CN102206130A - Process for the selective hydrogenation of a carbon-containing fraction - Google Patents
Process for the selective hydrogenation of a carbon-containing fraction Download PDFInfo
- Publication number
- CN102206130A CN102206130A CN2011100860485A CN201110086048A CN102206130A CN 102206130 A CN102206130 A CN 102206130A CN 2011100860485 A CN2011100860485 A CN 2011100860485A CN 201110086048 A CN201110086048 A CN 201110086048A CN 102206130 A CN102206130 A CN 102206130A
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- polymer
- presoma
- catalyst
- selection method
- complexing agent
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Links
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 12
- 230000008569 process Effects 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 56
- 238000002360 preparation method Methods 0.000 claims abstract description 49
- 229910052709 silver Inorganic materials 0.000 claims abstract description 29
- 229920000620 organic polymer Polymers 0.000 claims abstract description 25
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 24
- 239000011148 porous material Substances 0.000 claims abstract description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 50
- 229920000642 polymer Polymers 0.000 claims description 44
- 239000008139 complexing agent Substances 0.000 claims description 33
- 238000005303 weighing Methods 0.000 claims description 26
- 238000010187 selection method Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 125000000524 functional group Chemical group 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 9
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 8
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 8
- 239000005977 Ethylene Substances 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 6
- 238000007306 functionalization reaction Methods 0.000 claims description 6
- 238000005470 impregnation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 5
- 229920002521 macromolecule Polymers 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 5
- 230000000536 complexating effect Effects 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000004230 steam cracking Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000005336 cracking Methods 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims 1
- 239000000292 calcium oxide Substances 0.000 claims 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 1
- 239000000395 magnesium oxide Substances 0.000 claims 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims 1
- 230000002829 reductive effect Effects 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 1
- 239000001569 carbon dioxide Substances 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052737 gold Inorganic materials 0.000 abstract 1
- 239000010931 gold Substances 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 239000004709 Chlorinated polyethylene Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004800 polyvinyl chloride Substances 0.000 description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000007614 solvation Methods 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical group [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 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
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a selective hydrogenation method of carbon dioxide fraction, which adopts a pre-hydrogenation process method of pre-deethanization and is characterized in that a fixed bed reactor is filled with a Pd-Ag catalyst, wherein the Pd-Ag catalyst refers to Al2O3The catalyst is used as a main carrier, Pd and Ag are used as active components of the catalyst, and the Pd content is 0.01-0.04%; the Ag content is 0.02-0.2%, and the specific surface area of the catalyst is 2-20 m2(ii)/g; the pore volume is 0.2-0.35 ml/g, and the catalyst forms organic polymer gold in the preparation processBelongs to a complex. By adopting the method, the reaction can be carried out in an isothermal or adiabatic bed reactor, the energy consumption in the process is greatly reduced, the operation is convenient, the temperature runaway is not easy to occur, and the safety of a reaction system and the economic benefit of a device are improved.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly a kind of C 2 fraction selective hydrogenation removes the method for acetylene.
Background technology
The production of ethene is the tap of petrochemical industry, the selection hydrogenation of acetylene in the steam cracking product, the ethene processing industry there is important role, except the outlet acetylene content that guarantees hydrogenator is up to standard, selectivity of catalyst is good, can make the least possible generation ethane of ethene, significant to the yield of ethene, the raising device economic benefit that improve whole technological process.
In the present C-2-fraction acetylene hydrogenation, Duo employing carbon two front-end hydrogenation technologies more and more, the characteristics of this technology are that hydrogenator is before demethanizing tower, therefore a large amount of hydrogen arranged in reaction mass, it is particularly important that selectivity of catalyst shows, otherwise can be owing to more ethylene hydrogenation causes the catalyticreactor temperature runaway.
The front-end hydrogenation method of front-end deethanization, because the content of hydrogen is higher, and does not have C3 fraction in reaction mass, the thermal capacitance of reaction mass is lower, the bed temperature rise is higher than the front-end hydrogenation method of predepropanization.In this case, the catalyzed reaction selectivity is low, and reactor just is easy to take place temperature runaway, and the operation of installing is brought threat.Because the performance limitations of present catalyzer, this technology has to adopt the isothermal bed bioreactor.
The mechanism of this reaction is as follows:
Main reaction
C
2H
2+H
2→C
2H
4 ΔH＝-175.7kJ/mol (1)
Side reaction
C
2H
4+H
2→C
2H
6 ΔH＝-138.1kJ/mol (2)
C
2H
2+2H
2→C
2H
6 (3)
Even when adopting the isothermal bed bioreactor, the selectivity of reaction also can only reach 50～60%, that is to say, react 2 odds and be reaction 1 50% in addition higher, have quite a few conversion of ethylene to become ethane.
