CN100486699C - Catalyst used for producing refined benzene by hydrogenation, desulfurization and denitrification of crude benzene, and preparation method thereof - Google Patents
Catalyst used for producing refined benzene by hydrogenation, desulfurization and denitrification of crude benzene, and preparation method thereof Download PDFInfo
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- CN100486699C CN100486699C CNB2006100222572A CN200610022257A CN100486699C CN 100486699 C CN100486699 C CN 100486699C CN B2006100222572 A CNB2006100222572 A CN B2006100222572A CN 200610022257 A CN200610022257 A CN 200610022257A CN 100486699 C CN100486699 C CN 100486699C
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 37
- 238000006477 desulfuration reaction Methods 0.000 title claims description 24
- 230000023556 desulfurization Effects 0.000 title claims description 24
- 238000002360 preparation method Methods 0.000 title claims description 12
- 238000000034 method Methods 0.000 claims abstract description 26
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 150000001868 cobalt Chemical class 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 241000219782 Sesbania Species 0.000 claims description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 9
- 239000000806 elastomer Substances 0.000 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 8
- 150000002751 molybdenum Chemical class 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 7
- 229910003296 Ni-Mo Inorganic materials 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- -1 rare earth metal salt Chemical class 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 4
- 229910052691 Erbium Inorganic materials 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 150000000914 Dysprosium Chemical class 0.000 claims description 2
- 150000000917 Erbium Chemical class 0.000 claims description 2
- 150000000922 Holmium Chemical class 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 229910003294 NiMo Inorganic materials 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000007670 refining Methods 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 150000002602 lanthanoids Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012451 post-reaction mixture Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000001833 catalytic reforming Methods 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
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical class C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
Abstract
A catalyst for preparing refined benzene from crude benzene by hydrodesulfurizing and denitrifying is composed of gamma-Al2O3-MgO as carrier and active component. It features low reaction temp and long service life. Its preparing process is also disclosed.
Description
Technical field
The present invention relates to be used for the Catalysts and its preparation method of crude benzole hydrogenation desulfurization removing nitric producing refined benzene
Background technology
Benzene is obtained by the dry distillation of coal, oil catalytic pyrolysis, catalytic reforming, therefore contains some unsaturated hydrocarbons and sulfur-bearing nitrogen-containing compound, as linear paraffin mercaptan, aromatic radical mercaptan, thioether, thiophene, dibenzothiophenes, benzo-thiophene, pyridine etc.When benzene during as the organic synthesis raw material, these impurity need remove.Crude benzole hydrogenation is to generate hydrocarbon and sulfide in order to incite somebody to action wherein sulfur-containing impurities hydrogenation, make nitrogen-containing impurity hydrogenation generate ammonia and hydrocarbon, make oxygenate impurity hydrogenation generate hydrocarbon and water, the unsaturated hydrocarbons compounds is generated saturated alkane derivative by hydrogenation, thereby reaches the purpose of purification.
The crude benzole hydrogenation commercial benzene is divided into high-temperature hydrogenation (600～630 ℃), moderate temperature hydrogenation (480～550 ℃) and low temperature hydrogenation (350～380 ℃) according to the difference of operating condition, and the catalyst that is adopted is CoMo catalyst, NiMo catalyst etc. mostly.With respect to high temperature and moderate temperature hydrogenation, low temperature hydrogenation has more competitive advantage.Because the development of petroleum refining industry, CoMo catalyst and NiMo catalyst quoting aspect hydrodesulfurization is very extensive, the patent of application is also a lot, common employing γ-Al203, MCM-41 mesoporous molecular sieves etc. are as carrier, a certain amount of active component of load forms, but present CoMo catalyst and NiMo catalyst can not well be taken into account at aspects such as denitrogenation, reduction reaction temperatures.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene.It is effective to adopt this catalyst to carry out the crude benzole hydrogenation desulfurization removing nitric, and reaction temperature is than conventional temperature required the decreasing of hydrogenation technique simultaneously.
