CN105727991A - Palladium-copper series supported hydrogenation catalyst - Google Patents
Palladium-copper series supported hydrogenation catalyst Download PDFInfo
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- CN105727991A CN105727991A CN201410773569.1A CN201410773569A CN105727991A CN 105727991 A CN105727991 A CN 105727991A CN 201410773569 A CN201410773569 A CN 201410773569A CN 105727991 A CN105727991 A CN 105727991A
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- copper
- bipyridyl
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 57
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 79
- 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 69
- 239000010949 copper Substances 0.000 claims abstract description 68
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 53
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 53
- 229910052802 copper Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 32
- 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 28
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005755 formation reaction Methods 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
- 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
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052799 carbon Inorganic materials 0.000 abstract description 13
- 238000007614 solvation Methods 0.000 abstract description 4
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- 230000002411 adverse Effects 0.000 abstract description 2
- 229910045601 alloy Inorganic materials 0.000 abstract description 2
- 239000000956 alloy Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000004939 coking Methods 0.000 abstract 1
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- 229920002521 macromolecule Polymers 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 238000005303 weighing Methods 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 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 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 125000002648 azanetriyl group Chemical group *N(*)* 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000006396 nitration reaction Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
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- 239000012752 auxiliary agent Substances 0.000 description 3
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- 239000004332 silver Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002500 ions Chemical class 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
- 239000003921 oil Substances 0.000 description 2
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing 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
- 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 1
- 229910018516 Al—O Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- NFFYXVOHHLQALV-UHFFFAOYSA-N copper(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Cu].[Cu] NFFYXVOHHLQALV-UHFFFAOYSA-N 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
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- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
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- 238000004230 steam cracking Methods 0.000 description 1
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- 230000002194 synthesizing effect Effects 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a palladium-copper series supported catalyst, which contains palladium and copper, and the carrier mainly contains Al2O3The method is characterized in that: the mass of the catalyst is 100%, wherein the Pd content is 0.01-0.5%; the Cu content is 0.02-1%, the catalyst is an alloy type bimetallic catalyst, adverse effects of surface tension of an impregnating solution and solvation effect on palladium-copper dispersion are overcome in the preparation process, the prepared catalyst is more beneficial to forming palladium-copper alloy, and the catalyst has excellent selectivity. The catalyst can be used in the selective hydrogenation process of fractions such as carbon two, carbon three and the like, and has good hydrogenation activity, excellent selectivity and better coking resistance; the catalyst is particularly suitable for carbon two and carbon three hydrogenation devices with higher requirements on the activity of the catalyst.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst, be specifically related to a kind of system supported hydrogenation catalyst of palladium-copper.
Background technology
Ethylene is one of most important basic material of petro chemical industry, and as the monomer-ethylene synthesizing various polymer, the overwhelming majority is prepared by petroleum hydrocarbon (such as ethane, propane, butane, Petroleum and light diesel fuel etc.) steam cracking.Possibly together with the acetylene of 0.5%～2.5% (molar fraction) in the C2 fraction based on ethylene that this method obtains.The existence of acetylene can make the polymerization process of ethylene complicate, and worsens polymer performance.When producing polyethylene by high-pressure process, due to the accumulation of acetylene, have the danger of blast；It addition, when producing polyethylene, the existence of acetylene also can reduce polymerization catalyst, increase the consumption of catalyst.So the acetylene in ethylene must be dropped to below certain value, could as the monomer of synthetic high polymer.
Current industry generally adopts and selects hydrogenation and dissolve extracting to remove the acetylene in C2 fraction.Dissolving extraction process and can obtain essence ethylene, recyclable product acetylene again, but its flow process is complicated, operation easier is bigger.At present, catalysis selective hydrogenation is that acetylene is converted into the most economical and the most generally accepted method of ethylene.