Reaction conditions is: 50～110 ℃ of reactor inlet temperatures, reaction pressure 3.0～4.5MPa, gas volume air speed 5000～30000h
-1
Form in the material and be generally C-2-fraction 40～55 (v/v%), acetylene 0.4～1.0% (v/v%), methane 20～30% (v/v%), hydrogen 19～30% (v/v%), CO 0.02～0.2 (v/v%).
When adopting the isothermal bed process, use shell and tube reactor, heat-eliminating medium is arranged, to take away the heat that reaction produces between tubulation.For this processing method, generally adopt methyl alcohol as heat-eliminating medium, its flow must more accurately be controlled, so that the temperature-stable in the reactor is in suitable scope, temperature is crossed the low alkynes that easily takes place to leak, the temperature height is easy temperature runaway again.At the device driving initial stage, the catalyst activity height, to temperature sensitive, especially true.
Patent US 4484015 discloses a kind of catalyzer, and adopting with Pd is main active ingredient, is carrier with the Alpha-alumina, adds promotor silver, with immersion process for preparing carbon two hydrogenation catalysts of excellent property.This catalyzer has the excessive hydrogenation that can effectively reduce ethene, reduces the risk of bed temperature runaway.
Patent US 5587348 is a carrier with the aluminum oxide, adds promotor silver and palladium effect, adds basic metal, and the fluorine of chemical bonding has prepared carbon two hydrogenation catalysts of excellent property.This catalyzer has the green oil of minimizing and generates, improve ethylene selectivity, reduce the characteristics of oxygenatedchemicals growing amount, US 5510550 adopts the method for wet reducing to prepare catalyzer, by in steeping fluid, adding reductive agent, make Pd, Ag solution is not reduced when dry, reduce the active ingredient that solvation effect causes and disperseed problem of non-uniform, prepared the catalyzer of the good adaptation carbon two front-end hydrogenation technologies of selectivity.
Above hydrogenation catalyst all is to adopt aqueous solution preparation, is subjected to the influence of solvation effect in the dipping of catalyzer and drying treatment process, and the metal active constituent presoma is deposited on carrier surface with aggregate form.Because dispersive heterogeneity, high-temperature roasting cause metallics migration gathering easily and form big crystal grain; Influence the repeatability of Preparation of Catalyst, reduce the utilization ratio of active ingredient, adopt the microemulsion method to carry out the preparation of one-component noble metal catalyst in addition among the US 4714692.When adopting this method to prepare multicomponent catalyst, still keep away the influence that unavoidable solvation effect distributes to the catalyst activity component.
Summary of the invention
The object of the present invention is to provide a kind of method of C-2-fraction front-end hydrogenation, a kind of C-2-fraction front-end deethanization front-end hydrogenation processing method particularly is provided,, improved hydrogenation selectivity by selecting to have the catalyzer of complete alloy structure.
The inventor finds that active ingredient Pd, Ag influence the performance of catalyzer greatly in the distribution of catalyst surface, and when Pd, Ag formed alloy, selectivity of catalyst was more excellent.
The selection method of hydrotreating of C-2-fraction of the present invention, adopt the front-end hydrogenation processing method of front-end deethanization, with in the ethylene unit from the overhead product of front-end deethanization tower, select hydrogenation to remove acetylene wherein, this material is with the cracking cut from steam cracking furnace, through over-quenching, washing, behind the oil wash, separate carbon three and carbon two following cuts through the front-end deethanization tower again, carbon two following cuts enter hydrogenator and select hydrogenation, this hydrogenation reaction is (hotbed such as to comprise at fixed bed, adiabatic reactor) reactor carries out, and it is characterized in that being equipped with in the fixed-bed reactor Pd-Ag series catalysts, and the Pd-Ag series catalysts is meant with Al
2O
3Being main carrier, is the activity of such catalysts component with Pd, Ag, and wherein containing Pd content is 0.01～0.04%; Ag content is 0.02～0.2%, and the specific surface area of catalyzer is 2～20m preferably
2/ g; Pore volume is 0.2～0.35ml/g preferably, and this catalyzer has formed the organic polymer metal complex in preparation process.
The preparation method that catalyzer is recommended is: make palladium and silver form the organic polymer metal complex with organic polymer by complexing agent, obtain Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is 2～6h, obtains required catalyzer.
Complexing agent is both can carry out functionalization with the organic macromolecule side-chain radical, ionic complexing agent that can complexing Pd, Ag after reaction again, and the functional group of complexing agent can be amido or two amidos.
Contain on the organic macromolecule side chain of the present invention can with the group of complexing agent reaction, this group can be one or more in halogen, the cyano group.
