective with high activity and to biphenyl dibenzofuran, and dibenzofuran conversion ratio is up to 100%, and for biphenyl selectivity up to 100%, one-step method obtains pure biphenyl.The material liquid of heating enters the catalyst bed of circulation under atmospheric hydrogen drive.Catalyst is sufficiently mixed in pre lift zone and hydrogen, and partial reduction.Raw material riser after the reaction was completed, reaction product and solvent enter evaporator, and the solvent isolated continues cycling through, and tower bottom obtains biphenyl.In settler under gravity, into regenerator, by air or ammonia by catalyst regeneration, the catalyst after regeneration enters reaction unit to catalyst, reaches catalyst circulation.Catalyst of the invention has the characteristics that high activity to dibenzofuran, has highly selective, Yi Zaisheng to biphenyl, and simple process substantially reduces equipment and operating cost, has good prospects for commercial application.
Description
Technical field
The invention belongs to catalyst preparation technical fields, and in particular to industrial dibenzofuran adds hydrogen under to a kind of atmospheric hydrogen
The method for refining biphenyl.
Background technique
Biphenyl (BP) is a kind of very important compound, is widely used in medicine, pesticide, dyestuff, preservative.Plasticizer
In equal fields, there is extremely vast potential for future development.With biphenyl synthesis technology constantly to clean, inexpensive, high yield side
To development, domestic and international market is to the demand cumulative year after year of biphenyl, especially domestic biphenyl market even more much for not answering
It asks, most of biphenyl relies on import.Domestic market notch is larger, has good market prospects, and is the development band of biphenyl industry
Opportunity is carried out.Dibenzofuran, also known as dibenzofurans (DBF) are a kind of basic coal tar separation products, can be big from coal tar
Amount obtains.With the development of coal chemical industry, the source of coal tar is also more abundant, and the production scale of dibenzofuran is also increasing.It utilizes
The washing oil extract component of low value-dibenzofuran processing biphenyl has high economic benefit.The preparation method of biphenyl has before
The chemical synthesis of biphenyl processed etc. is pyrolyzed by benzene and passes through the separation and Extraction method of various coal tar fraction biphenyl.Utilize dibenzofuran
The synthesis report for carrying out biphenyl as raw material is less, mainly has following, but all comes with some shortcomings:
Chinese patent, publication number: referring in CN106495991A, adds hydrogen using supported CoMo catalyst catalysis dibenzofuran
The method of biphenyl and o-phenyl phenol processed.But the selectivity of biphenyl only has more than 60%, yield is only 30% or so.
Chinese patent, publication number: CN107445786A describes a kind of method that dibenzofuran adds hydrogen biphenyl, has selected body
The MoO of phase3,Mo2C,Mo2N and MoP is as catalyst, and for dibenzofuran conversion ratio up to 96%, biphenyl is selective up to 99.3%.Though to reach
Preferable reaction effect, but still have a small amount of by-product and unconverted dibenzofuran, this brings difficulty for the separation of product below, and increases
The cost of equipment is added.Moreover, required reaction pressure is higher than this patent, this also proposed certain requirement to equipment.
Summary of the invention
The object of the present invention is to provide a kind of method of dibenzofuran hydrofinishing biphenyl industrial under atmospheric hydrogen, this method as a means of
For the purpose of source rationally utilizes dibenzofuran, for the more problem of dibenzofuran hydrogenation products, develops with product specificity plus hydrogen and urge
Agent, the biphenyl of high added value is hydroconverted into using dibenzofuran, and selectivity and conversion ratio are all up to 100%.This method improves
The yield of biphenyl to 100%, reduce the separation costs of equipment, and catalyst is can be recycled.
Technical solution of the present invention:
A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen, steps are as follows:
With Pt/MoO3、Pt/Mo2N、Co/MoO3、Co/Mo2N、Ni/MoO3Or Ni/Mo2N is Hydrobon catalyst, is utilized
Fluidized bed is reacted；Industrial dibenzofuran is dissolved in heater using organic solvent, is driven through atmospheric hydrogen and enters circulation
Catalyst bed carries out hydrofining reaction；Reaction temperature is 340~380 DEG C；Catalyst is sufficiently mixed in pre lift zone and hydrogen
It closes, and partial reduction, also preheats hydrogen；The reaction riser after the reaction was completed, through whirlwind gas-liquid separator by product and
Catalyst separation；Reaction product and solvent enter evaporator to get pure biphenyl is arrived；Catalyst is in settler by the effect of gravity
Under, into separator, minimal amount of hydrogen is displaced with nitrogen purging；Last urges catalyst by air or ammonia realization
Agent regeneration, the catalyst after regeneration remove a small amount of oxygen or ammonia with nitrogen purging again；Subsequently into reaction unit, reaches and urge
The purpose of agent circulation；The condition of the catalyst regeneration are as follows: temperature is 400~600 DEG C, and pressure is normal pressure, gas flow
Not less than 2L h-1。
The Hydrobon catalyst is loaded catalyst, and wherein constituent content is based on mass fraction: Pt is 0.5~
2%, Co are that 1~10%, Ni is 1~10%.