In ethylene unit, catalysis selective hydrogenation is divided into front-end hydrogenation and back end hydrogenation, ethylene front-end hydrogenation refers to the relative domethanizing column position of acetylene hydrogenation reactor with back end hydrogenation, 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.At present, the commercial plant of front-end hydrogenation and back end hydrogenation technique is adopted respectively to account for about half in ethylene industry.
US4404124 is prepared for the selective hydrogenation catalyst of active component shell distribution by step impregnation method, can be applicable to the selection hydrogenation of carbon two, C3 fraction, to eliminate the acetylene in ethylene and the propine allene in propylene.US5587348 with aluminium oxide for carrier, regulate promoter silver with palladium effect, add alkali metal, chemical bonding fluorine be prepared for the C2 hydrogenation catalyst of function admirable.This catalyst has minimizing green oil and generates, and improves ethylene selectivity, reduces the feature of oxygenatedchemicals growing amount.US5519566 discloses the method for a kind of wet reducing preparation silver and palladium catalyst, by adding organic or inorganic reducing agent in impregnation liquid, prepares silver and palladium bi-component selective hydrogenation catalyst.
Above traditional C2 hydrogenation catalyst all adopts infusion process to prepare, and its activity is Pd, Ag bimetallic mutually.The method has the disadvantage in that (1) impact by carrier hole structure, and active component dispersion can not accurately control, and randomness is stronger.(2) by the impact of impregnation liquid surface tension, solvation effect, metal active constituent presoma is deposited on carrier surface with aggregate form, it is impossible to is formed and is uniformly distributed.(3) catalyst selectivity is required higher by C2 hydrogenation, the interaction of auxiliary agent A g and active component Pd is the key factor improving catalyst selectivity, catalyst prepared by traditional method, due to the surface tension that Pd, Ag solution is different, Pd, Ag cannot be formed be distributed with layer, the promoter effect of Ag shows inconspicuous, must flow through the amount strengthening Ag to promote the performance of its promoter effect, thus cause that the transmission of hydrogen is hindered, the probability that oligomerisation reaction occurs increases, green oil generating amount increases, and affects the life-span of catalyst.Three of the above phenomenon is easily caused the bad dispersibility of metal active constituent, and the selectivity of reaction is low, and then has influence on the performance of catalyst.
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.Adopt this patented method, the specific macromolecular compound of carrier adsorption, carry out chemisorbed by the hydroxyl of aluminium oxide and macromolecule, 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.
Higher in air speed, alkynes and the higher carbon two of diene content, carbon three select in hydrogenation plant, particularly in the carbon two front-end hydrogenation device that CO content is higher, catalyst activity is required higher by hydrogenation operating mode, and with Pd be active component, Ag be auxiliary agent bimetal supported catalyst for the type device, there is reaction temperature height, the shortcoming that activity can not better meet matching requirements, need to select more suitable auxiliary agent to prepare catalyst, to meet the hydrogenation requirements of device.
Summary of the invention
In view of the above circumstances, the present invention proposes a kind of better hydrogenation catalyst of selectivity.
Palladium-copper system support catalysts provided by the invention, containing palladium, copper in catalyst, Al2O3It is carrier, it is characterised in that: with the quality of catalyst for 100%, wherein Pd content is 0.01～0.5%；Cu content is 0.02～1%；Specific surface area of catalyst is 2～100m2/ g, pore volume is 0.2～0.6mL/g, and bulk density is 0.6～1.1g/cm3；This catalyst is to impregnate Al by the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, after drying again by the mixed-cation solution impregnation containing Pd, Cu, dry roasting, obtains Pd-Cu series catalysts.
The method for preparing catalyst recommended is: by hydroxyl dipyridyl derivatives organic solution, impregnate Al2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Cu2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor.At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
Al in carrier2O3The hydroxyl dipyridyl derivatives of absorption, is hydroxyl 2,2, and-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives, it can be ensured that Al2O3While it is produced extensive chemical absorption, the nitrilo of unnecessary hydroxyl and bipyridyl and active component Pd, Cu combine.
