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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- biphenyl
- hydrogen
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- dibenzofuran
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- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 47
- 239000004305 biphenyl Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000001257 hydrogen Substances 0.000 title claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 title claims description 53
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 9
- 238000011069 regeneration method Methods 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 230000005484 gravity Effects 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims abstract description 3
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 229910015421 Mo2N Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000010926 purge Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000006227 byproduct Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 4
- 239000000203 mixture Substances 0.000 claims 2
- 238000005243 fluidization Methods 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 2
- 239000012847 fine chemical Substances 0.000 abstract 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000011280 coal tar Substances 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910003178 Mo2C Inorganic materials 0.000 description 1
- 229910015723 MoP Inorganic materials 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004826 dibenzofurans Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000010292 orthophenyl phenol Nutrition 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
一种常压氢气下工业氧芴加氢精制联苯的方法，属于精细化学品合成技术领域。所用催化剂对氧芴加氢具有高活性和对联苯高选择性，氧芴转化率达100％，联苯选择性达100％，一步法得到纯联苯。加热的原料液在常压氢气带动下进入循环的催化剂床层。催化剂在预提升段和氢气充分混合，并部分还原。原料在提升管反应完成后，反应产物和溶剂进入蒸发器，分离出的溶剂继续循环，塔底得到联苯。催化剂在沉降器中在重力的作用下，进入再生器，通过空气或氨气将催化剂再生，再生后的催化剂进入反应装置，达到催化剂循环。本发明的催化剂对氧芴具有高活性、对联苯具有高选择性、易再生等特点，工艺简单，大大降低设备和操作成本，具有良好的工业应用前景。
The invention discloses a method for hydrogenating industrial oxyfluorene to refine biphenyl under normal pressure hydrogen, belonging to the technical field of fine chemical synthesis. The used catalyst has high activity for hydrogenation of oxyfluorene and high selectivity to biphenyl, the conversion rate of oxyfluorene reaches 100%, the selectivity of biphenyl reaches 100%, and pure biphenyl is obtained by one-step method. The heated feed liquid is driven by atmospheric hydrogen into the circulating catalyst bed. The catalyst is thoroughly mixed with hydrogen in the pre-lift section and partially reduced. After the raw materials are reacted in the riser, the reaction product and the solvent enter the evaporator, the separated solvent continues to circulate, and biphenyl is obtained at the bottom of the tower. Under the action of gravity in the settler, the catalyst enters the regenerator, and the catalyst is regenerated by air or ammonia gas, and the regenerated catalyst enters the reaction device to achieve the catalyst cycle. The catalyst of the invention has the characteristics of high activity to oxyfluorene, high selectivity to biphenyl, easy regeneration, etc., the process is simple, the equipment and operating costs are greatly reduced, and the catalyst has good industrial application prospects.
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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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811305302.4A CN109438154A (en) | 2018-11-05 | 2018-11-05 | A kind of method of industrial dibenzofuran hydrofinishing biphenyl under atmospheric hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797842A (en) * | 2021-01-27 | 2022-07-29 | 上海中化科技有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN115584283A (en) * | 2022-10-26 | 2023-01-10 | 大连理工大学 | A method for preparing adamantane-based high-density fuels from crude fluorene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114797842A (en) * | 2021-01-27 | 2022-07-29 | 上海中化科技有限公司 | Hydrogenation catalyst and preparation method thereof |
| CN115584283A (en) * | 2022-10-26 | 2023-01-10 | 大连理工大学 | A method for preparing adamantane-based high-density fuels from crude fluorene |
| CN115584283B (en) * | 2022-10-26 | 2024-01-30 | 大连理工大学 | A method for preparing adamantane-based high-density fuel from crude fluorene |
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Application publication date: 20190308 |