The molar ratio of the hydrogen and industrial dibenzofuran is 10~200, the volume ratio of hydrogen and catalyst is 100~
1000。
The organic solvent is the mixing of one or both of hexamethylene, n-decane, decahydronaphthalene, dioxane, ethyl alcohol
Object；The molar ratio of organic solvent and industrial dibenzofuran is 20~60:1.
It is all connected with a gas-solid separator before and after dead catalyst enters regenerator, is also purged with nitrogen, by institute
It is clean with gas displacement.
The evaporator is calandria type evaporator, and temperature is 80~200 DEG C.
Compared with prior art, the present invention has the advantage that
(1) present invention synthesizes the biphenyl of high added value using cheap washing oil ingredient dibenzofuran catalytic hydrogenation.Conversion ratio and choosing
Selecting property is all up 100%, and yield is up to 100%.Therefore it in the last separation for not having to carry out product, is brought to reduce separation
Equipment cost and operating cost.
(2) one-step synthesis, simple process.
(3) catalyst used in the present invention can be reused by simple regeneration treatment.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Fig. 2 is the 3Co/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst, to reaction result when different empty
It influences.
Fig. 3 is the 3Ni/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst, to reaction result when different empty
It influences.
Specific embodiment
With reference to the accompanying drawing and technical solution, further description of the specific embodiments of the present invention.
Embodiment one: MoO3Synthetic method: a certain amount of ammonium molybdate aqueous solution is mixed with melamine aqueous solution, solution
It becomes cloudy, rear to filter, obtained filter cake is warming up to 500 DEG C, constant temperature 4h in air with 2 DEG C/min, and Temperature fall is spare.
Mo2N synthetic method: by a certain amount of MoO3In N2/H2It is nitrogenized under atmosphere, specific ammonifying process: with 1 DEG C/min from room temperature
It is raised to 800 DEG C, constant temperature 6h, Temperature fall to room temperature, Passivation Treatment.Pt/MoO3、Pt/Mo2N、Co/MoO3、Co/Mo2N、Ni/
MoO3And Ni/Mo2N process for synthetic catalyst: using common dipping method, obtained catalyst is dry, roasting, rear reduction
It is spare.
Embodiment two: the 3Co/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst.Temperature is investigated to reaction result
Influence.Biphenyl (BP), the following table 1 is shown in reaction result.
Known by table 1, the raising of temperature is conducive to DBF conversion, and the selectivity of BP is not affected by temperature and is always maintained at
100%.
Embodiment three: the 3Ni/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst.Temperature is investigated to reaction result
Influence.Biphenyl (BP), cyclohexyl benzene (CHB) the following table 2 are shown in reaction result.
Known by table 2, the raising of temperature is conducive to DBF conversion, and the selectivity of BP increases with temperature and increased.Therefore high temperature
Be conducive to improve BP yield.
Example IV: the 0.5Pt/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst.Temperature is investigated to tie reaction
The influence of fruit.Biphenyl (BP), the following table 3 is shown in reaction result.
Known by table 3, the raising of temperature is conducive to DBF conversion, and the selectivity of BP is not affected by temperature and is always maintained at
100%.
Embodiment five: the 3Co/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst.To reaction when investigating different skies
As a result influence.Fig. 2 is reaction result.
Embodiment six: the 3Ni/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst.To reaction when investigating different skies
As a result influence.Fig. 3 is reaction result.
Embodiment seven: the Pt/MoO prepared with embodiment 13、Pt/Mo2N、Co/MoO3、Co/Mo2N、Ni/MoO3And Ni/
Mo2N is fixed bed hydrogenation catalyst.Investigate influence of the different catalysts to reaction result.Biphenyl (BP), cyclohexyl benzene (CHB),
The following table 4 is shown in reaction result.
Embodiment eight: with the Co/MoO of different loadings prepared by embodiment 13For fixed bed hydrogenation catalyst.It investigates not
Influence with loading to reaction result.Biphenyl (BP), cyclohexyl benzene (CHB), the following table 5 is shown in reaction result.
Known by table 5, loading influences DBF conversion, the catalyst activity highest as 3wt.%.
Embodiment nine: the 3Co/MoO prepared with embodiment 13For fixed bed hydrogenation catalyst.Investigate catalyst inactivation with
Regeneration, can be by roasting activity recovery.