The acquisition of catalyst preferably includes following steps:
A. by the organic solution of hydroxyl dipyridyl derivatives and Al2O3It is carrier mixing, makes solution be absorbed, at 20 DEG C～60 DEG C temperature, react 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor.Organic solution volume is preferably the 60%～200% of carrier cumulative volume
B. prepare the mixed-cation solution of Pd, Cu, at 30 DEG C～100 DEG C temperature, react 2～24h with step A gained hydroxyl-bipyridyl/Al2O3 precursor, take out solid particle, dry at 60 DEG C～150 DEG C, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor.The mixed-cation liquor capacity of Pd, Cu is hydroxyl-bipyridyl/Al preferably2O3The 60%～200% of precursor cumulative volume, the ratio of the molal quantity of Cu and the molal quantity of Pd is preferably 0.4～5, it is desirable to regulating pH value is 1.0～4.0.
C. the PdCu-hydroxyl-bipyridyl/Al2O3 precursor prepared by step B is at 300～600 DEG C of roasting temperature 2～12h so that PdCu-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
Carrier of the present invention is alumina series carrier, it is possible to be Al2O3, or mainly contain Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.Described Al2O3For γ, δ, θ, alpha-crystal form or wherein several mixing crystal formation Al2O3, 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..
In the present invention, in the presoma of catalyst, palladium and copper define organic polymer complex.
In the present invention, complex reaction is the in-situ chemical reaction of complex-metal ion, metal ion is to be attached on macromolecule by chemical reaction but not physical absorption, therefore palladium, copper atom be in uniform sequential distribution on macromolecule, in the process of roasting, palladium-copper atom can carry out oxidation reaction in position, in the process of oxidation reaction, form the oxide eutectic of palladium, copper.
Adopting the method that impregnation liquid surface tension and solvation effect can be overcome the scattered impact of palladium-copper, preparing catalyst is alloy-type bimetallic catalyst, therefore possesses more excellent selectivity.
Due to Al in the present invention2O3Be the Al-O key of carrier by the hydroxyl in hydroxyl-dipyridyl derivatives being produced strong absorption, therefore can effectively guarantee Al2O3It it is that carrier is to high molecular adsorbance, it is to avoid the loss of hydroxyl-dipyridyl derivatives in solution.Simultaneously as be adsorbed on Al2O3Be the hydroxyl of hydroxyl-dipyridyl derivatives on carrier and adjacent nitrilo with active component Pd, help active component Cu complexing power stronger, it can be ensured that active component Pd in solution, help active component Cu by hydroxyl-bipyridyl/Al2O3Adsorb completely, it is to avoid active component Pd in solution, help the loss of active component Cu, reduce production cost.
Hydroxyl-the dipyridyl derivatives introduced in the present invention is because of the existence of polymer effect, metallic atom can be made to reach the scattered effect of high uniformity, hydroxyl-bipyridyl of the present invention can be hydroxyl 2,2 ,-dipyridyl derivatives, hydroxyl 3,3,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.
Hydrogenation catalyst of the present invention, roasting preferably carries out in having oxygen atmosphere, sintering temperature of the present invention preferably 350 DEG C～500 DEG C.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
The molal quantity of hydroxyl-dipyridyl derivatives/(Pd+Cu) is 1～100.Adding solvent in step to make hydroxyl-bipyridyl be completely dissolved, to be conducive to macromolecule absorption on carrier, solvent can be ethanol and ether.The addition of solvent is how many, mainly controls institute's solubilizer and macromolecule can be made to be completely dissolved.
In stepb, the consumption of palladium, copper in the solution of described configuration palladium-copper, can make Pd, Cu content of final catalyst, wherein Pd is preferably 0.01～0.5%, Cu content preferably 0.02～1%.
The solution of palladium-copper can be the soluble salt solutions of palladium, copper, as being Pd (NO3)2、CuNO3Mixed solution.