The acquisition of this catalyzer preferably includes following steps: with organic polymer (polymer) grafted functional group and load on the support of the catalyst, obtain functionalized-polymer/Al by complexing agent
2O
3Presoma; The solution of preparation palladium-Yin has load functionalized-polymer/Al
2O
3Presoma is impregnated in palladium-Yin solution of having prepared and reacts, and palladium, silver are complexed on the functionalized macromolecular chain, and palladium and silver have formed the organic polymer metal complex with organic polymer, obtain Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is 2～6h, obtains required catalyzer.Because this catalyzer has higher selectivity, is not easy to cause temperature runaway, therefore reactor of the present invention both applicable to waiting hotbed, also went for adiabatic reactor, and the use of adiabatic reactor reduces energy consumption of reaction greatly.
The present invention is not limited especially to the bed number of the catalyzer of fixed-bed reactor, single or many all can, two sections beds preferably.
Reaction conditions was when fixed-bed reactor were the isothermal bed bioreactor: 50～110 ℃ of reactor inlet temperatures, reaction pressure 3.0～4.5MPa, gas volume air speed 4000～30000h
-1(referring to single bed bioreactor, as follows).
Reaction conditions was when fixed-bed reactor were the adiabatic reactor reactor: 45～100 ℃ of reactor inlet temperatures, and reaction pressure is preferably 3.0～4.5MPa, and single bed bioreactor gas volume air speed is preferably 5000～25000h
-1
The method of hydrotreating that the present invention proposes, the Preparation of catalysts method that is adopted can be: will have the macromolecular material uniform loading of reactive group on the side chain on support of the catalyst, by complexing agent grafted functional group on the macromolecular chain of institute's load, described functional group can form complexing ion with the ion of Pd, Ag, can also be earlier by complexing agent with the organic polymer grafted functionalization after, be carried on the support of the catalyst again; The solution of preparation palladium-Yin has functionalized high molecular precursor to be impregnated in the solution of the palladium-Yin that has prepared load, reacts under certain conditions, makes palladium, silver-colored network and to the macromolecular chain of load.Can also be added in the palladium-Yin solution of preparation after with the organic polymer grafted functionalization by complexing agent, again load carriers.Because complex reaction is the chemical reaction of complex-metal ion, metal ion is by chemical reaction but not physical adsorption is attached on the macromolecular chain, therefore the atom of palladium, silver is uniform sequential distribution on macromolecular chain, in the process of roasting, palladium-silver atoms can carry out oxidizing reaction in position, in the process of oxidizing reaction, form the oxide eutectic of palladium, silver.
Catalyzer prepared by this method has overcome the dispersive influence to palladium-Yin of steeping fluid surface tension and solvation effect, possesses excellent selectivity.
Preparation of Catalyst of the present invention can adopt following process to implement, this process can be divided into 3 the step carry out:
(1). at first prepare functionalized-polymer/Al
2O
3Presoma;
(2). preparation Pd-Ag-polymer/Al
2O
3Presoma;
(3). carry out roasting 2～6h at 380～550 ℃ of presomas to step 2 preparation.
This Preparation of catalysts method of recommending comprises the steps:
A. functionalized-polymer/Al
2O
3The preparation of presoma
Organic polymer is dissolved in the organic solvent, forms macromolecular solution, again with carrier impregnation in above-mentioned solution, leave standstill and make organic polymer (polymer) be deposited on Al
2O
3The surface, drying; Add the complexing agent backflow 0.5～300min that contains functional group again, prepare functionalized-polymer/Al
2O
3Presoma;
More specifically method as: under 20～35 ℃, the organic polymer that has reactive group on the side chain is dissolved in the organic solvent, carrier impregnation in above-mentioned solution, is left standstill 2～6h, make described polymer be deposited on Al
2O
3The surface after the drying, adds complexing agent down at 20～35 ℃.Described complexing agent both can carry out functionalization with the organic macromolecule side-chain radical, and ion that can complexing Pd, Ag after reaction again with the above-mentioned solution 1～4h that refluxes, is cooled to 20～35 ℃, uses deionized water wash, drying.
Have reactive group on the described side chain of organic polymer and be meant that polymer side chain contains halogen, the polymer of groups such as cyano group, as polyvinyl chloride (PVC), polystyrene vinyl cyanide (SAN) etc., described complexing agent is for providing the micromolecular compound of amido or two amido functional groups, can be Dyhard RU 100, thanomin, quadrol or oxammonium hydrochloride can be wherein one or more; In mole number, the reactive group mole number preferably 100～1 in complexing agent mole number/polymer;
B. (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Preparation palladium-Yin solution, and, take by weighing the functionalized-polymer/Al that has prepared with inorganic acid for adjusting pH value 1～4
2O
3Presoma joins the solution of preparing palladium-Yin on the precursor, and 20～35 ℃ flood 5～30min down, and washing, drying obtain Pd-Ag-polymer/Al
2O
3Presoma; The mole number of functional group's mole number on the macromolecular chain of functionalized back/(Pd+Ag) preferably 100～1.
