CN105732269A - Selective hydrogenation method for carbon two-fraction in sequential separation process - Google Patents
Selective hydrogenation method for carbon two-fraction in sequential separation process Download PDFInfo
- Publication number
- CN105732269A CN105732269A CN201410771389.XA CN201410771389A CN105732269A CN 105732269 A CN105732269 A CN 105732269A CN 201410771389 A CN201410771389 A CN 201410771389A CN 105732269 A CN105732269 A CN 105732269A
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- catalyst
- reactor
- bipyridyl
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 50
- 238000000926 separation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 50
- 239000003054 catalyst Substances 0.000 claims abstract description 108
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 86
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 60
- 229910052593 corundum Inorganic materials 0.000 claims description 57
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 57
- 239000010931 gold Substances 0.000 claims description 43
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 229910052737 gold Inorganic materials 0.000 claims description 31
- MWPGSUYGVCNVKP-UHFFFAOYSA-N 2-pyridin-2-ylpyridin-3-ol Chemical group OC1=CC=CN=C1C1=CC=CC=N1 MWPGSUYGVCNVKP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 17
- 238000010187 selection method Methods 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 12
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- -1 hydroxyl bipyridyl forms metal complex Chemical class 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 4
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- DDYSHSNGZNCTKB-UHFFFAOYSA-N gold(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Au+3].[Au+3] DDYSHSNGZNCTKB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 15
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 4
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract 2
- 239000001569 carbon dioxide Substances 0.000 abstract 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 238000005303 weighing Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- 230000008569 process Effects 0.000 description 12
- 238000005470 impregnation Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000000956 alloy Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 7
- 239000004800 polyvinyl chloride Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 6
- 230000001476 alcoholic effect Effects 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 229920002521 macromolecule Polymers 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- GALBDYCQIHJLFP-UHFFFAOYSA-N 2-pyridin-2-yl-3H-pyridine-4,4-diol Chemical group C1=CC(O)(O)CC(C=2N=CC=CC=2)=N1 GALBDYCQIHJLFP-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000006471 dimerization reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NPOJSRFZNPCHGN-UHFFFAOYSA-N 5-(6-oxo-1h-pyridin-3-yl)-1h-pyridin-2-one Chemical group C1=NC(O)=CC=C1C1=CC=C(O)N=C1 NPOJSRFZNPCHGN-UHFFFAOYSA-N 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- DDHGHUCXYQKHDF-UHFFFAOYSA-N 3-hydroxy-2-pyridin-2-yl-1H-pyridin-4-one Chemical group OC1=CC=NC(C=2N=CC=CC=2)=C1O DDHGHUCXYQKHDF-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 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
- Y02P20/141—Feedstock
-
- 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 relates to a carbon two selective hydrogenation method in a sequential separation process, wherein a fixed bed reactor for hydrogenation is positioned behind a demethanizer, and a carbon dioxide material from a front deethanizer in an ethylene device is pressurized, hydrogen is added, and then the carbon dioxide material enters an adiabatic bed reactor for selective hydrogenation, and the method is characterized in that: Pd-Au series catalyst is filled in the fixed bed reactor, and in the preparation process of the catalyst, an alumina series carrier is combined with a bipyridyl derivative with hydroxyl, and the hydroxyl bipyridyl combined on the carrier and an active component form a metal complex; the method of the present invention has greatly improved hydrogenation activity and selectivity, obviously raised ethylene increment and greatly reduced green oil yield. Meanwhile, the reduction of the green oil ensures that the active center of the catalyst is not covered by the by-product, and the activity and the selectivity of the catalyst are well maintained.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly in a kind of order separation process, carbon two selects method of hydrotreating.
Background technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the most basic raw materials of downstream polymerisation device.Wherein ethylene processing industry is had extremely important impact by the selection hydrogenation of acetylene, except the outlet acetylene content of guarantee hydrogenation reactor is up to standard, selectivity of catalyst is excellent, the generation ethane that ethylene is the least possible can be made, to the yield of ethene improving whole technical process, improve device economic benefit significant.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%-2.5%, when producing polyethylene, a small amount of acetylene in ethylene can reduce the activity of polymerization catalyst, and make the deterioration in physical properties of polymer, so the acetylene content in ethylene must be dropped to certain limit, could as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are one of processes important in ethylene unit flow process.