Claims (10)
1. a kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen, which is characterized in that steps are as follows:
With Pt/MoO3、Pt/Mo2N、Co/MoO3、Co/Mo2N、Ni/MoO3Or Ni/Mo2N is Hydrobon catalyst, utilizes fluidisation
Bed is reacted；Industrial dibenzofuran is dissolved in heater using organic solvent, the catalysis for entering circulation is driven through atmospheric hydrogen
Agent bed carries out hydrofining reaction；Reaction temperature is 340~380 DEG C；Catalyst is sufficiently mixed in pre lift zone and hydrogen, and
Partial reduction also preheats hydrogen；The reaction riser after the reaction was completed, through whirlwind gas-liquid separator by product and catalyst
Separation；Reaction product and solvent enter evaporator to get pure biphenyl is arrived；Catalyst in settler by gravity under the action of, into
Enter separator, displaces minimal amount of hydrogen with nitrogen purging；Last realizes catalyst by air or ammonia for catalyst
Regeneration, the catalyst after regeneration remove a small amount of oxygen or ammonia with nitrogen purging again；Subsequently into reaction unit, reach catalyst
The purpose of circulation；The condition of the catalyst regeneration are as follows: temperature is 400~600 DEG C, and pressure is normal pressure, and gas flow is not low
In 2L h-1。
2. the method according to claim 1, wherein the Hydrobon catalyst be loaded catalyst,
Wherein constituent content is based on mass fraction: it be 1~10%, Ni is 1~10% that Pt, which is 0.5~2%, Co,.
3. method according to claim 1 or 2, which is characterized in that the molar ratio of the hydrogen and industrial dibenzofuran is 10
~200, the volume ratio of hydrogen and catalyst is 100~1000.
4. method according to claim 1 or 2, which is characterized in that the organic solvent is hexamethylene, n-decane, ten
One or both of hydrogen naphthalene, dioxane, ethyl alcohol mixture；The molar ratio of organic solvent and industrial dibenzofuran is 20~60:1.
5. according to the method described in claim 3, it is characterized in that, the organic solvent is hexamethylene, n-decane, decahydro
One or both of naphthalene, dioxane, ethyl alcohol mixture；The molar ratio of organic solvent and industrial dibenzofuran is 20~60:1.
6. according to claim 1, method described in 2 or 5, which is characterized in that before and after dead catalyst enters regenerator
It is all connected with a gas-solid separator, is also purged with nitrogen, gases used displacement is clean.
7. according to the method described in claim 3, it is characterized in that, being all connected with before and after dead catalyst enters regenerator
One gas-solid separator, is also purged with nitrogen, and gases used displacement is clean.
8. according to the method described in claim 4, it is characterized in that, being all connected with before and after dead catalyst enters regenerator
One gas-solid separator, is also purged with nitrogen, and gases used displacement is clean.
9. according to claim 1, method described in 2,5,7 or 8, which is characterized in that the evaporator is central circulating tube steaming
Device is sent out, temperature is 80~200 DEG C.
10. according to the method described in claim 6, it is characterized in that, the evaporator is calandria type evaporator, temperature
It is 80~200 DEG C.
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| CN201811305302.4A CN109438154A (en) | 2018-11-05 | 2018-11-05 | A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen |
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| CN201811305302.4A CN109438154A (en) | 2018-11-05 | 2018-11-05 | A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115584283A (en) * | 2022-10-26 | 2023-01-10 | 大连理工大学 | Method for preparing adamantane high-density fuel from crude fluorene |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701897A (en) * | 2012-05-23 | 2012-10-03 | 河南宝舜化工科技有限公司 | Method for preparing cyclic hydrocarbon compounds by hydrogenation of wash oil fraction |
| CN106478378A (en) * | 2016-08-31 | 2017-03-08 | 大连理工大学 | A kind of low pressure hydrogen vaporizes the method that dibenzofuran is hydrogenated with open loop o-phenyl phenol |
| CN106495991A (en) * | 2016-08-31 | 2017-03-15 | 大连理工大学 | A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol |
| CN107445786A (en) * | 2017-09-11 | 2017-12-08 | 大连理工大学 | A kind of method of dibenzofuran Hydrogenation biphenyl |
-
2018
- 2018-11-05 CN CN201811305302.4A patent/CN109438154A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102701897A (en) * | 2012-05-23 | 2012-10-03 | 河南宝舜化工科技有限公司 | Method for preparing cyclic hydrocarbon compounds by hydrogenation of wash oil fraction |
| CN106478378A (en) * | 2016-08-31 | 2017-03-08 | 大连理工大学 | A kind of low pressure hydrogen vaporizes the method that dibenzofuran is hydrogenated with open loop o-phenyl phenol |
| CN106495991A (en) * | 2016-08-31 | 2017-03-15 | 大连理工大学 | A kind of method that industrial dibenzofuran hydrofinishing prepares biphenyl and o-phenyl phenol |
| CN107445786A (en) * | 2017-09-11 | 2017-12-08 | 大连理工大学 | A kind of method of dibenzofuran Hydrogenation biphenyl |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115584283A (en) * | 2022-10-26 | 2023-01-10 | 大连理工大学 | Method for preparing adamantane high-density fuel from crude fluorene |
| CN115584283B (en) * | 2022-10-26 | 2024-01-30 | 大连理工大学 | Method for preparing adamantane high-density fuel from crude fluorene |
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