C. Preparation of catalysts
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h obtain (Pd-Ag)/Al
2O
3Catalyzer.
Above-mentioned roasting can be carried out in oxygen atmosphere is arranged, and effect is better.
When catalyzer used, the catalyzer that above method can be made used H in reactor
2Reduce processing, obtain going back the ortho states catalyzer.
Polymer of the present invention is the polymer that contains reactive group on the side chain, and described reactive group is preferably cyano group or chlorine atom.
Described complexing agent is to carry out graft reaction with above-mentioned reactive group, and the molecule that can carry out complex reaction with palladium, silver ions.Specifically can be Dyhard RU 100, thanomin, quadrol, oxammonium hydrochloride etc.
The mole number of functional group's mole number on the macromolecular chain of functionalized back/(Pd+Ag) preferably 100～1, the mole number of reactive group-CN among concrete example such as the SAN (cyanogen root) mole number/(Pd+Ag) preferably 100～1.The mole number of complexing agent mole number/(Pd+Ag) preferably 10000～1.
Add solvent be in steps A for polymer is dissolved fully, to help the absorption of polymer on carrier, solvent can be tetrahydrofuran (THF) (THF), toluene, dimethyl formamide (DMF) equal solvent.The add-on of solvent what, mainly be that control institute solubilizing agent can make polymer dissolve fully to get final product.
In step B, palladium, silver salt consumption in the solution of described preparation palladium-Yin, with Pd, the Ag content that can make final catalyst, wherein to be preferably in be 0.01～0.4% to Pd, Ag content preferably 0.02～0.2%.
Using plasma emission spectrometer or atomic absorption spectrum can record this catalyst P d content and Ag content (standard GB/T 15337-94).
The inventor also finds, when adopting method of hydrotreating of the present invention, under isothermal bed process condition, catalyzer can move moving than traditional catalyst under the much lower condition of desired minimum safe air speed, improve the security of technological operation greatly, improved the level of safety of device operation.After adopting this catalyzer, the safe air speed of device can be reduced to 4000h
-1
The inventor finds, adopt method of hydrotreating of the present invention after, can change traditional isothermal bed bioreactor into the adiabatic reactor reactor, reduce the consumption of energy, simplified the operation of reactor greatly, improve reliability, significant to the steady running that improves device.
Description of drawings
Fig. 1 is the carbon two front-end hydrogenation technical process of front-end deethanization technology.
Among the figure: 1---oil scrubber; 2---water wash column; 3---alkali is inhaled tower; 4---drying tower; 5---the front-end deethanization tower; 6---carbon two hydrogenators; 7---demethanizing tower.
Embodiment
Analytical procedure and standard:
Specific surface area: GB/T-5816
Pore volume: GB/T-5816
Catalyst P d, Ag assay: use plasma emission spectrometer to record.
The selectivity method of calculation:
Ethylene selectivity: S=1-| Δ ethane/Δ acetylene |
Embodiment 1
Preparation of catalysts
A, functionalized PVC/Al
2O
3Preparation
Take by weighing Φ 4mm, length is 4mm, and specific surface area is 15m
2/ g, pore volume are the column Al of 0.25ml/g
2O
3Carrier 250g.
PVC4.45g is dissolved in the 400ml tetrahydrofuran (THF) (THF) fully, and 0.5h in the above-mentioned solution makes PVC be deposited on Al with the carrier impregnation that weighed up
2O
3The surface, inclining raffinate, and drying obtains 208gPVC/Al
2O
3Product.
Add 59.64g Dyhard RU 100 and 2.0gNa
2CO
3, add 208g PVC/Al
2O
3Refluxed 2 hours, and be cooled to room temperature, extremely neutral with deionized water wash, drying for standby.Obtain functionalized PVC/Al
2O
3Reactive group Cl mole number=10 on complexing agent Dyhard RU 100 mole number/macromolecular chain.
B, (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Take by weighing 0.077gPd (NO
3)
2, 0.08gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing the functionalized-polymer/Al that has prepared
2O
3Presoma 254.45g is with functionalized-polymer/Al
2O
3Join Pd (NO
3)
2, Ag NO
3Mixing solutions in, absorption 0.5h, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-polymer/Al
2O
3Presoma, mole number=100 of reactive group Cl mole number on the macromolecular chain/(Pd+Ag)).