In ethylene unit, catalysis selective hydrogenation includes being divided into front-end hydrogenation and back end hydrogenation, ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene hydrogenation reactor is for domethanizing column position, hydrogenation reactor is front-end hydrogenation before being positioned at domethanizing column, and hydrogenation reactor is back end hydrogenation after being positioned at domethanizing column.Back end hydrogenation is order separation process, and the advantage of technique is that hydrogenation process control device is many, and not easily temperature runaway is easy to operate, but the shortcoming easy coking that is catalyst, the reproduction ratio of catalyst is more frequent.Its reason is in hydrogenation process, owing to the amount of allocating into of hydrogen is few, it is easy to the hydrogenation dimerization reaction of acetylene occurs, and generates 1,3-butadiene, and generates the oligomer that molecular weight is wider further, is commonly called as " green oil ".Green oil is adsorbed on catalyst surface, and forms coking further, blocks catalyst duct, makes catalyst activity and selectivity decline.
Current carbon two back end hydrogenation mainly adopts two sections or three sections of reactors in series techniques, the device that air speed is relatively low or alkynes content is low, it is possible to adopt two reactor series connection.Current commercial plant, mainly based on three sections of reactors in series techniques.
Back end hydrogenation material generally consists of: the acetylene of 1.0～2.2% (v), the ethylene of 65～85%, and all the other are ethane, and hydrogen is by allocating into after measuring.
This reaction is exothermic reaction, but temperature rise is relatively low, according to air speed size, single reactor maximum temperature rise from 30～60 DEG C not etc., so substantially adopting adiabatic reactor.
To two reactor, first paragraph reactor requires to convert the acetylene of more than 70%, and remaining acetylene is converted to its content less than 1 μ L/L by second segment reactor.
Air speed is higher or that acetylene content is higher device, is generally adopted three sections of reactor process, and first paragraph converts about 50%, and all the other two sections convert remaining acetylene, and three sections of reactor outlet acetylene contents are less than 1 μ L/L.
The amount of allocating into of hydrogen is relevant with acetylene content and employing technique.To three sections of reactor process, general first paragraph reactor hydrogen/acetylene is 0.8～1.2, and second segment reactor hydrogen/acetylene is 1～1.5, and the 3rd section of reactor hydrogen/acetylene is 1.5～3.
To two reactor technique, general first paragraph reactor hydrogen/acetylene is 1～1.5, and second segment reactor hydrogen/acetylene is 2～4.
This reaction mechanism is as follows:
Primary response C2H2+H2→C2H4Δ H=-175.7kJ/mol (1)
Side reaction
C2H4+H2→C2H6Δ H=-138.1kJ/mol (2)
C2H2+2H2→C2H6(3)
2C2H2+H2→C4H6(4)
C2H2+nC2H2+H2→C2n+2H2n+4(5)
In these are answered, reaction (1) is acetylene hydrogenation, and reaction (2) and (3) is ethylene hydrogenation.Reaction (4) is the hydrogenation dimerization of acetylene, has important contribution, reaction (5) to be the General reactions formulas generating green oil to generating green oil.
In these reactions, only respond (1) is desirable to the reaction occurred, and all the other are all undesirable reactions.
US5856262 reports with the modified silicon oxide of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) for carrier, and the method for preparation low in acidity palladium catalyst, at air speed 3000h-1, inlet temperature 35 DEG C, entrance acetylene molar fraction 0.71%, when hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity reaches 56%.Patent US4404124, with aluminium oxide for carrier, adds promoter silver and palladium effect, is prepared for the C2 hydrogenation catalyst of function admirable.This catalyst has minimizing ethane growing amount, it is suppressed that is adsorbed on the acetylene on catalyst surface and carries out partial hydrogenation dimerization reaction, it is suppressed that 1,3-butadiene generates, and reduces green oil and generates, improves ethylene selectivity, reduce the feature of oxygenatedchemicals growing amount, be applied widely in ethylene industry.But, above-mentioned catalyst all adopts infusion process to prepare, and by the restriction of preparation method, metal dispersity is only about 30%, and catalyst performance there is also many deficiencies, still has necessity of improvement further.
Traditional Pd-Ag bimetallic selective hydrogenation catalyst is all adopt aqueous impregnation method to prepare.When adopting sub-dip method, what a kind of component can be more is enriched in carrier surface, and another kind of component is enriched in outer surface, and only part metals atom interpenetrates, and defines alloy structure.Meanwhile, adopt total immersion method, owing to the presoma of two metal ion species and the interaction of carrier are different, and surface tension and solvation, it is hardly formed the uniform load of two kinds of components, also can only partly form alloy structure.When this catalyst is applied to C 2 fraction selective hydrogenation, often better at initial reaction stage selectivity, with the prolongation of the time of operation, selectivity constantly declines, and generally runs 3～6 months and is accomplished by regeneration, and economic loss is bigger.