Using plasma emission spectrometer or atomic absorption spectrum can record this catalyst Pd content and Cu content (standard GB/T15337-94), adopt XRD can measure the existing forms of Pd-Cu on catalyst.
In the present invention, being loaded to by hydroxyl-dipyridyl derivatives on alumina series carrier, the cation of the hydroxyl unnecessary again through hydroxyl-bipyridyl and/or adjacent nitrilo and Pd, Cu forms complex ion.The solution of configuration palladium-copper, is impregnated into being loaded with functionalized high molecular predecessor in the palladium-copper solution prepared, reacts under certain conditions, make palladium, copper ion be complexed on the macromolecular chain of load simultaneously.The ion of palladium-copper is attached on macromolecule by chemical reaction, palladium-copper atom the number combined on each macromolecule is proportional to the quantity of hydroxyl on macromolecule, nitrilo, and the quantity of described hydroxyl-bipyridyl is preferably 1～100 times of (palladium+copper) molal quantity.In course of reaction, orderly being distributed on macromolecule of palladium, copper particle.In roasting process, palladium-copper atom can carry out oxidation reaction in position, catalyst prepared by this method is alloy-type bimetallic catalyst, this preparation method is adopted to overcome impregnation liquid surface tension and solvation effect to the scattered adverse effect of palladium-copper, the catalyst of preparation, being more conducive to form palladium-copper alloy, catalyst possesses the selectivity of excellence.
Catalyst of the present invention can be used for the selection hydrogenation process of carbon two, the third fraction of carbon, has good hydrogenation activity, excellent selectivity and good anticoking capability.
Meanwhile, the inventive method prepares palladium-copper catalyst, and its alloy structure is more suitably applied to the working condition that catalyst activity requirement is higher.Higher in air speed, alkynes and the higher carbon two of diene content, carbon three select in hydrogenation process, particularly in the carbon two front-end hydrogenation process that CO content is higher, have reaction temperature low, the advantage that hydrogenation activity is good.
Detailed description of the invention
Analysis test method:
Specific surface area: GB/T-5816
Pore volume: GB/T-5816
Bulk density: Q/SY142-2006
Catalyst Pd, Cu assay: using plasma emission spectrometer records this catalyst Pd content and Cu content.Standard GB/T1537-94
Ethylene selectivity=Δ ethylene/Δ acetylene
Embodiment 1
Weighing Φ 4.2mm, length is 4.2mm, specific surface 3.0m2Column α-the Al of/g, pore volume 0.22mL/g2O3Carrier 500g.
By 21.53g4,4-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, 80 DEG C of dry 10h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.25gPd (NO3)2、0.59gCu(NO3)2, add in the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 2.1.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 3h, pours out residual liquid, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=35).After 125 DEG C of dry 4h at 550 DEG C of temperature roasting 4h in air atmosphere, obtain (Pd-Cu)/Al2O3Catalyst.It is positioned over before using in fixed-bed reactor, is N by mol ratio2:H2The mixing gas of=1:1, reduces at 120 DEG C of temperature, obtains loaded catalyst S-1.Recording this catalyst Pd content is 0.02%, and Cu content is 0.04%.
Comparative example 1:
Weighing Φ 4.2mm, length is 4.2mm, specific surface 3.0m2Column α-the Al of/g, pore volume 0.22mL/g2O3Carrier 500g.
Weigh 0.25gPd (NO3)2、0.59gCu(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 2.1.Above-mentioned carrier joining the solution prepared, stirs 10min, pour out residual liquid, roasting 6h in air atmosphere at 550 DEG C of temperature, obtains (Pd-Cu)/Al after drying2O3Catalyst.It is positioned over before using in fixed-bed reactor, is N by mol ratio2:H2The mixing gas of=1:1, at 120 DEG C of temperature, obtains support type comparative catalyst D-1.Recording this catalyst Pd content is 0.02%, and Cu content is 0.04%.
Adopting the front-end hydrogenation technique of predepropanization, reaction raw materials is from predepropanization column overhead, and composition is as shown in table 1.