Another object of the present invention provides the above-mentioned Preparation of catalysts method that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene.
The technical solution adopted for the present invention to solve the technical problems is: a kind of catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene, it is with γ-Al
2O
3-MgO is a carrier, a certain amount of active component of load and making.
Above-mentioned γ-Al
2O
3The material of-MgO carrier for making by following method: with weight ratio is the Mg (NO of 0.5～10:1
3)
2Be dissolved in the deionized water with red fuming nitric acid (RFNA), the back adding that stirs accounts for the aluminum hydroxide solid elastomer powder of total mixture weight 30～90%, wherein MgO content is 3～15%, add the sesbania powder that accounts for total mixture weight 0.1～10% again, mix aftershaping, in 110～150 ℃ of down oven dry, 300～550 ℃ of following roastings 4～6 hours, promptly make γ-Al
2O
3-MgO carrier;
Load on above-mentioned γ-Al
2O
3Active component on the-MgO carrier can be preferably the Ni of 1-6% and the Mo of 2-10%, to make the NiMo catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene; Perhaps be preferably the rare earth metal of Mo, 0.01-1% of Co, 5-20% of 2-8% and 0.1～6% P, to make the CoMoXP catalyst (X is a rare earth metal, and P is a phosphorus) that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene.
Rare earth metal X in the above-mentioned CoMoXP catalyst is meant 17 kinds of lanthanide series La (lanthanum), Ce (cerium) in the periodic table of chemical element, Pr (praseodymium), Dy (dysprosium), Ho (holmium), Er (erbium), Yb (ytterbium) etc. and the Sc (scandium) similar to the chemical property of lanthanide series and Y (yttrium) etc.; Wherein be preferably Dy (dysprosium), Er (erbium), Ho (holmium) etc.
The above-mentioned NiMo catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene can prepare by the method that may further comprise the steps:
(1), with weight ratio is the Mg (NO of 0.5～10:1
3)
2Be dissolved in the deionized water with red fuming nitric acid (RFNA), the back adding that stirs accounts for the aluminum hydroxide solid elastomer powder of total mixture weight 30～90%, wherein MgO content is 3～15%, add the sesbania powder that accounts for total mixture weight 0.1～10% again, mix aftershaping, in 110～150 ℃ of down oven dry, 300～550 ℃ of following roastings 4～6 hours, promptly make γ-Al
2O
3-MgO carrier;
(2), a certain amount of nickel salt is joined concentration is in 5～28% the ammonia spirit, adds a certain amount of ethylenediamine under constantly stirring, the addition of ethylenediamine is 1/25～1/5 of a nickel salt, adds the molybdenum salt of aequum then, makes the Ni-Mo co-impregnated solution;
(3), adopt the equivalent impregnation method that carrier is immersed in the Ni-Mo co-impregnated solution, dip time 3～12 hours, in 110～150 ℃ of oven dry down, 400～600 ℃ of following roastings 4～8 hours make Ni, Mo content and are respectively 1～6% and 2～10% catalyst.
The concentration of the ammonia spirit in above-mentioned (2) step is preferably 12～18%; The addition of ethylenediamine is preferably 1/15～1/8 of nickel salt.
The above-mentioned CoMoXP catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene can prepare by the method that may further comprise the steps:
(1), with weight ratio is the Mg (NO of 0.5～10:1
3)
2Be dissolved in the deionized water with red fuming nitric acid (RFNA), the back adding that stirs accounts for the aluminum hydroxide solid elastomer powder of total mixture weight 30～90%, wherein MgO content is 3～15%, add the sesbania powder that accounts for total mixture weight 0.1～10% again, mix aftershaping, in 110～150 ℃ of down oven dry, 300～550 ℃ of following roastings 4～6 hours, promptly make γ-Al
2O
3-MgO carrier;
(2), a certain amount of cobalt salt being joined concentration is in 5～28% the ammonia spirit, under constantly stirring, add a certain amount of citric acid, the amount of citric acid is 1/3～7/4 of a cobalt salt, the molybdenum salt and the phosphate that add aequum then, wherein the weight ratio of molybdenum salt, phosphate and cobalt salt is 9～37:0.5～29:10～40, makes the Co-Mo-P co-impregnated solution;
(3), the γ-Al that adopts the equivalent impregnation method that (1) step is made
2O
3-MgO carrier immerses (2) and goes on foot in the Co-Mo-P co-impregnated solution that makes, and dip time 3～18 hours in 110～150 ℃ of oven dry down, makes catalyst precarsor;
(4), the rare earth metal salt that will account for cobalt salt weight 0.01～0.25 dissolves in the deionized water, under constantly stirring, add a certain amount of citric acid, the amount of citric acid is 1/3～7/4 of a cobalt salt, then the catalyst precarsor that makes is impregnated in this solution, dip time 3～12 hours, in 400～600 ℃ of following roastings 4～8 hours, make Co, Mo, rare earth metal, P content and be respectively 2～8%, 5～20%, 0.01～1% and 0.1～6% catalyst under the blanket of nitrogen.
The concentration of the ammonia spirit described in above-mentioned (2) step is preferably 12～18%; The addition of citric acid is preferably 1/2～4/3 of nickel salt.
Cobalt salt used among the above-mentioned preparation method can be selected from cobalt acetate, cobalt nitrate, cobalt chloride or cobalt oxalate etc.; Molybdenum salt can be selected ammonium molybdate etc. for use; Rare earth metal salt can be selected from dysprosium salt, holmium salt and erbium salt etc.; Phosphate can be selected from ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP) etc.
Catalyst of the present invention mainly as the catalyst in the crude benzole hydrogenation desulfurization removing nitric producing refined benzene process, need be used CS before use
2Or H
2The S sulfuration.
Compared with prior art, the invention has the beneficial effects as follows: it is effective that catalyst of the present invention is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene, hydrodesulfurization efficient height can become sulfur content less than 1mg/l, the nitrogen content refining benzene less than 5mg/l greater than 5000mg/l, nitrogen content less than the crude benzene refining of 500mg/l sulfur content.Reaction temperature is than conventional temperature required the decreasing of hydrogenation technique simultaneously; And the long service life of this catalyst.Remove the catalyst that can be used as crude benzol producing refined benzene hydrogenation desulfurization and denitrogenation, also can be widely used as the catalyst that other needs hydrogenation desulfurization and denitrogenation technology, have good market prospects, be suitable for industrialization promotion.
Description of drawings
Fig. 1 is the process flow diagram that catalyst of the present invention is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene.
The specific embodiment
The present invention is described in further detail below in conjunction with the specific embodiment.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.
Embodiment 1
Present embodiment is a NiMo Preparation of catalysts method, may further comprise the steps:
(1), with 11 gram Mg (NO
3)
2Be dissolved in the 100ml ionized water with 8 gram nitric acid, it is 1.25ml/g that the back that stirs adds 97 gram pore volumes, and specific area is 290m
2The aluminum hydroxide solid elastomer powder of/g adds 15 gram sesbania powder again, makes the spheric granules of 2～3mm after mixing; In about 4 hours of 110～150 ℃ of down oven dry, 300～400 ℃ of following roastings, make MgO content and be 3%, pore volume is that 1.07ml/g, specific area are 301m
2γ-Al of/g
2O
3-MgO carrier.
(2), with 15 gram Ni (NO
3)
26H
2O joins in 18% the ammonia spirit, adds a certain amount of ethylenediamine under constantly stirring, and the addition of ethylenediamine is about 1/15 of Ni salt amount, adds 18 gram (NH then
4)
6Mo
7O
244H
2O makes the Ni-Mo co-impregnated solution.
(3), adopt the equivalent impregnation method respectively 90 gram carriers to be immersed in the Ni-Mo co-impregnated solutions, about 12 hours of dip time, in 110～150 ℃ of oven dry down, about 4 hours of 400～500 ℃ of following roastings make Ni, Mo content and are respectively 2.95% and 9.53% catalyst.
Embodiment 2
Present embodiment is a CoMoXP Preparation of catalysts method, may further comprise the steps:
(1), with 55 gram Mg (NO
3)
2Be dissolved in the 100ml ionized water with 6 gram nitric acid, it is 1.25ml/g that the back that stirs adds 85 gram pore volumes, and specific area is 290m
2The aluminum hydroxide solid elastomer powder of/g adds 15 gram sesbania powder again, makes the spheric granules of 2～3mm after mixing; In about 6 hours of 110～150 ℃ of down oven dry, 400～500 ℃ of following roastings, make MgO content and be 15%, pore volume is that 0.75ml/g, specific area are 270m
2γ-Al of/g
2O
3-MgO carrier.
(2), with 30 gram Co (NO
3)
26H
2O joins in 12% the ammonia spirit, adds a certain amount of citric acid under constantly stirring, and the addition of citric acid is about 4/3 of cobalt salt, adds 25 gram (NH then
4)
6Mo
7O
244H
2O and 15 gram (NH
4)
3PO
4, make the Co-Mo-P co-impregnated solution.
(3), with in the 80 gram carriers immersion Co-Mo-P co-impregnated solutions, about 18 hours of dip time in 110～150 ℃ of oven dry down, makes catalyst precarsor to employing equivalent impregnation method respectively.
(4), with 1.2 gram Dy (NO
3)
25H
2O dissolves in the deionized water, under constantly stirring, add a certain amount of citric acid, the addition of citric acid is about 5/4 of cobalt salt, the 102 gram catalyst precarsors that will make then are impregnated in this solution, about 3 hours of dip time, in 400～600 ℃ of following roastings 8 hours, make Co, Mo, rare earth metal Dy (dysprosium), P content and be respectively 5.9%, 13.2%, 0.5% and 2.87% CoMoXP catalyst under the blanket of nitrogen.
Embodiment 3
Present embodiment is a CoMoXP Preparation of catalysts method, may further comprise the steps:
(1), with 11 gram Mg (NO
3)
2Be dissolved in the 100ml ionized water with 8 gram nitric acid, it is 0.50/g that the back that stirs adds 97 gram pore volumes, and specific area is 225m
2The aluminum hydroxide solid elastomer powder of/g adds 15 gram sesbania powder again, makes the spheric granules of 2～3mm after mixing; About 5 hours of the oven dry down in 11O～150 ℃, 450～550 ℃ of following roastings make MgO content and are 3%, pore volume is that 0.46ml/g, specific area are 203m
2γ-Al of/g
2O
3-MgO carrier.
(2), with 30 gram Co (NO
3)
26H
2O joins in 28% the ammonia spirit, adds a certain amount of citric acid under constantly stirring, and the addition of citric acid is about cobalt salt 1/2, adds 25 gram (NH then
4)
6Mo
7O
244H
2O and 15 gram (NH
4)
3PO
4, make the Co-Mo-P co-impregnated solution.
(3), with in the 80 gram carriers immersion Co-Mo-P co-impregnated solutions, about 3 hours of dip time in 110～150 ℃ of oven dry down, makes catalyst precarsor to employing equivalent impregnation method respectively.
(4), with 1.2 gram Er (NO
3)
25H
2O dissolves in the deionized water, under constantly stirring, add a certain amount of citric acid, the amount of citric acid is 1/4 of a cobalt salt, the 102 gram catalyst precarsors that will make then are impregnated in this solution, about 12 hours of dip time, in about 4 hours of 400～600 ℃ of following roastings, make Co, Mo, rare earth metal Er (erbium), P content and be respectively 5.9%, 13.2%, 0.5% and 2.87% CoMoXP catalyst under the blanket of nitrogen.
Embodiment 4
Present embodiment is the application test that the above embodiment of the present invention 1 and embodiment 2 described catalyst are used for coking benzene hydrogenation desulfurization denitrogenation producing refined benzene technology, and its process flow diagram is seen Fig. 1, and concrete grammar and experimental result are as follows:
Each 100 gram of catalyst that example 1 and example 2 are made are respectively charged in the A reactor and second reactor of Φ 32 * 3.5.Use CS before the use
2(containing 10% benzole soln) sulfuration, conditions of vulcanization is: 200 ℃ of temperature, hydrogen pressure 2.5Mpa, liquid air speed 2h
-1, hydrogen: CS
2Solution (volume ratio) 500:1, cure time 10 hours, standby.The 200 gram ZnO desulfurizing agents of in three reactor, packing into.
Be communicated with flow process, coking benzene is through preliminary treatment rectifying, obtain benzene content greater than 97%, sulfur content is less than 5000ppm, nitrogen content is less than the crude benzol of 500mg/l, crude benzol mixes (hydrogen: crude benzol=800:1 in blender with hydrogen, volume ratio) enters heater 1, after temperature is heated to 270 ℃, enter A reactor and carry out the preliminary hydrogenation desulfurization and denitrogenation reaction of I level, after coming out, A reactor enters heater 2, temperature is heated to 350 ℃, enter second reactor then and carry out II level hydrodesulfurization reaction, post reaction mixture, enters three reactor again and carries out the inorganic desulphurization reaction of III level but to 200 ℃ through cooler 1.Post reaction mixture enters separator and separates after cooler 2 is cooled to normal temperature, separating obtained hydrogen can be recycled, liquid benzene then enters the benzene treating column and makes with extra care, thus obtain benzene content greater than 99.9%, sulfur content is less than the product refining benzene of 1mg/l nitrogen content less than 5mg/l.
Claims (8)
1. catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene, it is with γ-Al
2O
3-MgO is a carrier, and a certain amount of active component of load and making is characterized in that: described γ-Al
2O
3The material of-MgO carrier for making by following method:
With weight ratio is the Mg (NO of 0.5～10:1
3)
2Be dissolved in the deionized water with red fuming nitric acid (RFNA), the back adding that stirs accounts for the aluminum hydroxide solid elastomer powder of total mixture weight 30～90%, wherein MgO content is 3～15%, add the sesbania powder that accounts for total mixture weight 0.1～10% again, mix aftershaping, in 110～150 ℃ of down oven dry, 300～550 ℃ of following roastings 4～6 hours, promptly make γ-Al
2O
3-MgO carrier.
2. the catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene according to claim 1 is characterized in that: described active component is the Ni of 1-6% and the Mo of 2-10%.
3. the catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene according to claim 1 is characterized in that: described active component is the rare earth metal of Mo, 0.01-1% of Co, 5-20% of 2-8% and 0.1～6% P.
4. the catalyst that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene according to claim 3 is characterized in that: described rare earth metal is one or more of Dy, Er, Ho.
5. the described Preparation of catalysts method that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene of claim 2 comprises the steps:
(1), with weight ratio is the Mg (NO of 0.5～10:1
3)
2Be dissolved in the deionized water with red fuming nitric acid (RFNA), the back adding that stirs accounts for the aluminum hydroxide solid elastomer powder of total mixture weight 30～90%, wherein MgO content is 3～15%, add the sesbania powder that accounts for total mixture weight 0.1～10% again, mix aftershaping, in 110～150 ℃ of down oven dry, 300～550 ℃ of following roastings 4～6 hours, promptly make γ-Al
2O
3-MgO carrier;
(2), a certain amount of nickel salt is joined concentration is in 5～28% the ammonia spirit, adds a certain amount of ethylenediamine under constantly stirring, the addition of ethylenediamine is 1/25～1/5 of a nickel salt, adds the molybdenum salt of aequum then, makes the Ni-Mo co-impregnated solution;
(3), adopt the equivalent impregnation method that carrier is immersed in the Ni-Mo co-impregnated solution, dip time 3～12 hours, in 110～150 ℃ of oven dry down, 400～600 ℃ of following roastings 4～8 hours make Ni, Mo content and are respectively 1～6% and 2～10% catalyst.