CN201110086174.0 by adsorbing specific macromolecular compound on carrier, macromolecule wrapped layer is formed at carrier surface certain thickness, with with the compound of function base and high molecular weight reactive, can with the function base of active component complexation so as to have, on carrier surface function base, complex reaction is there is, it is ensured that active component is in order and high degree of dispersion by active component.Adopting this patented method, the specific macromolecular compound of carrier adsorption carries out chemisorbed by the hydroxyl of aluminium oxide and macromolecule, and the amount of carrier adsorption macromolecular compound is subjected to the hydroxyl value quantitative limitation of aluminium oxide；Not strong with the complexing of Pd through the macromolecule of functionalization, activity component load quantity does not reach requirement sometimes, goes back residual fraction active component in impregnation liquid, causes catalyst cost to improve；Adopt the method to prepare C2 hydrogenation catalyst and there is also the shortcoming that technological process is complicated.
In recent years, the requirement of C2 hydrogenation catalyst is improved by ethylene unit day by day, it is desirable to catalyst at a lower reaction temperature, has activity and the selectivity of excellence, to reach to save energy and reduce the cost, improves device ethylene increment, thus reaching to improve the purpose of device economic benefit.
Summary of the invention
It is an object of the invention to provide carbon two in a kind of order separation process and select method of hydrotreating, by selecting active component high degree of dispersion, there is the Pd-Au catalyst of height alloy structure, improve hydrogenation selectivity, improve ethylene increment, improve plant running stability and economic benefit.
Inventor have found that, when the catalyst adopting preparation method of the present invention to prepare, the Pd in catalyst is separated by Au so that the spacing in active center widens, and occurs hydrodimerized probability to be greatly reduced during two acetylene molecule hydrogenation.The growing amount of 1,3-butadiene significantly declines, and therefore the surface coking rate of catalyst is greatly reduced, and catalyst on-stream cycle time extends, and economic benefit is obvious.
The invention provides the selection method of hydrotreating of C-2-fraction in a kind of order separation process, after adiabatic reactor reactor for being hydrogenated with is positioned at domethanizing column, by C2 hydrogenation material from front-end deethanization in ethylene unit, pressurized join hydrogen after, enter adiabatic reactor reactor to carry out selecting hydrogenation, it is characterized in that: equipped with Pd-Au series catalysts in adiabatic reactor reactor, with Al2O3Or Al2O3Being carrier with other hopcalite, with the quality of catalyst for 100%, wherein Pd content 0.01～0.05%, Au content is 0.03～0.5%, and the specific surface area of catalyst is 20～60m2/ g, pore volume is 0.15～0.70mL/g；This catalyst, in preparation process, is combined with hydroxyl-bipyridyl by carrier, and hydroxyl bipyridyl forms metal complex with active component；Reaction condition is: adiabatic reactor reactor inlet temperature 30～80 DEG C, reaction pressure 1.5～3.0MPa, gas space velocity 2000～15000h-1。
The feature of the Pd-Au series catalysts used in the present invention is: this catalyst is the PdAu-hydroxyl-bipyridyl/Al adopting the present invention2O3Prepared by the method for precursor.
The catalyst preparation process recommended, at least includes: load on carrier by hydroxyl dipyridyl derivatives, and the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or adjacent nitrilo and Pd, Au forms complex ion.
The hydroxyl dipyridyl derivatives of the present invention, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives.Good complex reaction can be there is in two nitrilo at hydroxyl unnecessary after being combined with aluminium oxide and ortho position because of it with Pd, Au.
The present invention selects method of hydrotreating for carbon two in order separation process, in entrance raw material, composition is mainly C-2-fraction, wherein acetylene 1.0～2.5% (molar fraction), ethane 11.2～30.3% (molar fraction), ethylene 68.8～88.9% (molar fraction).The present invention is not specially limited the hydrogen alkynes ratio of each reactor, uses common hydrogen alkynes ratio, is generally 0.8～4.To three sections of reactor process, general first paragraph reactor hydrogen/acetylene is 0.8～1.2, and second segment reactor hydrogen/acetylene is 1～1.5, and the 3rd section of reactor hydrogen/acetylene is 1.5～3.To two reactor technique, general first paragraph reactor hydrogen/acetylene is 1～1.5, and second segment reactor hydrogen/acetylene is 2～4.