Shown in table 1 hydrogenating materials table composed as follows
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (Φ %) | 18.0 | 0.7 | 36.0 | 6.2 | 24.5 | 11 | 3.0 | 0.55 | 0.2 | 0.3 |
Reaction condition: material air speed: 4500h-1；Operation pressure: 3.2MPa,；Loaded catalyst: 500mL.
Adiabatic reactor reactor, two-stage nitration tandem process, carry out hydrogenation reaction.Second stage reactor result after the examination of 1000 hours is as shown in table 2.
Table 2 1000 hours result of appraisal of two-stage nitration adiabatic reactor reactor
Embodiment 2
Weighing Φ 2.4mm, specific surface area is 45m2/ g, pore volume is the ball type carrier 500g of 0.24mL/g, wherein containing θ-Al2O3Carrier 440g, titanium oxide 60g.
By 13.97g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL 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 100 DEG C of dry 8h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.59gPd (NO3)2, 2.35gCu (NO3)2, add in the 600mL deionized water containing appropriate nitric acid, adjusting pH is 2.7, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 6h, pours out residual liquid, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=5).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 6h in air atmosphere, obtain catalyst S-2.Recording this catalyst Pd content is 0.048%, and Cu content is 0.16%.
Comparative example 2:
The functionalized SAN/Al of A2O3Preparation
Weighing Φ 2.4mm, specific surface area is 45m2/ g, pore volume is the ball type carrier 500g of 0.24mL/g, wherein containing θ-Al2O3Carrier 440g, titanium oxide 60g.
Weighing SAN resin 2.2g, be dissolved in 600mLDMF solvent, under room temperature, stirring makes SAN resin be completely dissolved, and adds in this solution and above-mentioned has weighed carrier, stands 1 hour after being sufficiently stirred for, dry after separating solvent, obtains SAN/ θ-Al2O3Presoma.
By functionalized-SAN/ θ-Al obtained above2O3Presoma, joins in 1000mL deionized water, adds 57.6g ethylenediamine, backflow 60min, takes out product after cooling, and washing, to neutral, dry and obtains functionalized-SAN/Al2O3Presoma.
B(Pd-Cu)-SAN/Al2O3The preparation of precursor
Weigh appropriate Pd (NO3)2、Cu(NO3)2Being dissolved in the 1200mL deionized water containing appropriate nitric acid, adjusting pH value is 2.7, is configured to mixed solution, takes the step A functionalized-SAN/Al prepared2O3Presoma, joins Pd (NO3)2、Cu(NO3)2Mixed solution in, stir 120min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, obtain (Pd-Cu)-SAN/Al2O3Precursor.
The preparation of C catalyst
By the presoma of above-mentioned preparation, 500 DEG C of roasting 6h in air atmosphere, obtain comparative catalyst D-2.Recording this catalyst Pd content is 0.048%, and Cu content is 0.16%.
Adopting back end hydrogenation technique, its raw material consists of:
C2H2: 1.9% (Φ), C2H4: 74.1% (Φ), C2H6: 24.0% (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: 3000h-1, operate pressure: 1.5MPa, each reactor catalyst loadings: 500mL.First stage reactor H2/C2H2=1.6:1 (mol ratio)；Second stage reactor H2/C2H2=2.8:1 (mol ratio), after the examination of 500 hours, result is as shown in table 3.
Table 3 catalyst 500h performance meansigma methods
Embodiment 3:
Weighing diameter 4.2mm, length is 4.2mm, and specific surface area is 18m2/ g, pore volume is the cylindric carrier 500g, wherein Al of 0.31mL/g2O3400g, magnesium oxide 100g, Al2O3For α-Al2O3。
By 16.68g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 700mL 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.
Weigh 0.39gPd (NO3)2, 0.83gCu (NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 3.3, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, obtain PdCu-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=15).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 8h in air atmosphere, obtain catalyst S-3.Recording this catalyst Pd content is 0.032%, and Cu content is 0.056%.
