CN106701158A - Desulfurization treatment method of phenol-containing oil and desulfurated phenolic-containing oil - Google Patents
Desulfurization treatment method of phenol-containing oil and desulfurated phenolic-containing oil Download PDFInfo
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- CN106701158A CN106701158A CN201510783159.XA CN201510783159A CN106701158A CN 106701158 A CN106701158 A CN 106701158A CN 201510783159 A CN201510783159 A CN 201510783159A CN 106701158 A CN106701158 A CN 106701158A
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- desulfurization
- dephenolize
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- catalyst
- carrier
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 159
- 230000023556 desulfurization Effects 0.000 title claims abstract description 147
- 238000000034 method Methods 0.000 title claims abstract description 59
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 93
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000011787 zinc oxide Substances 0.000 claims abstract description 30
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 22
- 239000011593 sulfur Substances 0.000 claims abstract description 22
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000005864 Sulphur Substances 0.000 claims description 15
- 239000012265 solid product Substances 0.000 claims description 14
- 238000003672 processing method Methods 0.000 claims description 11
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 74
- 150000002989 phenols Chemical class 0.000 abstract description 11
- 238000007670 refining Methods 0.000 abstract description 3
- 230000003009 desulfurizing effect Effects 0.000 abstract 4
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 229910052814 silicon oxide Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 25
- 150000001299 aldehydes Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 241000219782 Sesbania Species 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- 239000011280 coal tar Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000011269 tar Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910003294 NiMo Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 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
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000013455 disruptive technology Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to the field of oil refining, and discloses a desulfurization treatment method of phenol-containing oil and desulfurated phenol-containing oil produced by the method. The method includes contacting the phenol-containing oil with a desulfurizing non-dephenolizing catalyst to perform treatment of desulfurizing without dephenolizing under a hydrogen condition. The desulfurizing non-dephenolizing catalyst comprises a carrier and an active metal component supported on the carrier. The carrier is one or at least two of zinc oxide, aluminum oxide and silicon oxide, and the active metal component is at least one of nickel, copper, palladium, platinum and ruthenium, wherein, based on the total weight of the desulfurizing non-dephenolizing catalyst, the content of the carrier is 80-98 wt%, and the content of the active metal component is 2-20 wt%. The hydrogen condition refers to that the reaction is carried out in a hydrogen atmosphere under normal pressure. The method in the invention can decrease the sulfur content to the utmost degree under a premise of decreasing the phenols content as little as possible, so as to enhance economic benefits to a greater degree.
Description
Technical field
The present invention relates to refining art, in particular it relates to a kind of desulfuration processing method of carbolic oil and by
The desulfurization carbolic oil that the method is prepared.
Background technology
Coal tar contains substantial amounts of phenolic compound, if coal tar is directly carried out into hydrogenation upgrading, a side
Face phenolic compound is hydrogenated deoxidation, causes added value to reduce, while also add hydrogenation process
Hydrogen consumes；The water of another aspect phenolic compound deoxidation generation may result in the active metal centre of catalyst
Aggregation, influences the activity of catalyst.It can be seen that, phenolic compound rationally utilizes significant in coal tar.
At present, the mode of phenolic compound is that coal tar is carried out into dephenolize in conventional upgrading coal tar, is obtained
It is smart phenol to crude phenols or further purification, remaining dephenolize oil carries out hydrotreating.The dephenolize process can be produced
, there is serious pollution hidden trouble in a large amount of spent acid of life and salkali waste, it is carried out to clean treatment, can increase
Plus the burden of enterprise.
Wherein, phenol content evaporates section (- 210 DEG C of distillates of initial boiling point) and enriches the most in the carbolic oil of coal tar,
The phenolic compound of the 40-50% in tar is concentrated in this section of cut, predominantly phenol and methylphenol.
The yield of carbolic oil is about the 5-7% of anhydrous tar.Phenol mode is put forward relative to traditional, by carbolic oil
Phenolic compound be converted into antiknock component to prepare high-knock rating gasoline ready-mixed oil be a kind of more clear
The more wide upgrading mode in clean and market.However, the presence of sulphur is the grading process in carbolic oil
One of obstacle, the exhaust emission of sulphur, therefore limitation are easily caused due to the sulfide in gasoline in use
Sulfur content is an important indicator in gasoline standard.In response to country call and realize the performance of enterprises
Maximization, it is a kind of inexorable trend that exploitation energy consumption is low, pollute small desulfurization technology.