Defining the catalyst type of use in the present invention, such catalyst selectivity and traditional catalyst have bigger difference.
Principles of the invention is: in selective hydrogenation reaction, along with the catalyst activity component Pd, the Au that use form alloy, the quantity of the hydrogen that caltalyst phase is adsorbed is greatly reduced, and the trend of acetylene generation deep hydrogenation is substantially reduced, and catalyst selectivity significantly improves.
The acquisition of this catalyst preferably includes following steps: by hydroxyl dipyridyl derivatives organic solution, impregnates carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed solution dipping hydroxyl-bipyridyl/Al of preparation Pd, Au2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor.At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
Carrier of the present invention can be alumina support or mainly contain Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.Described aluminium oxide can be γ, δ, θ, α or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
In the present invention, carrier can be spherical, cylindrical, annular, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc..
Catalyst preparing of the present invention can adopt procedure below to implement, and the preparation method of this catalyst comprises the steps:
A. the organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, make solution be absorbed, at 20 DEG C～60 DEG C temperature, react 2～24h, after cooling, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl bipyridyl/Al2O3Precursor.The molal quantity of hydroxyl-bipyridyl/(Pd+Au) is preferably 1～100；The volume of organic solution is preferably equal to or greater than the 80% of carrier cumulative volume.
B. the mixed solution of Pd, Au is prepared, with step A gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle after cooling, dry at 60 DEG C～150 DEG C, obtains PdAu-hydroxyl-bipyridyl/Al2O3Precursor.
The ratio of the molal quantity of Au and the molal quantity of Pd is preferably 2～10, it is desirable to regulating pH value is 1.5～4.0；The volume of the mixed solution of Pd, Au is hydroxyl-bipyridyl/Al preferably2O3The 60%～200% of precursor cumulative volume.
C. the PdAu-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdAu-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
In the present invention, reactor refers to adiabatic reactor reactor.It can be single or many, it is preferred to 2～3.
The inventors have also found that, when adopting the method to carry out selective hydrogenation reaction, the activity of catalyst reaction, selectivity are all significantly improved, and ethylene increment increases, and green oil generating amount reduces, and anticoking capability strengthens.
Simultaneously, the inventive method prepares palladium-gold catalyst, owing to its alloy structure is obvious, alloy effect is stronger, it is more suitably applied to the carbon two back end hydrogenation device that catalyst activity, selectivity requirement is all higher, this alloy catalyst is applied to carbon two back end hydrogenation device, at a lower reaction temperature, has activity and the selectivity of excellence.
Accompanying drawing explanation
A kind of C 2 fraction selective hydrogenation process chart adopting order separation process that accompanying drawing 1 is the application present invention.
1 oil scrubber；2 water scrubbers；3 caustic wash towers；4 exsiccators；5 domethanizing columns；6 front-end deethanization towers；7 Acetylene converter；8 compressors.
Detailed description of the invention
Embodiment 1
Weighing Φ 3.5, specific surface area is 20.0m2Spherical α-the Al of/g, pore volume 0.31mL/g, bulk density 0.82g/ml2O3Carrier 500g.
By 23.88g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 2h, make 4,4-dihydroxy-2,2-bipyridyl loads to after on alumina support completely, 60 DEG C of dry 10h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate Palladous chloride., gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=30).After 120 DEG C of dry 4h at 550 DEG C of temperature roasting 3h in air atmosphere, obtain (Pd-Au)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst S-1.Recording this catalyst Pd content is 0.018%, and Au content is 0.21%.
Comparative example 1
Weighing Φ 3.5, specific surface area is 20.0m2Spherical α-the Al of/g, pore volume 0.31mL/g, bulk density 0.82g/ml2O3Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC8.9g is dissolved completely in 800mlTHF (oxolane), in above-mentioned carrier impregnation to above-mentioned solution, after standing 2h, PVC will be made to be adsorbed in Al2O3Surface, drying for standby.Obtain PVC/Al2O3。
Add 119.28g dicyandiamide and 4.0gNa2CO3, add the PVC/Al prepared2O3Backflow 1h, is cooled to room temperature, with deionized water wash to neutral, and drying for standby.Obtain functionalized PVC/Al2O3。
B, Pd-Au-high-molecular complex/Al2O3The preparation of presoma
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, is made into mixed solution.Take the functionalized-PVC/Al prepared2O3Presoma, adds it in the mixed solution prepared, and stirs 30min, pours out residual liquid, and by above-mentioned product deionized water wash to neutral, 120 DEG C of dry 4h obtain (Pd-Au)-PVC/Al2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h in air atmosphere, obtain oxidation state (Pd-Au)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst D-1.Recording this catalyst Pd content is 0.018%, and Au content is 0.21%.Adopting back end hydrogenation technique, as shown in Figure 1, raw material consists of its process chart:
C2H2: 1.6% (Φ), C2H475.3% (Φ), C2H623.1% (Φ).