Comparative example 3:
The functionalized SAN/Al of A2O3Preparation
Weighing diameter 4.2mm, length is 4.2mm, and specific surface area is 18m2/ g, pore volume is the cylindric carrier 500g, wherein Al of 0.31mL/g2O3400g, magnesium oxide 100g, Al2O3For α-Al2O3。
Weighing SAN resin 1.92g, be dissolved in 600mLDMF solvent, under room temperature, stirring makes SAN resin be completely dissolved, and adds in this solution and above-mentioned has weighed carrier, stands 2 hours after being sufficiently stirred for, dry after separating solvent, obtains SAN/ α-Al2O3。
By SAN/ α-Al obtained above2O3, join in 1000mL deionized water, add 250g oxammonium hydrochloride., stir backflow 60min after making it be completely dissolved.Taking out product after cooling, washing, to neutral, dry and obtains functionalized-SAN/Al2O3Precursor.
BPd-Ag-SAN/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2、CuNO3Being dissolved in the 2400mL deionized water containing appropriate nitric acid, adjusting pH value is 3.3, takes the step A functionalized-SAN/Al prepared2O3Presoma, adds it to Pd (NO3)2、AgNO3Mixed solution in, stir 60min, pour out residual liquid, by above-mentioned product deionized water wash to neutral.Obtain Pd-Cu-SAN/Al2O3Presoma.
The preparation of C catalyst
By the presoma of above-mentioned preparation, 450 DEG C of roasting 8h in air atmosphere, obtain comparative catalyst D-3.Recording this catalyst Pd content is 0.032%, and Cu content is 0.056%.
Reaction mass is from front-end deethanization column overhead, and composition is as shown in table 4.
Table 4 hydrogenating materials forms
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | C3H6 | CH4 | CO | C4 + |
| Content (v/v%) | 30 | 0.8 | 32.0 | 6.88 | 28 | 31 | 0.005 | 0.315 |
Reaction condition 1: adopting front-end deethanization front-end hydrogenation technique, single hop isothermal bed bioreactor, material air speed is 15000h-1, operating pressure 3.5MPa, loaded catalyst is 500mL.
Table 5 single hop isothermal bed bioreactor was through 1000 hours reaction results
Embodiment 4
Weigh Φ 2.4mm, specific surface 38.0m2Ball-type α-the Al of/g, pore volume 0.2mL/g2O3Carrier 500g.
By 106.52g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 16h, make 4,4-dihydroxy-2,2-bipyridyl loads to after on alumina support completely, 110 DEG C of dry 6h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.49gPd (NO3)2、1.77gCu(NO3)2, add in the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 3.9.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 12h, pours out residual liquid, obtain PdAg-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Cu)=50).After 95 DEG C of dry 10h at 400 DEG C of temperature roasting 10h in air atmosphere, obtain (Pd-Cu)/Al2O3Catalyst.It is positioned over before using in fixed-bed reactor, is N by mol ratio2:H2The mixing gas of=1:1, reduces at 120 DEG C of temperature, obtains loaded catalyst S-4.Recording this catalyst Pd content is 0.040%, and Cu content is 0.12%.
Comparative example 4:
Weigh Φ 2.4mm, specific surface 38.0m2Ball-type α-the Al of/g, pore volume 0.2mL/g2O3Carrier 500g.
Weighing appropriate 4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 16h, make 4,4-dihydroxy-2,2-bipyridyl loads to after on alumina support completely, 110 DEG C of dry 6h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2、Ag(NO3)2, add in the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 3.9.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 12h, pours out residual liquid, obtain PdAg-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ag)=50).After 95 DEG C of dry 10h at 400 DEG C of temperature roasting 10h in air atmosphere, obtain (Pd-Ag)/Al2O3Catalyst.It is positioned over before using in fixed-bed reactor, is N by mol ratio2:H2The mixing gas of=1:1, reduces at 120 DEG C of temperature, obtains loaded catalyst D-4.Recording this catalyst Pd content is 0.040%, and Cu content is 0.12%.
Adopting the front-end hydrogenation technique of predepropanization, reaction raw materials is from predepropanization column overhead, and composition is as shown in table 6.
Shown in table 6 hydrogenating materials table composed as follows
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (Φ %) | 18.0 | 0.75 | 34.1 | 6.2 | 26.0 | 12 | 2.0 | 0.55 | 0.2 | 0.3 |
Reaction condition: material air speed: 5000h-1；Operation pressure: 3.0MPa；Loaded catalyst: 500mL.
Adiabatic reactor reactor, two-stage nitration tandem process, carry out hydrogenation reaction.Second stage reactor result after the examination of 500 hours is as shown in table 7.
Table 7 500 hours result of appraisal of two-stage nitration adiabatic reactor reactor
From above embodiments it can be seen that compared with adopting tradition preparation catalyst, after adopting the method for the present invention, the activity of C-2-fraction hydrogenation reaction, selectivity, anticoking capability increase substantially.
Claims (11)
1. the system supported hydrogenation catalyst of palladium-copper, containing palladium, copper in catalyst, Al2O3It is carrier, it is characterised in that: with the quality of catalyst for 100%, wherein Pd content is 0.01～0.5%；Cu content is 0.02～1%；Specific surface area of catalyst is 1～200m2/ g, pore volume is 0.15～0.8mL/g, and bulk density is 0.5～1.2g/cm3；This catalyst preparation process includes: impregnate Al by the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, after drying again by the mixed-cation solution impregnation containing Pd, Cu, dry roasting.
2. the system supported hydrogenation catalyst of palladium-copper according to claim 1, it is characterised in that Al2O3Be carrier it is Al2O3Or it is mainly Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.
3. the system supported hydrogenation catalyst of palladium-copper according to claim 1, is characterized in that: described Al2O3For γ, δ, θ, alpha-crystal form or wherein several mixing crystal formations.
4. the system supported hydrogenation catalyst of palladium-copper according to claim 1, it is characterised in that catalyst Pd content is 0.01～0.5%, and Cu content is 0.02～1%.
5. the system supported hydrogenation catalyst of palladium-copper according to claim 1, it is characterised in that the specific surface area of catalyst is 2～100m2/ g, pore volume is 0.20～0.60mL/g, and bulk density is 0.60～1.1g/cm3。
6. the system supported hydrogenation catalyst of palladium-copper according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives is hydroxyl 2,2,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.
7. according to the arbitrary described system supported hydrogenation catalyst of palladium-copper of claim 1-6, it is characterised in that the preparation of catalyst includes following process:
A. by the organic solution of hydroxyl dipyridyl derivatives and Al2O3It is carrier mixing, 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. the mixed-cation solution of Pd, Cu is prepared, 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 PdCu-hydroxyl-bipyridyl/Al2O3Precursor；
C. the PdCu-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdCu-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
8. the system supported hydrogenation catalyst of palladium-copper according to claim 7, it is characterised in that the mol ratio of hydroxyl-bipyridyl and (Pd+Cu) is 1～100:1.
9. the system supported hydrogenation catalyst of palladium-copper according to claim 7, it is characterised in that in stepb, the mixed solution that mixed-cation solution is Palladous nitrate. and copper nitrate of Pd, Cu.
10. the system supported hydrogenation catalyst of palladium-copper according to claim 7, it is characterised in that in stepb, the ratio of the molal quantity of Cu and the molal quantity of Pd is 1～10:1；The mixed-cation solution ph regulating Pd, Cu is 1.5～4.0.
11. the system supported hydrogenation catalyst of palladium-copper according to claim 1, it is characterised in that roasting carries out at 300～600 DEG C, it is preferred to 350 DEG C～500 DEG C；Roasting 2～12h.
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