C, Preparation of catalysts
With the presoma of above-mentioned preparation, 550 ℃ of roasting 4h obtain oxidation state Pd-Ag/Al in air atmosphere
2O
3Catalyzer is positioned over before the use in the reaction unit, is N with mol ratio
2: H
2=1: 1 mixed gas, 120 ℃ of temperature, 12h is handled in reduction.Recording this catalyst P d content is 0.01%, and Ag content is 0.02%.
Comparative Examples 1
Take by weighing Φ 4mm, length is 4mm, and specific surface area is 15m
2/ g, pore volume are the column Al of 0.25ml/g
2O
3Carrier 250g.
Take by weighing 0.077gPd (NO
3)
2, 0.08gAg NO
3, measure 0.5ml nitric acid, be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, ultrasonic vibrations 0.5h, dry back obtains Pd-Ag/Al at 550 ℃ of roasting temperature 4h
2O
3Catalyzer.Being positioned over before the use in the reaction unit, is N with mol ratio
2: H
2=1: 1 mixed gas, 120 ℃ of temperature, 12h is handled in reduction.Recording this catalyst P d content is 0.01%, and Ag content is 0.02%.
Reaction raw materials: from the front-end deethanization column overhead, material is formed as table 1.
Table 1 reaction raw materials is formed
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C + 3 |
| Content (V%) | 19 | 1.0 | 46 | 8. | 25.5 | 0.2 | 0.3 |
Reaction conditions 1: adopt two sections isothermal bed bioreactors; Single hop reactor content volume space velocity 8000h
-1, working pressure 3.0MPa, each section reactor catalyst loadings 800ml.
Two sections isothermal bed bioreactors of table 2 are average result after reaction in 800 hours
Reaction conditions 2: adopt two sections adiabatic reactor reactors; Single hop reactor content volume space velocity 7000h
-1, working pressure 3.0MPa, each section reactor catalyst loadings 700ml.
Reaction result is as follows:
Two sections adiabatic reactor reactors of table 3 are average result after reaction in 800 hours
Find out that from embodiment 1 under same reaction conditions, adopt processing method of the present invention, its reactive activity and selectivity all are better than traditional method.
Embodiment 2
Catalyzer adopts method preparation of the present invention.
A, functionalized SAN/Al
2O
3Preparation
Take by weighing Φ 4.5 * 4.5mm, specific surface area is 20m
2/ g, pore volume are the cylindrical vector 250g of 0.35ml/g, wherein contain Al
2O
3200g, TiO
250g.
Take by weighing SAN resin 1.1g, be dissolved in 300ml dimethyl formamide (DMF) solvent, stirring is dissolved the SAN resin fully under the room temperature, adds the above-mentioned carrier of weighing in this solution, leaves standstill 1 hour after fully stirring, and separates the solvent after drying, obtains SAN/ (Al
2O
3+ TiO
2).
With the above-mentioned SAN/ (Al that obtains
2O
3+ TiO
2), join in the 500ml deionized water, add the 28.8g quadrol, back flow reaction 1h, product is taken out in the cooling back, and washing is to neutral, and drying obtains functionalized SAN/ (Al
2O
3+ TiO
2) presoma.Reactive group Cl mole number=19 on the mole number/macromolecular chain of complexing agent quadrol.
B (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Take by weighing 0.22gPd (NO
3)
2, 0.4gAg NO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing the functionalized-SAN/Al that has prepared
2O
3+ TiO
2Presoma 251.1g is with functionalized polymer/Al
2O
3+ TiO
2Join Pd (NO
3)
2, Ag NO
3Mixing solutions in, absorption 6h, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag) polymer/Al
2O
3+ TiO
2Presoma, mole number=54.71 of reactive group CN mole number on the macromolecular chain/(Pd+Ag).
The C Preparation of catalysts
With the presoma of above-mentioned preparation, 380 ℃ of roasting 6h obtain (Pd-Ag)/Al in air atmosphere
2O
3+ TiO
2Catalyzer, recording this catalyst P d content is 0.04%, Ag content is 0.1%.
Comparative Examples 2:
Method according to patent US 4484015 embodiment 1.
Take by weighing Φ 4.5 * 4.5mm, specific surface area is 20m
2/ g, pore volume are 0.35ml/g
3Cylindrical vector 250g, wherein contain Al
2O
3200g, TiO
250g.
Take by weighing 0.22gPd (NO
3)
2Being dissolved in the 100ml deionized water, is 2.8 with the pH value of dilute hydrochloric acid regulator solution, and described carrier impregnation in the solution that has prepared, 120 ℃ of dryings 10 hours, is obtained catalyst A.
Take by weighing 0.4gAg NO
3, measure 0.5ml nitric acid and be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, absorption 1h, dry back obtains (Pd-Ag)/(Al at 380 ℃ of roasting temperature 8h
2O
3+ TiO
2) catalyzer.Recording this catalyst P d content is 0.04%, and Ag content is 0.1%.Reaction mass: from the front-end deethanization column overhead, raw material is formed as table 4.
Table 4 hydrogenating materials is formed
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C + 3 |
| Content (V%) | 23.64 | 0.73 | 44 | 7.5 | 24. | 0.1 | 0.3 |
Reaction conditions 1: adopt two sections isothermal bed bioreactors; Single hop volume of material air speed: 4000h
-1, working pressure: 2.5MPa, each section reactor catalyst loadings: 500ml.
Two sections isothermal bed bioreactors of table 5 were through 200 hours reaction results
2: two sections adiabatic reactor reactors of reaction conditions; Single hop reactor content volume space velocity: 5000h
-1, working pressure: 2.5MPa, each section reactor catalyst loadings: 700ml.
Two sections adiabatic reactor reactors of table 6 were through 200 hours reaction average results
Can find out from the above embodiments and Comparative Examples, when adopting catalyzer of the present invention, the isothermal bed bioreactor can be changed into the adiabatic reactor reactor.Equity hotbed reactor can drop to 4000h with air speed
-1
Embodiment 3
Preparation of catalysts adopts method of the present invention to be prepared.
A, functionalized SAN/Al
2O
3Preparation
Take by weighing 4.0 * 4.0mm, specific surface area is 2m
2/ g, pore volume are the cylindric Al of 0.2ml/g
2O
3Carrier 250g.
Take by weighing SAN resin 25g, be dissolved in the 300ml DMF solvent, stirring is dissolved the SAN resin fully under the room temperature, adds the 20g oxammonium hydrochloride, adds 5gK
2CO
3, be heated to it and dissolve fully.After stirring half an hour, carrier 250g is added above solution, drip 200ml ethanol, and constantly stir, take out product after 1 hour, washing obtains functionalized SAN/Al to neutral after the drying
2O
3Reactive group CN mole number=1.21 on complexing agent oxammonium hydrochloride mole number/macromolecular chain.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take by weighing 0.11gPd (NO
3)
2, 0.8gAg NO
3, 3.17gK
2CO
3, be mixed with the mixing solutions of 1200ml, take by weighing the functionalized-SAN/Al that has prepared
2O
3Presoma 258g joins Pd (NO
3)
2, Ag NO
3Mixing solutions in, behind the absorption 1h, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-polymer/Al
2O
3Presoma.Mole number=90.53 of reactive group CN mole number on the macromolecular chain/(Pd+Ag).
C, Preparation of catalysts
With the presoma of above-mentioned preparation, 550 ℃ of roasting 2h obtain Pd-Ag/Al in air atmosphere
2O
3Catalyzer.Recording this catalyst P d content is 0.02%, and Ag content is 0.2%.
Comparative Examples 3
Take by weighing 4.0 * 4.0mm, specific surface area is 2m
2/ g, pore volume are the cylindric Al of 0.2ml/g
2O
3Carrier vector 250g.
Take by weighing 0.11g Pd (NO
3)
22H
2O is dissolved in the 235ml deionized water.
In the above-mentioned solution behind the 1h, inclining raffinate, at 120 ℃ of dry 3h, obtains catalyst A with carrier impregnation.
Take by weighing 0.8gAgNO
3, be dissolved in the 225ml deionized water, be 2.5 with rare nitre acid for adjusting pH value.Above-mentioned catalyst A be impregnated in the solution that has prepared, place the vibration still, behind the vibration 30min, take out at 120 ℃ of dry 2h, at 550 ℃ of roasting temperature 8h.
Recording this catalyst P d content is 0.02%, and Ag content is 0.2%, and the total metal dispersity of Pd and Ag is 5.2%.
Embodiment 4
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 20.m
2/ g, pore volume are 0.35ml/g, and bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
The preparation of A, functionalized chlorinatedpolyethylene (CPE)
CPE 8.0g is dissolved among the 400mlTHF fully, adds 240g Dyhard RU 100 and 2.0gNa
2CO
3, refluxed 2 hours, be cooled to room temperature, obtain functionalized CPE solution for standby.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take by weighing 0.11gPd (NO
3)
2, 0.47gAgNO
3, measure 0.5ml nitric acid, join in the above-mentioned functionalized CPE solution, stir 0.5h, obtain (Pd-Ag)-polymer.
The 250g carrier is added in the mixing solutions, leave standstill 1h after fully stirring, above-mentioned product is extremely neutral with deionized water wash.Obtain (Pd-Ag)-polymer/Al
2O
3Presoma.
C, Preparation of catalysts
With the presoma of above-mentioned preparation, 500 ℃ of roasting 4h in air atmosphere obtain oxidation state (Pd-Ag)/Al
2O
3Catalyzer.Being positioned over before the use in the fixed-bed reactor, is N with mol ratio
2: H
2=0.1: 1 mixed gas, 120 ℃ of temperature, 12h is handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is 0.02%, and Ag content is 0.1%.
Comparative Examples 4
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 20.m
2/ g, pore volume are 0.35ml/g, and bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
Take by weighing 0.11gPd (NO
3)
2, 0.47gAgNO3 adds 0.5ml nitric acid, prepare 87.5ml solution, with the concussion 0.5 hour to the above-mentioned carrier of this solution spraying, after the drying, 500 ℃ of roasting 4h obtain (Pd-Ag)/Al in air atmosphere
2O
3Catalyzer.Recording this catalyst P d content is 0.02%, and Ag content is 0.1%.
Reaction mass: from the front-end deethanization column overhead, raw material is formed as table 7.
Table 7 hydrogenating materials is formed
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C 4 + |
| Content (v/v%) | 30 | 0.4 | 33.4 | 5.88 | 30 | 0.02 | 0.3 |
Reaction conditions 1: adopt the front-end deethanization front-end hydrogenation technology shown in the accompanying drawing 1, single hop isothermal bed bioreactor, the material air speed is 30000h
-1, working pressure is 4.5MPa, loaded catalyst is 300ml.
Table 8 single hop isothermal bed bioreactor reaction in 600 hours average result
Reaction conditions 2: single hop adiabatic reactor reactor, material air speed are 25000h
-1, working pressure is 4.5MPa, loaded catalyst is 300ml.
Table 9 single hop adiabatic reactor reactor reaction in 600 hours average result
From above embodiment as can be seen, adopt method of the present invention after, the selectivity of C-2-fraction hydrogenation reaction increases substantially.
Claims (17)
1. the selection method of hydrotreating of a C-2-fraction, adopt the front-end hydrogenation processing method of front-end deethanization, with in the ethylene unit from the overhead product of front-end deethanization tower, select hydrogenation to remove acetylene wherein, this material is with the cracking cut from steam cracking furnace, through over-quenching, washing, behind the oil wash, separate carbon three and carbon two following cuts through the front-end deethanization tower again, carbon two following cuts enter hydrogenator and select hydrogenation, and this hydrogenation reaction is carried out at fixed-bed reactor, it is characterized in that being equipped with in the fixed-bed reactor Pd-Ag series catalysts, the Pd-Ag series catalysts is meant with Al
2O
3Being main carrier, is the activity of such catalysts component with Pd, Ag, and wherein containing Pd content is 0.01～0.04%; Ag content is 0.02～0.2%, and the specific surface area of catalyzer is 2～20m
2/ g; Pore volume is 0.2～0.35ml/g, and this catalyzer has formed the organic polymer metal complex in preparation process.
2. selection method of hydrotreating according to claim 1 is characterized in that catalyzer is to make palladium and silver form the organic polymer metal complex with organic polymer by complexing agent, obtains Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is that 2～6h obtains.
3. selection method of hydrotreating according to claim 2 is characterized in that complexing agent is both can carry out functionalization with high molecular side-chain radical, again ionic complexing agent that can complexing Pd, Ag after reaction.
4. selection method of hydrotreating according to claim 3 is characterized in that the contained functional group of complexing agent can be amido or two amidos.
5. selection method of hydrotreating according to claim 2, it is characterized in that containing on the organic macromolecule side chain can with the group of complexing agent reaction.
6. selection method of hydrotreating according to claim 5, it is characterized in that containing on the organic macromolecule side chain can be in halogen, the cyano group one or more with the group of complexing agent reaction.
7. selection method of hydrotreating according to claim 1, the acquisition that it is characterized in that catalyzer comprise the steps: by complexing agent to obtain functionalized-polymer/Al with the organic polymer grafted functional group and load on the support of the catalyst
2O
3Presoma; The solution of preparation palladium-Yin has load functionalized-polymer/Al
2O
3Presoma is impregnated in palladium-Yin solution of having prepared and reacts, and palladium, silver are complexed on the functionalized macromolecular chain, and palladium and silver have formed the organic polymer metal complex with organic polymer, obtain Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is 2～6h.
8. selection method of hydrotreating according to claim 1, when it is characterized in that fixed-bed reactor are the isothermal bed bioreactor, reaction conditions is: 50～110 ℃ of reactor inlet temperatures, reaction pressure 3.5～4.5MPa, single bed bioreactor gas volume air speed 4000～30000h
-1
9. selection method of hydrotreating according to claim 1, reaction conditions is when it is characterized in that fixed-bed reactor are the adiabatic reactor reactor: 45～100 ℃ of reactor inlet temperatures, reaction pressure is preferably 3.0～4.5MPa, and single bed bioreactor gas volume air speed is preferably 5000～25000h
-1
10. selection method of hydrotreating according to claim 1 is characterized in that carrier is Al
2O
3Or Al
2O
3In be doped with other hopcalite, other oxide compound is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.
11. selection method of hydrotreating according to claim 10 is characterized in that Al
2O
3Crystal formation be that θ, α or its mix crystal formation.
12. selection method of hydrotreating according to claim 7, when it is characterized in that Preparation of Catalyst, by complexing agent with the organic polymer grafted functional group and load on the support of the catalyst, be meant: organic polymer is loaded on the support of the catalyst, then by complexing agent grafted functional group on the macromolecular chain of institute's load.
13. selection method of hydrotreating according to claim 7, when it is characterized in that Preparation of Catalyst, by complexing agent with the organic polymer grafted functional group and load on the support of the catalyst, be meant: first with after the organic polymer grafted functionalization by complexing agent, be carried on again on the support of the catalyst, prepare functionalized-polymer/Al
2O
3Presoma.
14. selection method of hydrotreating according to claim 7 is characterized in that the acquisition of catalyzer comprises the steps: that the Preparation of catalysts method comprises the steps:
A. functionalized-polymer/Al
2O
3The preparation of presoma
Organic polymer is dissolved in the organic solvent, forms macromolecular solution, again with carrier impregnation in above-mentioned solution, leave standstill and make organic polymer be deposited on Al
2O
3The surface, drying; Add the complexing agent backflow 0.5～300min that contains functional group again, prepare functionalized-polymer/Al
2O
3Presoma;
B.Pd-Ag-high-molecular complex/Al
2O
3The preparation of presoma
Preparation palladium-Yin solution, and, take by weighing the functionalized-polymer/Al that has prepared with inorganic acid for adjusting pH value 1～4
2O
3Presoma joins the solution of preparing palladium-Yin on the precursor, and 20～35 ℃ flood 5～30min down, and washing, drying obtain Pd-Ag-high-molecular complex/Al
2O
3Presoma;
C. Preparation of catalysts
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h obtain Pd-Ag/Al
2O
3Catalyzer.
15. selection method of hydrotreating according to claim 14, it is characterized in that on the macromolecular chain of functionalized back functional group's mole number/(Pd+Ag) mole number is 100～1.
16. selection method of hydrotreating according to claim 14 is characterized in that in mole number, the reactive group mole number is 100～1 in complexing agent mole number/polymer.
17. selection method of hydrotreating according to claim 14 is characterized in that the mole number of complexing agent mole number/(Pd+Ag) is 10000～1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2792645B1 (en) * | 1999-04-26 | 2003-06-13 | Inst Francais Du Petrole | PROCESS FOR THE SELECTIVE HYDROGENATION OF UNSATURATED COMPOUNDS IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL AND AN ADDITIONAL IV METAL INTRODUCED IN THE FORM OF A HYDROSOLUBLE ORGANOMETALLIC COMPOUND |
| CN101906014A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | Selective hydrogenation method for carbon-containing fraction |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for carbon-dioxide fraction |
| CN101913976A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Process for the selective hydrogenation of a carbon-containing fraction |
-
2011
- 2011-04-07 CN CN2011100860485A patent/CN102206130B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2792645B1 (en) * | 1999-04-26 | 2003-06-13 | Inst Francais Du Petrole | PROCESS FOR THE SELECTIVE HYDROGENATION OF UNSATURATED COMPOUNDS IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL AND AN ADDITIONAL IV METAL INTRODUCED IN THE FORM OF A HYDROSOLUBLE ORGANOMETALLIC COMPOUND |
| CN101906014A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | Selective hydrogenation method for carbon-containing fraction |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for carbon-dioxide fraction |
| CN101913976A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Process for the selective hydrogenation of a carbon-containing fraction |
Non-Patent Citations (3)
| Title |
|---|
| 《催化学报》 20060228 王寰等 以Beta-环糊精为介质的高分散钯催化剂的制备及其催化性能 第27卷, 第02期 * |
| 徐筠等: "负载型钯催化剂用于不饱和化合物的加氢反应", 《应用化学》, vol. 5, no. 05, 31 December 1988 (1988-12-31) * |
| 王寰等: "以Β-环糊精为介质的高分散钯催化剂的制备及其催化性能", 《催化学报》, vol. 27, no. 02, 28 February 2006 (2006-02-28) * |
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