Reaction condition: two sections of adiabatic reactor reactors in series reactions, namely first stage reactor outlet material enters second stage reactor.Every section of reactor all has independent air distribution system.
Material gas space velocity: 2000h-1, operate pressure: 1.7MPa, each reactor catalyst loadings: 450ml.First stage reactor H2/C2H2=1.5:1 (mol ratio)；Second stage reactor H2/C2H2=3:1 (mol ratio), after the examination of 500 hours, result is as shown in table 1.
Table 1 catalyst 500h performance meansigma methods
Embodiment 2
Weighing Φ 4.0mm, high 4.0mm, specific surface area is 55.0m2/ g, pore volume is 0.45ml/g, and bulk density is the cylindrical θ-Al of 0.68g/ml2O3Carrier 500g.
By 1.5g4,4-dihydroxy-2,2-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 90 DEG C of dry 8h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.5, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and at remaining solid 110 DEG C, dry 6h, obtains PdAu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=1.5).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst S-2.Recording this catalyst Pd content is 0.038%, and Au content is 0.036%.
Comparative example 2
Catalyst preparing
Weighing Φ 4.0mm, high 4.0mm, specific surface area is 55.0m2/ g, pore volume is 0.45ml/g, and bulk density is the cylindrical θ-Al of 0.68g/ml2O3Carrier 500g.
A, functionalized polystyrene acrylonitrile (SAN)/Al2O3Preparation
Weighing SAN resin 2.2g, be dissolved in 600mlDMF (dimethylformamide) solvent, under room temperature, stirring makes SAN resin be completely dissolved, add in this solution and above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred for, dry after separating solvent, obtain SAN/Al2O3。
By SAN/Al obtained above2O3, joining in 500ml deionized water, add 57.6g ethylenediamine, backflow 4h, after cooling, take out product, washing, to neutral, dry and obtains functionalized-SAN/Al2O3。
B、(Pd-Au)-SAN/Al2O3The preparation of presoma
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 1200mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.5, is made into mixed solution.Take the functionalized-SAN/Al prepared2O3Presoma, by functionalized-SAN/Al2O3Join in the mixed solution prepared, stir 5min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, obtain (Pd-Au)-SAN/Al after drying2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, at 500 DEG C of roasting 4h of air atmosphere, obtain Pd-Au/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst D-2.Recording this catalyst Pd content is 0.038%, and Au content is 0.036%.
Adopting back end hydrogenation technique, as shown in Figure 1, raw material consists of its process chart:
C2H2: 1.4% (Φ), C2H480.0% (Φ), C2H618.6% (Φ).
Reaction condition: two sections of adiabatic reactor reactors in series reactions, namely first stage reactor outlet material enters second stage reactor.Every section of reactor all has independent air distribution system.
Material gas space velocity: 6000h-1, operate pressure: 1.5MPa, each reactor catalyst loadings: 450ml.First stage reactor H2/C2H2=1.5:1 (mol ratio)；Second stage reactor H2/C2H2=4:1 (mol ratio), after the examination of 500 hours, result is as shown in table 2.
2500 hours catalyst performance meansigma methodss of table
Embodiment 3
Weighing Φ 3.0mm, specific surface area is 35.0m2/ g, pore volume is 0.20ml/g, and heap is than the tooth ball type carrier 500g, wherein Al for 0.75g/ml2O3460g, titanium oxide 40g, Al2O3Mixing crystal formation for θ, α.By 49.75g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 12h, make 6,6'-dihydroxy-3,3'-bipyridyl loads to after on alumina support completely, 120 DEG C of dry 4h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 650mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 12h, pours out residual liquid, and 100 DEG C of dry 8h obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=90).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst S-3.Recording this catalyst Pd content is 0.037%, and Au content is 0.20%.
Comparative example 3
Catalyst preparing
Weighing Φ 3.0mm, specific surface area is 35.0m2/ g, pore volume is 0.20ml/g, and heap is than the tooth ball type carrier 500g, wherein Al for 0.75g/ml2O3460g, titanium oxide 40g, Al2O3Mixing crystal formation for θ, α.