6. Preparation of catalysts method according to claim 5 is characterized in that: the concentration of the ammonia spirit described in (2) step is 12～18%; The addition of ethylenediamine is 1/15～1/8 of a nickel salt.
7. the described Preparation of catalysts method that is used for crude benzole hydrogenation desulfurization removing nitric producing refined benzene of claim 3 comprises the steps:
(1), with weight ratio is the Mg (NO of 0.5～10:1
3)
2Be dissolved in the deionized water with red fuming nitric acid (RFNA), the back adding that stirs accounts for the aluminum hydroxide solid elastomer powder of total mixture weight 30～90%, wherein MgO content is 3～15%, add the sesbania powder that accounts for total mixture weight 0.1～10% again, mix aftershaping, in 110～150 ℃ of down oven dry, 300～550 ℃ of following roastings 4～6 hours, promptly make γ-Al
2O
3-MgO carrier;
(2), a certain amount of cobalt salt being joined concentration is in 5～28% the ammonia spirit, under constantly stirring, add a certain amount of citric acid, the amount of citric acid is 1/3～7/4 of a cobalt salt, the molybdenum salt and the phosphate that add aequum then, wherein the weight ratio of molybdenum salt, phosphate and cobalt salt is 9～37:0.5～29:10～40, makes the Co-Mo-P co-impregnated solution;
(3), the γ-Al that adopts the equivalent impregnation method that (1) step is made
2O
3-MgO carrier immerses (2) and goes on foot in the Co-Mo-P co-impregnated solution that makes, and dip time 3～18 hours in 110～150 ℃ of oven dry down, makes catalyst precarsor;
(4), the rare earth metal salt that will account for cobalt salt weight 0.01～0.25 dissolves in the deionized water, under constantly stirring, add a certain amount of citric acid, the amount of citric acid is 1/3～7/4 of a cobalt salt, then the catalyst precarsor that makes is impregnated in this solution, dip time 3～12 hours, in 400～600 ℃ of following roastings 4～8 hours, make Co, Mo, rare earth metal, P content and be respectively 2～8%, 5～20%, 0.01～1% and 0.1～6% catalyst under the blanket of nitrogen.
8. Preparation of catalysts method according to claim 7 is characterized in that: the cobalt salt described in (2) step is selected from cobalt acetate, cobalt nitrate, cobalt chloride or cobalt oxalate; Molybdenum salt is ammonium molybdate; Phosphate is selected from ammonium phosphate, ammonium hydrogen phosphate or ammonium dihydrogen phosphate (ADP); (3) rare earth metal salt described in the step is selected from dysprosium salt, holmium salt and erbium salt.
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| CN101648149B (en) * | 2009-08-24 | 2011-08-31 | 邢台旭阳煤化工有限公司 | High-activity low-dropout hydrofining catalyst of coking crude benzene |
| CN102658160A (en) * | 2012-05-10 | 2012-09-12 | 无锡市强亚耐火材料有限公司 | Crude benzene hydrogenation catalyst and preparation method thereof |
| CN103122260B (en) * | 2013-01-29 | 2015-06-03 | 沈阳三聚凯特催化剂有限公司 | Hydrofining technique of mixture of heavy benzene and absorber oil |
| CN103120943B (en) * | 2013-01-29 | 2014-12-17 | 沈阳三聚凯特催化剂有限公司 | Application of Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| CN103566958B (en) * | 2013-11-12 | 2015-10-28 | 西南化工研究设计院有限公司 | A kind of Catalysts and its preparation method for crude benzole hydrogenation producing refined benzene |
| CN113198500A (en) * | 2021-05-28 | 2021-08-03 | 平顶山市拓青科技有限公司 | Novel crude benzene hydrofining desulfurization and denitrification catalyst and preparation method thereof |
| CN113578337B (en) * | 2021-08-26 | 2023-05-02 | 青岛中瑞泰丰新材料有限公司 | Residual oil hydrogenation catalyst and preparation method and application thereof |
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