The method that CN103695030A discloses the producing diesel by hydrogenating anthrancene oil in a kind of coal tar, and specifically
Disclose and first carbolineum is reacted in the hydroconversion reaction zone containing the first catalyst, then by hydroconversion reaction zone
Products therefrom oil enter the hydrocracking reaction area containing the second catalyst in reaction be obtained diesel component into
Product.Auxiliary agent potassium is added in the Hydrobon catalyst of the prior art, it is suppressed that easy green coke in coal tar
The coking and blocking reactor of material, improves the stability of catalyst, by adjusting titanium dioxide in carrier
With the additional proportion of ceria, the acidity of carrier is effectively controlled, be conducive to just improving the work being hydrocracked
Property and selectivity；Meanwhile, titanium dioxide has stronger adsorption capacity to sulphur, is conducive to desulfurization, titanium dioxide
The fusing point of cerium is high, improves the stability of carrier, so that the service life of catalyst is improved, but the hydrogenation
Catalyst for refining can simultaneously take off oxygen while hydrodesulfurization and denitrogenation.
US5730860 discloses the sulfur method of gasoline and hydrocarbon raw material, and the prior art is Black
The IRVAD technologies that ＆Veatch Pritchard Inc and Alcon Industrial Chemicals are developed jointly,
It is a disruptive technology of low cost removing sulfur-bearing or other heteroatomic compounds from hydro carbons.The technology
Using multi-stage absorption mode, using aluminum oxide-based selective solid absorbent treatment liquid hydro carbons, in low pressure
Lower operation, desulfurization degree is up to more than 90%.However, the method for the prior art is utilized under hydrogen-free gaseity
Polar adsorbent removes sulfur-nitrogen compound in absorber is segmented, and the method for belonging to physical absorption is present
The shortcomings of adsorption capacity is not big enough.
US6350422, US6346190 and US6338794 are that the S-Zorb of Phillips oil companies is only
Some sulphur removing sulfuldioxide adsorbents, adsorbent is loaded in carrier by Zn and other metals and is constituted, and carrier is adopted
With the mixture of zinc oxide, silica and aluminum oxide, the content of zinc oxide is 10-90%, silica in carrier
For 5-85%, aluminum oxide are 5-30%.Metal component can be Co and Ni or Ni and Cu, Ni and Co
Weight ratio be 1：The weight ratio about 3: 1 of 1, Ni and Cu, blended, granulating, drying, forges
It is fired into adsorbent.The adsorbent can adsorb sulfur-containing compound molecule, and sulphur atom is removed, and make molecule
In sulphur atom can retain on the sorbent, and hydrocarbon moiety is discharged, in returning to gasoline.The suction
Attached dose can carry out reaction absorption desulfurization under relatively low hydrogen consumption, but the octane number of product gasoline has brighter
Aobvious loss, Sulfur capacity is also not big enough, the short life of single hop reaction.
Therefore, traditional desulfurization technology is mainly hydrodesulfurization.However, in traditional hydrodesulfurization catalytic
Also phenolic hydroxyl group deoxidation conversion is fallen while hydrodesulfurization in agent, phenols is retained while not reaching desulfurization
The purpose of compound, therefore a kind of new sulfur method is developed to realize the mesh to carbolic oil desulfurization not dephenolize
The utilization to carbolic oil it is significant.
The content of the invention
The purpose of the present invention is the defect for overcoming prior art, on the premise of phenol content is reduced as little as possible
Sulfur content is reduced to greatest extent, there is provided a kind of desulfuration processing method of carbolic oil and be prepared into by the method
The desulfurization carbolic oil for arriving.
To achieve these goals, the present invention provides a kind of desulfuration processing method of carbolic oil, the method bag
Include：Under hydro condition, carbolic oil is contacted with desulfurization not dephenolize catalyst to carry out desulfurization not dephenolize place
Reason, the desulfurization not dephenolize catalyst contains carrier and load active metal component on the carrier,
The carrier is one kind or at least two combination in zinc oxide, aluminum oxide and silica, the activity
Metal component is at least one in nickel, copper, palladium, platinum and ruthenium, wherein, urged with the desulfurization not dephenolize
The gross weight meter of agent, the content of the carrier is 80-98 weight %, and the active metal component contains
It is 2-20 weight % to measure, and the hydro condition refers to carry out in reaction hydrogen atmosphere in atmospheric conditions.
The present invention also provides what a kind of desulfuration processing method by above-mentioned carbolic oil of the invention was prepared
Desulfurization carbolic oil.
Phenol content can as little as possible reduced using the desulfuration processing method of above-mentioned carbolic oil of the invention
On the premise of reduce sulfur content to greatest extent, so as to increase economic efficiency to a greater degree.
Be can be seen that by the result of embodiments of the invention：Using desulfuration processing method of the invention to containing
When carbolic oil carries out desulfurization process, sulphur therein can be optionally removed, and very small amount or do not remove
Aldehydes matter therein；And when carrying out desulfurization process to carbolic oil using the method for prior art, in removing
Also most of aldehydes matter therein is stripped of while sulphur in carbolic oil, so as to be unfavorable for product
Following process treatment, hence it is evident that reduce the economic worth of product.
And, the method for the present invention only needs to be carried out under the hydro condition of normal pressure, greatlys save production
Cost.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Specific embodiment of the invention is described in detail below.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to limit the invention.
On the one hand, the invention provides a kind of desulfuration processing method of carbolic oil, the method includes：Facing
Under hydrogen condition, carbolic oil is contacted with desulfurization not dephenolize catalyst to carry out desulfurization not phenol removal, it is described
Desulfurization not dephenolize catalyst contains carrier and load active metal component on the carrier, the carrier
It is the one kind in zinc oxide, aluminum oxide and silica or at least two combination, the active metal component
It is at least one in nickel, copper, palladium, platinum and ruthenium, wherein, with the total of the desulfurization not dephenolize catalyst
Weight meter, the content of the carrier is 80-98 weight %, and the content of the active metal component is 2-20
Weight %, the hydro condition refers to carry out in reaction hydrogen atmosphere in atmospheric conditions.
In the present invention, the hydro condition refers to and carries out in reaction hydrogen atmosphere in atmospheric conditions.
Phenol removal can not carried out in conventional use of various reactors for the desulfurization of the invention, right
There is no particular limitation for the number of the beds in the reactor, can be one or more,
As long as above-mentioned purpose of the invention can be realized.
Using the above method of the invention carbolic oil is carried out desulfurization not phenol removal when, can be optionally
Removing carbolic oil in sulphur and very small amount does not remove aldehydes matter therein even so that, it is of the invention on
The method of stating can increase economic efficiency to a greater degree.
Under preferable case, in the present invention, the carrier is further zinc oxide and/or aluminum oxide.
That is, the method for the present invention preferably carrier can for zinc oxide, aluminum oxide or for zinc oxide and
Aluminum oxide.
In the present invention, with the gross weight meter of the desulfurization not dephenolize catalyst, preferably described carrier contains
It is 80-98 weight % to measure, and the content of the active metal component is 2-20 weight %.
The first preferred embodiment of the invention, carrier of the present invention is zinc oxide
And aluminum oxide, with the gross weight meter of the desulfurization not dephenolize catalyst, the content of the zinc oxide is 40-90
Weight %, the content of the aluminum oxide is 8-58 weight %, and the content of the active metal component is 2-20
Weight %.Using the desulfurization not dephenolize catalyst of the first preferred embodiment of the present invention
Carry out the desulfurization not phenol removal when, can substantially reduce sulfur content in carbolic oil and reduce wherein
The removal efficiency of aldehydes matter.
Second preferred embodiment of the invention, carrier of the present invention is oxidation
Aluminium, with the gross weight meter of the desulfurization not dephenolize catalyst, the content of the aluminum oxide is 80-97 weights
Amount %, the content of the active metal component is 3-20 weight %.It is excellent using second of the present invention
The desulfurization not dephenolize catalyst of the specific embodiment of choosing carry out the desulfurization not phenol removal when, Neng Gouming
The removal efficiency of the aobvious sulfur content reduced in carbolic oil and reduction wherein aldehydes matter.
In the present invention, it is preferred to the active metal component is nickel and/or copper, the particularly preferred activity
Metal component is nickel or copper.It was found by the inventors of the present invention that using single base metal nickel or copper conduct
Active metal group in the desulfurization of carbolic oil of the invention desulfurization not dephenolize catalyst not in phenol removal
Timesharing, it becomes possible to significantly decrease the sulfur content in the carbolic oil, and reduce to greatest extent containing phenol
The removal efficiency of aldehydes matter in oil.
The third preferred embodiment of the invention, the carrier is zinc oxide and oxidation
Aluminium, the active metal component is nickel, with the gross weight meter of the desulfurization not dephenolize catalyst, the oxygen
The content for changing zinc is 70-90 weight %, the content of the aluminum oxide is 8-27 weight %, and the nickel contains
It is 2-15 weight % to measure.
4th kind of preferred embodiment of the invention, the carrier is zinc oxide and oxidation
Aluminium, the active metal component is copper, with the gross weight meter of the desulfurization not dephenolize catalyst, the oxygen
The content for changing zinc is 70-90 weight %, the content of the aluminum oxide is 8-15 weight %, and the copper contains
It is 2-15 weight % to measure.
5th kind of preferred embodiment of the invention, the carrier is aluminum oxide, the work
Property metal component be nickel, with the gross weight meter of the desulfurization not dephenolize catalyst, the content of the aluminum oxide
It is 85-97 weight %, the content of the nickel is 3-15 weight %.
Especially, it was found by the inventors of the present invention that using it is of the invention it is above-mentioned the third, the 4th kind and
The desulfurization not dephenolize catalyst provided in five kinds of preferred embodiments carries out of the present invention de-
Sulphur not phenol removal when, can significantly more reduce the sulfur content in the carbolic oil, and maximum limit
Degree ground reduces aldehydes matter in not even removing carbolic oil such that it is able to significantly more reduce production cost
To increase economic efficiency.
Under preferable case, in the present invention, inventor has found, the reaction bar of control desulfurization not phenol removal
When part is in following scope of the invention, the removal efficiency of the sulphur in the carbolic oil is higher, and the desulfurization is not
The condition of phenol removal includes：Temperature is 280-400 DEG C, and hydrogen flow rate is 5-50mL/min, body during liquid
Product air speed is 0.1-4h-1。
In the case of more preferably, in the present invention, the reaction condition of control desulfurization not phenol removal is in this hair
When in bright following scope, the removal efficiency of the sulphur in the carbolic oil is higher, and carbolic oil of the invention
In aldehydes matter removal efficiency it is lower, the condition of the desulfurization not phenol removal includes：Temperature is
320-380 DEG C, hydrogen flow rate is 10-30mL/min, and volume space velocity is 0.2-2h during liquid-1。
In the present invention, to the preparation method of the desulfurization not dephenolize catalyst, there is no particular limitation, this
Art personnel are met in the present invention using what conventional various preparation methods in the art were prepared
Stating the desulfurization not dephenolize catalyst of requirement can realize the purpose of selective desulfurization.However, of the invention
Inventor has found, using carrier is first prepared, then again by the solution containing active metal component element and institute
Stating carrier can have preferably choosing using the desulfurization not dephenolize catalyst that equi-volume impregnating is prepared
Selecting property desulfurized effect.In the present invention, the solution containing active metal component element is directed to this hair
For bright foregoing active metal component, the solution containing active metal component element of the invention
During catalyst is prepared, by can be obtained after follow-up drying and reduction step it is of the invention before
State active metal component.
There is no particular limitation for preparation method of the method for the present invention to carrier, during carrier is prepared
The conventional various additives such as sesbania powder for needing to add, acid binding agent etc. can be added, to additive
There is no particular limitation for addition, and those skilled in the art can according to actual needs determine adding for additive
Enter amount.
The method of the present invention is to the concentration of the solution containing active metal component element without special
Limit, as long as not taken off by the desulfurization prepared using the solution containing active metal component element
The content of the active metal component of phenol catalyst meets aforementioned range of the invention.The method of the present invention
To the species of the solution containing active metal component element, also there is no particular limitation, for example, can be
The form of the aqueous solution of the nitrate, sulfate and halide of the active metal component.
6th kind of the invention specific preferred embodiment, desulfurization not dephenolize place of the present invention
Reason method also includes being carried out in equal volume by by the carrier and the solution containing active metal component element
Dipping, and gained solid product after dipping is dried, be calcined and reduced successively be described de- to prepare
Sulphur not dephenolize catalyst.
In the present invention, the concrete operation method of the equi-volume impregnating is public those skilled in the art
Know, specifically, the equi-volume impregnating is with the deionized water that volume is carrier just saturated absorption
Catalyst-solvent presoma, is subsequently adding carrier and is sufficiently stirred for dipping.
Under preferable case, include in the present invention, the step of the reduction：In the presence of reducibility gas
Under, reduce 4-36h under conditions of being 300-500 DEG C in temperature by dried solid product.
The method of the present invention can be reduced using various reducibility gas to dried solid product,
Under preferable case, the dried solid product is reduced using hydrogen.
The method of the present invention does not require that the property of raw material carbolic oil the method for the present invention is applicable particularly
Process the carbolic oil of various properties.Under preferable case, when the sulfur content in the carbolic oil is
500-3800mg/L, when phenol content is 100-700g/L, using desulfurization of the invention not dephenolization treating method
The effect for carrying out selective desulfurization is more preferable.
In the present invention, the phenol is foregoing aldehydes matter, including phenol, methylphenol and diformazan
Base phenol.
The present invention also provides a kind of desulfurization by above-mentioned carbolic oil of the invention, and not prepared by dephenolization treating method
The desulfurization carbolic oil for obtaining.
Sulfur content is less than 100mg/L in the preferably desulfurization carbolic oil of the invention, and dephenolize rate is less than 10 weights
Amount %；Sulfur content is less than 50mg/L in more preferably described desulfurization carbolic oil.
In the case of particularly preferably, in the present invention, sulfur content is 0-30mg/L in the desulfurization carbolic oil,
Dephenolize rate is less than 5 weight %.
Below will the present invention will be described in detail by embodiment.
In following preparation example, embodiment and comparative example, in case of no particular description, used
Various materials are all from commercially available.
In the following Examples and Comparative Examples, using in gas chromatograph detection carbolic oil and desulfurization carbolic oil
The content of aldehydes matter, the sulfur content in carbolic oil and desulfurization carbolic oil is determined using elemental analyser.Adopt
The component content of the desulfurization not dephenolize catalyst with XRF methods to preparing is detected, described de-
Phenol content in phenol rate=(the phenol content in phenol content-desulfurization carbolic oil in carbolic oil)/carbolic oil ×
100%.
Preparation example 1
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 450g zinc oxide, 50g aluminum oxide, 15g sesbania powders are well mixed, the 3 dilute nitre of weight % are added
Acid makes dry-mixed sample that paste is presented, using screw rod banded extruder by paste sample extruded moulding, then in air blast
It is dried overnight at 120 DEG C in drier, is placed in Muffle furnace and is calcined 6h at 400 DEG C, obtains ZnO-Al2O3
Carrier.Then, support type desulfurization not dephenolize catalyst is prepared using equi-volume impregnating：Take 5g nickel nitrates
It is dissolved in 7ml deionized waters, adds the foregoing ZnO-Al of 20g2O3Carrier, stirs 30 minutes, room temperature
Steeped overnight under (25 DEG C).The solid product is dried into 6h at 120 DEG C, desulfurization not dephenolize is obtained
Catalyst precarsor.Desulfurization not dephenolize catalyst precarsor is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization
Not dephenolize catalyst C1.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C1, the desulfurization not dephenolize catalysis
The content of ZnO is 85.71 weight %, Al in agent C12O3Content be 9.52 weight %, balance of Ni.
Preparation example 2
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 500g aluminum oxide, 15g sesbania powders are well mixed, 3 weight % dust technologies are added to make dry-mixed sample
Paste is presented, using screw rod banded extruder by paste sample extruded moulding, then 120 DEG C in blast drier
Under be dried overnight, be placed in Muffle furnace and be calcined 6h at 400 DEG C, obtain Al2O3Carrier.Then, use
Equi-volume impregnating prepares support type desulfurization not dephenolize catalyst：Take 5g nickel nitrates and be dissolved in 7ml deionizations
In water, the foregoing Al of 20g are added2O3Carrier, stirs 30 minutes, steeped overnight at room temperature.By the solid
Product dries 6h at 120 DEG C, obtains desulfurization not dephenolize catalyst precarsor.Before desulfurization not dephenolize catalyst
Body is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization not dephenolize catalyst C2.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C2, the desulfurization not dephenolize is urged
Al in agent C22O3Content be 95.24 weight %, balance of Ni.
Preparation example 3
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 450g zinc oxide, 50g aluminum oxide, 15g sesbania powders are well mixed, the 3 dilute nitre of weight % are added
Acid makes dry-mixed sample that paste is presented, using screw rod banded extruder by paste sample extruded moulding, then in air blast
It is dried overnight at 120 DEG C in drier, is placed in Muffle furnace and is calcined 6h at 400 DEG C, obtains ZnO-Al2O3
Carrier.Then, support type desulfurization not dephenolize catalyst is prepared using equi-volume impregnating：Take 4.062g nitre
Sour copper dissolution adds the foregoing ZnO-Al of 20g in 9ml deionized waters2O3Carrier, stirs 30 minutes, room
The lower steeped overnight of temperature.The solid product is dried into 6h at 120 DEG C, desulfurization not dephenolize catalyst is obtained
Precursor.Desulfurization not dephenolize catalyst precarsor is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization not dephenolize
Catalyst C3.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C3, the desulfurization not dephenolize catalysis
The content of ZnO is 85.39 weight %, Al in agent C32O3Content be 9.49 weight %, balance of Cu.
Preparation example 4
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 500g zinc oxide, 15g sesbania powders are well mixed, 3 weight % dust technologies are added to make dry-mixed sample
Paste is presented, using screw rod banded extruder by paste sample extruded moulding, then 120 DEG C in blast drier
Under be dried overnight, be placed in Muffle furnace and be calcined 6h at 400 DEG C, obtain ZnO carriers.Then, use
Equi-volume impregnating prepares support type desulfurization not dephenolize catalyst：Take 5g nickel nitrates and be dissolved in 7ml deionizations
In water, the foregoing ZnO carriers of 20g are added, stirred 30 minutes, steeped overnight at room temperature.By the solid
Product dries 6h at 120 DEG C, obtains desulfurization not dephenolize catalyst precarsor.Before desulfurization not dephenolize catalyst
Body is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization not dephenolize catalyst C4.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C4, the desulfurization not dephenolize is urged
The content of ZnO is 95.24 weight %, balance of Ni in agent C4.
Preparation example 5
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 250g zinc oxide, 250g aluminum oxide, 15g sesbania powders are well mixed, the 3 dilute nitre of weight % are added
Acid makes dry-mixed sample that paste is presented, using screw rod banded extruder by paste sample extruded moulding, then in air blast
It is dried overnight at 120 DEG C in drier, is placed in Muffle furnace and is calcined 6h at 400 DEG C, obtains ZnO-Al2O3
Carrier.Then, support type desulfurization not dephenolize catalyst is prepared using equi-volume impregnating：Take 5g nickel nitrates
It is dissolved in 7ml deionized waters, adds the foregoing ZnO-Al of 20g2O3Carrier, stirring 30 minutes, at room temperature
Steeped overnight.The solid product is dried into 6h at 120 DEG C, desulfurization not dephenolize catalyst precarsor is obtained.
Desulfurization not dephenolize catalyst precarsor is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization not dephenolize catalyst
C5。
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C5, the desulfurization not dephenolize is urged
The content of ZnO is 47.62 weight %, Al in agent C52O3Content be 47.62 weight %, surplus
It is Ni.
Preparation example 6
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 450g zinc oxide, 50g aluminum oxide, 15g sesbania powders are well mixed, the 3 dilute nitre of weight % are added
Acid makes dry-mixed sample that paste is presented, using screw rod banded extruder by paste sample extruded moulding, then in air blast
It is dried overnight at 120 DEG C in drier, is placed in Muffle furnace and is calcined 6h at 400 DEG C, obtains ZnO-Al2O3
Carrier.Then, support type desulfurization not dephenolize catalyst is prepared using equi-volume impregnating：Take 2.52g nitric acid
Nickel and 2.01g copper nitrates are dissolved in 7ml deionized waters, add the foregoing ZnO-Al of 20g2O3Carrier, room temperature
Lower steeped overnight.The solid product is dried into 6h at 120 DEG C, before obtaining desulfurization not dephenolize catalyst
Body.Desulfurization not dephenolize catalyst precarsor is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization not dephenolize and urge
Agent C6.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C6, the desulfurization not dephenolize is urged
The content of ZnO is 85.55 weight %, Al in agent C62O3Content be 9.51 weight %, Ni contains
It is 2.38 weight %, balance of Cu to measure.
Preparation example 7
This preparation example is used to prepare desulfurization not dephenolize catalyst of the present invention, and specific method is as follows：
After 50g zinc oxide, 450g aluminum oxide, 15g sesbania powders are well mixed, the 3 dilute nitre of weight % are added
Acid makes dry-mixed sample that paste is presented, using screw rod banded extruder by paste sample extruded moulding, then in air blast
It is dried overnight at 120 DEG C in drier, is placed in Muffle furnace and is calcined 6h at 400 DEG C, obtains ZnO-Al2O3
Carrier.Then, support type desulfurization not dephenolize catalyst is prepared using equi-volume impregnating：Take 5g nitric acid
Nickel is dissolved in 7ml deionized waters, adds the foregoing ZnO-Al of 20g2O3Carrier, stirs 30 minutes, room temperature
Lower steeped overnight.The solid product is dried into 6h at 120 DEG C, before obtaining desulfurization not dephenolize catalyst
Body.Desulfurization not dephenolize catalyst precarsor is in H2Under atmosphere, 360 DEG C of reductase 12 0h, obtain desulfurization not dephenolize and urge
Agent C7.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst C7, the desulfurization not dephenolize is urged
The content of ZnO is 9.52 weight %, Al in agent C72O3Content be 85.71 weight %, it is balance of
Ni。
Comparative example 1
This contrast is using business NiMo/Al2O3Catalyst is used as desulfurization not dephenolize catalyst D1.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst D1, the desulfurization not dephenolize is urged
NiO and MoO in agent D13The content of component is respectively 5 weight % and 25 weight %, Al2O3's
Content is 70 weight %.
Contrast preparation example 2
This contrast preparation example prepares desulfurization not dephenolize catalyst, metal active using the method for incipient impregnation
Component is Ni and Mo, and carrier is silica.Silica is purchased from Qingdao Gui Chuan Fine Chemical Co., Ltd.
Take 5g nickel nitrates and ammonium molybdate is dissolved in 22ml deionized waters, add 20g aforementioned oxidation silicon carriers, stirring
Dried at room temperature after 30 minutes.The solid product is dried into 6h at 120 DEG C, desulfurization is obtained and is not taken off
Phenol catalyst precursor.Desulfurization not dephenolize catalyst precarsor is in H2Under atmosphere, 360 DEG C of reductase 12 0h, taken off
Sulphur not dephenolize catalyst D2.
After testing, with the gross weight meter of the desulfurization not dephenolize catalyst D2, the desulfurization not dephenolize is urged
NiO and MoO in agent D23The content of component is respectively 4.7 weight % and 25.5 weight %, SiO2
Content be 69.8 weight %.
Embodiment 1
The desulfurization not dephenolize Catalyst packing prepared in the above-mentioned preparation example 1-7 of 5mL is taken respectively in fixation
In bed reactor, beds are formed.Then in carbolic oil being pumped into reactor, carry out desulfurization and do not take off
Phenol treatment.Wherein, reaction temperature is 360 DEG C, and hydrogen flow rate is 20mL/min, and volume space velocity is during liquid
1h-1.Product liquid desulfurization carbolic oil is obtained in reactor exit.
Wherein, the property of the carbolic oil and the desulfurization carbolic oil is as shown in table 1.
Table 1
Comparative example 1
This comparative example is carried out using method similar to Example 1, except that, the desulfurization for being used
The species of not dephenolize catalyst is different, and this comparative example is not taken off using the desulfurization that contrast preparation example 1 is prepared
Phenol catalyst D1 as the desulfurization not dephenolize catalyst in the method for this comparative example, remaining with embodiment 1
In it is identical.
Wherein, the property of the carbolic oil and the desulfurization carbolic oil is as shown in table 1.
Embodiment 2
The desulfurization not dephenolize catalyst that the present embodiment is used is desulfurization not dephenolize catalysis described in preparation example 1
Agent, except that, change embodiment 1 reaction temperature and liquid hourly space velocity (LHSV), remaining with embodiment 1 in
It is identical.
Wherein, the property of reaction condition and liquid hourly space velocity (LHSV) and carbolic oil and desulfurization carbolic oil is as shown in table 2.
Table 2
Embodiment 3
The desulfurization not dephenolize catalyst that the present embodiment is used is desulfurization not dephenolize catalysis described in preparation example 1
Agent, except that, the sulfur content in carbolic oil is different, and remaining is in the same manner as in Example 1.
The desulfurization not dephenolize Catalyst packing prepared in the above-mentioned preparation examples 1 of 5mL is taken respectively in fixed bed
In reactor, beds are formed.Then in carbolic oil being pumped into reactor, desulfurization not dephenolize is carried out
Treatment.Wherein, reaction temperature is 320 DEG C, and hydrogen flow rate is 20mL/min, and volume space velocity is 0.2h during liquid-1。
Product liquid desulfurization carbolic oil is obtained in reactor exit.
Wherein, the property of the carbolic oil and the desulfurization carbolic oil is as shown in table 3.
Table 3
Do not taken off as can be seen that carrying out desulfurization to carbolic oil using desulfuration processing method of the invention by contrast
During phenol treatment, sulphur therein can be optionally removed, and very small amount or do not remove phenols therein
Material；And using the method for prior art carbolic oil is carried out desulfurization not phenol removal when, contain being stripped of
Also most of aldehydes matter therein is stripped of while sulphur in carbolic oil, after being unfavorable for product
Continuous working process, hence it is evident that reduce the economic worth of product.
And, the method for the present invention only needs to be carried out under the hydro condition of normal pressure, greatlys save production
Cost.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to above-mentioned reality
The detail in mode is applied, in range of the technology design of the invention, can be to technical side of the invention
Case carries out various simple variants, and these simple variants belong to protection scope of the present invention.
It is further to note that each particular technique described in above-mentioned specific embodiment is special
Levy, in the case of reconcilable, can be combined by any suitable means, in order to avoid need not
The repetition wanted, the present invention is no longer separately illustrated to various possible combinations.
Additionally, can also be combined between a variety of implementation methods of the invention, as long as its
Without prejudice to thought of the invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of desulfuration processing method of carbolic oil, including：Under hydro condition, by carbolic oil with it is de-
Sulphur not dephenolize catalyst contacts to carry out desulfurization not phenol removal, it is characterised in that：The desulfurization not dephenolize
Catalyst contains carrier and load active metal component on the carrier, the carrier be zinc oxide,
One kind or at least two combination in aluminum oxide and silica, the active metal component be nickel, copper,
At least one in palladium, platinum and ruthenium, wherein, with the gross weight meter of the desulfurization not dephenolize catalyst, institute
The content of carrier is stated for 80-98 weight %, the content of the active metal component is 2-20 weight %, institute
It refers to carry out in reaction hydrogen atmosphere in atmospheric conditions to state hydro condition.
2. method according to claim 1, wherein, the carrier further for zinc oxide and/or
Aluminum oxide.
3. method according to claim 2, the carrier is further zinc oxide and aluminum oxide,
Wherein, with the gross weight meter of the desulfurization not dephenolize catalyst, the content of the zinc oxide is further
40-90 weight %, the content of the aluminum oxide is further 8-58 weight %, the active metal component
Content further be 2-20 weight %；Or
The carrier is aluminum oxide, with the gross weight meter of the desulfurization not dephenolize catalyst, the aluminum oxide
Content be further 80-97 weight %, the content of the active metal component is further 3-20 weights
Amount %.
4. method according to claim 1, wherein, the active metal component is nickel and/or copper；
It is preferred that
The active metal component is nickel, with the gross weight meter of the desulfurization not dephenolize catalyst, the oxygen
The content for changing zinc is further 70-90 weight %, and the content of the aluminum oxide is further 8-27 weight %,
The content of the nickel is further 2-15 weight %.
5. the method according to any one in claim 1-3, wherein, the desulfurization not dephenolize
The condition for the treatment of includes：Temperature is 280-400 DEG C, and hydrogen flow rate is 5-50mL/min, and volume is empty during liquid
Speed is 0.1-4h-1；It is preferred that
The condition of the desulfurization not phenol removal includes：Temperature is 320-380 DEG C, and hydrogen flow rate is
10-30mL/min, volume space velocity is 0.2-2h during liquid-1。
6. the method according to any one in claim 1-3, wherein, methods described also includes
Incipient impregnation is carried out by by the carrier and the solution containing active metal component element, and will leaching
Gained solid product is dried, is calcined and reduces and is catalyzed with preparing the desulfurization not dephenolize successively after stain
Agent.
7. method according to claim 6, wherein, include the step of the reduction：In reduction
Property gas in the presence of, by dried solid product temperature be 300-500 DEG C under conditions of reduce
4-36h。
8. method according to claim 1, wherein, the sulfur content in the carbolic oil is
500-3800mg/L, phenol content is 100-700g/L.
9. the desulfuration processing method of the carbolic oil as described in any one in claim 1-8 is prepared
Desulfurization carbolic oil.
10. desulfurization carbolic oil according to claim 9, wherein, sulfur content in the desulfurization carbolic oil
Less than 100mg/L, dephenolize rate is less than 10 weight %；It is preferred that
Sulfur content is 0-30mg/L in the desulfurization carbolic oil, and dephenolize rate is less than 5 weight %.
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| CN111111688A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN114345329A (en) * | 2021-11-08 | 2022-04-15 | 大连理工大学 | Application of normal-pressure ultra-deep desulfurization catalyst |
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| CN100340639C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing IIB metal oxide and uses |
| CN102688772B (en) * | 2012-06-14 | 2014-04-23 | 山西盛驰科技有限公司 | Hydrodesulfurization catalyst for removing sulfur compounds in medium/low-temperature coal tar and application thereof |
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| CN111111688A (en) * | 2018-10-31 | 2020-05-08 | 中国石油化工股份有限公司 | Desulfurization catalyst, preparation method thereof and hydrocarbon oil desulfurization method |
| CN114345329A (en) * | 2021-11-08 | 2022-04-15 | 大连理工大学 | Application of normal-pressure ultra-deep desulfurization catalyst |
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