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 200mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3, it is made into mixed solution, by concussion after this solution spraying to above-mentioned carrier 0.5 hour, after 100 DEG C of dry 8h, in air atmosphere, 500 DEG C of roasting 4h obtained (Pd-Au)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst D-3.Recording this catalyst Pd content is 0.037%, and Au content is 0.20%.
Adopting back end hydrogenation technique, reaction raw materials is:
C2H2: 2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition: three sections of bed adiabatic reactor reactors in series techniques, namely first stage reactor outlet material enters second stage reactor, and second stage reactor outlet material enters three sections of reactors, and every section of reactor all has independent air distribution system.
Material gas space velocity: 15000h-1, operate pressure: 2.0MPa, each reactor catalyst loadings: 450ml.First stage reactor H2/C2H2=1:1 (mol ratio)；Second stage reactor H2/C2H2=1.5:1 (mol ratio)；Three sections of reactor H2/C2H2=3:1 (mol ratio)；After the examination of 500 hours, result is as shown in table 3.
Table 3 catalyst 500h performance meansigma methods
Embodiment 4
Weighing Φ 4.0mm, high 4.0mm, specific surface area is 50.0m2/ g, pore volume is 0.50ml/g, and heap is than the tooth ball type carrier 500g, wherein Al for 0.65g/ml2O3460g, titanium oxide 40g, Al2O3Mixing crystal formation for θ, α.
By 219g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, make 6,6'-dihydroxy-3,3'-bipyridyl loads to after on alumina support completely, 90 DEG C of dry 10h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 650mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3.5, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and 90 DEG C of dry 10h obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=100).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst S-4.Recording this catalyst Pd content is 0.015%, and Au content is 0.38%.
Comparative example 4
Catalyst preparing
Weighing Φ 4.0mm, high 4.0mm, specific surface area is 50.0m2/ g, pore volume is 0.50ml/g, and heap is than the tooth ball type carrier 500g, wherein Al for 0.65g/ml2O3460g, titanium oxide 40g, Al2O3Mixing crystal formation for θ, α.
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 200mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3.5, it is made into mixed solution, by concussion after this solution spraying to above-mentioned carrier 0.5 hour, after 90 DEG C of dry 10h, in air atmosphere, 600 DEG C of roasting 2h obtained (Pd-Au)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst D-4.Recording this catalyst Pd content is 0.015%, and Au content is 0.38%.
Adopting back end hydrogenation technique, reaction raw materials is:
C2H2: 2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition: three sections of bed adiabatic reactor tandem process, namely first stage reactor outlet material enters second stage reactor, and second stage reactor outlet material enters three sections of reactors, and every section of reactor all has independent air distribution system.
Material gas space velocity: 10000h-1, operate pressure: 2.5MPa, each reactor catalyst loadings: 450ml.First stage reactor H2/C2H2=1:1 (mol ratio)；Second stage reactor H2/C2H2=1.5:1 (mol ratio)；Three sections of reactor H2/C2H2=3:1 (mol ratio)；After the examination of 500 hours, result is as shown in table 4.
Table 4 catalyst 500h performance meansigma methods
Embodiment 5
Weighing Φ 3.5, specific surface area is 20.0m2Spherical α-the Al of/g, pore volume 0.31mL/g, bulk density 0.82g/ml2O3Carrier 500g.
By 34.12g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 2h, make 4,4-dihydroxy-2,2-bipyridyl loads to after on alumina support completely, 60 DEG C of dry 10h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weighing appropriate Palladous chloride., gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=30).After 120 DEG C of dry 4h at 550 DEG C of temperature roasting 3h in air atmosphere, obtain (Pd-Au)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst S-5.Recording this catalyst Pd content is 0.027%, and Au content is 0.30%.
Comparative example 5
Weighing Φ 3.5, specific surface area is 20.0m2Spherical α-the Al of/g, pore volume 0.31mL/g, bulk density 0.82g/ml2O3Carrier 500g.
By 34.12g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 2h, make 4,4-dihydroxy-2,2-bipyridyl loads to after on alumina support completely, 60 DEG C of dry 10h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Claiming appropriate Palladous nitrate., silver nitrate is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ag)=30).After 120 DEG C of dry 4h at 550 DEG C of temperature roasting 3h in air atmosphere, obtain (Pd-Ag)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain support type palladium-gold catalyst D-5.Recording this catalyst Pd content is 0.027%, and Ag content is 0.16%.
Adopting back end hydrogenation technique, as shown in Figure 1, raw material consists of its process chart:
C2H2: 1.6% (Φ), C2H475.3% (Φ), C2H623.1% (Φ).
Reaction condition: two sections of adiabatic reactor reactors in series reactions, namely first stage reactor outlet material enters second stage reactor.Every section of reactor all has independent air distribution system.
Material gas space velocity: 2000h-1, operate pressure: 1.7MPa, each reactor catalyst loadings: 450ml.First stage reactor H2/C2H2=1.5:1 (mol ratio)；Second stage reactor H2/C2H2=3:1 (mol ratio), after the examination of 500 hours, result is as shown in table 5.
Table 5 catalyst 500h performance meansigma methods
Can be seen that, compared with adopting tradition preparation catalyst, with when active component content is identical, with organic polymer grafted functional group load on a catalyst support, the solution of this carrier impregnation activity Pd, Au obtains the method for organic polymer metal complex again prepare catalyst and compare, have employed the method for hydrotreating of the present invention, the activity of hydrogenation reaction and selectivity are significantly better than traditional method of hydrotreating, and in hydrogenation process, the growing amount of green oil is also greatly lowered.The reduction of green oil simultaneously so that the active center of catalyst is not covered by by-product, and catalyst activity and selectivity are able to good maintenance.
Claims (14)
1. the selection method of hydrotreating of C-2-fraction in an order separation process, after adiabatic reactor reactor for being hydrogenated with is positioned at domethanizing column, by carbon two material from front-end deethanization tower in ethylene unit, pressurized join hydrogen after, enter adiabatic reactor reactor to carry out selecting hydrogenation, it is characterized in that: equipped with Pd-Au series catalysts in adiabatic reactor reactor, with Al2O3Or Al2O3Being carrier with other hopcalite, with the quality of catalyst for 100%, wherein Pd content 0.01～0.05%, Au content is 0.03～0.5%, and the specific surface area of catalyst is 20～60m2/ g, pore volume is 0.15～0.70mL/g；This catalyst, in preparation process, is combined with hydroxyl dipyridyl derivatives by carrier, and hydroxyl bipyridyl forms metal complex with active component；Reaction condition is: adiabatic reactor reactor inlet temperature 30～80 DEG C, reaction pressure 1.5～3.0MPa, gas space velocity 2000～15000h-1。
2. selection method of hydrotreating according to claim 1, it is characterized in that catalyst preparation process at least includes: load on carrier by hydroxyl dipyridyl derivatives, the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Au forms complex ion.
3. selection method of hydrotreating according to claim 2, it is characterised in that hydroxyl dipyridyl derivatives is hydroxyl 2,2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives.
4. selection method of hydrotreating according to claim 1, it is characterised in that the acquisition of catalyst comprises the steps:, by hydroxyl dipyridyl derivatives organic solution, to impregnate carrier, obtain hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed solution dipping hydroxyl-bipyridyl/Al of preparation Pd, Au2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdAu-hydroxyl-bipyridyl/Al2O3Precursor；At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
5. selection method of hydrotreating according to claim 1, it is characterised in that carrier is aluminium oxide, or mainly contains Al2O3, wherein also doped with other oxide, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide；Described aluminium oxide is γ, δ, θ, α or wherein several mixing crystal formation Al2O3, it is desirable to for θ, α or its mixing crystal formation.
6. selection method of hydrotreating according to claim 1, it is characterised in that carrier is spherical, cylinder, annular, bar shaped, cloverleaf pattern or Herba Galii Bungei shape.
7. according to the arbitrary described selection method of hydrotreating of claim 1-6, it is characterised in that the preparation method of catalyst comprises the steps:
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, at 20 DEG C～60 DEG C temperature, reacts 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdAu-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed solution of preparation Pd, Au, with step A gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle, dry at 60 DEG C～150 DEG C, obtains PdAu-hydroxyl-bipyridyl/Al2O3Precursor；
C. the preparation of catalyst
PdAu-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdAu-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
8. selection method of hydrotreating according to claim 7, it is characterised in that in step A, the molal quantity of hydroxyl-bipyridyl/(Pd+Au) is 1～100:1.
9. selection method of hydrotreating according to claim 7, it is characterised in that in stepb, the mixed solution of Pd, Au is the mixed solution of Palladous chloride. and gold chloride.
10. selection method of hydrotreating according to claim 7, it is characterised in that in stepb, the ratio of the molal quantity of Au and the molal quantity of Pd is 2～10:1.
11. selection method of hydrotreating according to claim 7, it is characterised in that in stepb, the mixed solution pH value regulating Pd, Au is 1.5～4.0.
12. selection method of hydrotreating according to claim 1, it is characterised in that hydrogen and acetylene volume ratio are 0.8～4:1.
13. selection method of hydrotreating according to claim 1, it is characterised in that adiabatic reactor reactor reaction bed number is two sections or three sections of beds.
14. selection method of hydrotreating according to claim 13, it is characterised in that when adiabatic reactor reactor reaction bed number is two sections, first paragraph reactor hydrogen and acetylene volume ratio are 1～1.5:1, and second segment reactor hydrogen and acetylene volume ratio are 2～4:1；When adiabatic reactor reactor reaction bed number is three sections, first paragraph reactor hydrogen and acetylene volume ratio are 0.8～1.2:1, and second segment reactor hydrogen and acetylene volume ratio are 1～1.5:1, and the 3rd section of reactor hydrogen is 1.5～3.0:1 with acetylene volume ratio.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410771389.XA CN105732269B (en) | 2014-12-12 | 2014-12-12 | Selective hydrogenation method for carbon two-fraction in sequential separation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410771389.XA CN105732269B (en) | 2014-12-12 | 2014-12-12 | Selective hydrogenation method for carbon two-fraction in sequential separation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105732269A true CN105732269A (en) | 2016-07-06 |
| CN105732269B CN105732269B (en) | 2019-04-09 |
Family
ID=56241628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410771389.XA Active CN105732269B (en) | 2014-12-12 | 2014-12-12 | Selective hydrogenation method for carbon two-fraction in sequential separation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105732269B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4484015A (en) * | 1981-05-06 | 1984-11-20 | Phillips Petroleum Company | Selective hydrogenation |
| CN102206131A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for carbon-dioxide fraction |
-
2014
- 2014-12-12 CN CN201410771389.XA patent/CN105732269B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4484015A (en) * | 1981-05-06 | 1984-11-20 | Phillips Petroleum Company | Selective hydrogenation |
| CN102206131A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for carbon-dioxide fraction |
Non-Patent Citations (1)
| Title |
|---|
| 何炳林 等: "高分子负载加氢催化剂中钯流失的研究 Ⅰ.高分子载体的影响", 《应用化学》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105732269B (en) | 2019-04-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105732264A (en) | Selective hydrogenation method for trace acetylene in methanol-to-olefin (MTO) process | |
| CN105732261A (en) | Selective hydrogenation method for trace acetylene in methanol-to-olefin device | |
| CN105732260A (en) | Method for selective hydrogenation of carbon-containing distillate | |
| CN105732274A (en) | Ethylene selective hydrogenation refining method | |
| CN105732266A (en) | Selective hydrogenation method for trace acetylene in methanol-to-olefin device | |
| CN105732263A (en) | Selective hydrogenation method for trace acetylene in methanol-to-olefin device | |
| CN105732281A (en) | Pre-depropanization pre-hydrogenation method for carbon-dioxide fraction | |
| CN105727992A (en) | Palladium-nickel series supported hydrogenation catalyst | |
| CN105732265A (en) | Carbon two selective hydrogenation method in sequential separation process | |
| CN105753625A (en) | Selective hydrogenation method for carbon-dioxide fraction | |
| CN105732268A (en) | Hydrogenation method of trace acetylene in methanol-to-olefin device | |
| CN105732279A (en) | Method for post-hydrogenation of carbon-containing distillate | |
| CN105732271A (en) | Front hydrogenation method of trace acetylene in methanol-to-olefin device | |
| CN105732267B (en) | Process for the selective hydrogenation of a carbon-containing fraction | |
| CN105732269A (en) | Selective hydrogenation method for carbon two-fraction in sequential separation process | |
| CN105732276A (en) | Hydrogenation method before deethanization of carbon-containing fraction | |
| CN105732262A (en) | Ethylene selective hydrogenation refining method | |
| CN105732277A (en) | Method for pre-depropanizing and pre-hydrogenating carbon-containing fraction | |
| CN105732282A (en) | Carbon two selective hydrogenation method in sequential separation flow | |
| CN105732270A (en) | Front hydrogenation method for trace acetylene in methanol-to-olefin device | |
| CN105777475A (en) | Method for pre-hydrogenation of trace acetylene in methanol-to-olefin device | |
| CN105777476A (en) | Ethylene selective hydrogenation refining method | |
| CN105732275A (en) | Ethylene hydrofining method | |
| CN105732283A (en) | Method for selective hydrofining of ethylene | |
| CN105732280A (en) | Hydrogenation method before deethanization of carbon-containing distillate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |