CN105749910B - Palladium-lead supported hydrogenation catalyst - Google Patents
Palladium-lead supported hydrogenation catalyst Download PDFInfo
- Publication number
- CN105749910B CN105749910B CN201410806061.7A CN201410806061A CN105749910B CN 105749910 B CN105749910 B CN 105749910B CN 201410806061 A CN201410806061 A CN 201410806061A CN 105749910 B CN105749910 B CN 105749910B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- hydroxyl
- hydrogenation catalyst
- palladium
- bipyridyl
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 56
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 90
- 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 74
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 58
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 58
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000011133 lead Substances 0.000 claims description 73
- 239000000243 solution Substances 0.000 claims description 40
- 239000002243 precursor Substances 0.000 claims description 27
- 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 25
- 229910052745 lead Inorganic materials 0.000 claims description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 17
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000002245 particle Substances 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
- 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
- 239000011148 porous material Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 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 1
- 239000000376 reactant Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- IFYDWYVPVAMGRO-UHFFFAOYSA-N n-[3-(dimethylamino)propyl]tetradecanamide Chemical compound CCCCCCCCCCCCCC(=O)NCCCN(C)C IFYDWYVPVAMGRO-UHFFFAOYSA-N 0.000 abstract description 9
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000007614 solvation Methods 0.000 abstract description 4
- 238000004939 coking Methods 0.000 abstract description 2
- 229910000978 Pb alloy Inorganic materials 0.000 abstract 1
- 230000002411 adverse Effects 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 239000000956 alloy Substances 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 17
- 239000005977 Ethylene Substances 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 11
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead(II) nitrate Inorganic materials [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 10
- 229920002521 macromolecule Polymers 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 239000003643 water by type Substances 0.000 description 9
- 239000004800 polyvinyl chloride Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229920000915 polyvinyl chloride Polymers 0.000 description 7
- 229910052709 silver Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000002803 maceration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- RDRCCJPEJDWSRJ-UHFFFAOYSA-N pyridine;1h-pyrrole Chemical compound C=1C=CNC=1.C1=CC=NC=C1 RDRCCJPEJDWSRJ-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052594 sapphire Inorganic materials 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
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 206010013786 Dry skin Diseases 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
- 240000005702 Galium aparine Species 0.000 description 1
- 235000014820 Galium aparine Nutrition 0.000 description 1
- 241000612118 Samolus valerandi Species 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001361 allenes Chemical class 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
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 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
- 230000002779 inactivation Effects 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 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
- 230000003647 oxidation Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920002939 poly(N,N-dimethylacrylamides) Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910006415 θ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a palladium-lead series supported hydrogenation catalyst, which contains palladium and lead, and the carrier mainly contains Al2O3The method is characterized in that: the mass of the catalyst is 100%, wherein the Pd content is 0.01-0.8%; the Pb content is 0.04-3%, the catalyst is an alloy type bimetallic catalyst, adverse effects of surface tension of an impregnating solution and solvation effect on dispersion of palladium-lead are overcome in the preparation process, the prepared catalyst is more beneficial to forming palladium-lead alloy, and the catalyst has excellent selectivity; meanwhile, as Pb has better function of preventing Pd loss, the catalyst is more suitable for being applied to C with higher MAPD content and higher MAPD content4Selective hydrogenation process of the fractions containing high fraction of carbon two, carbon three, etc. 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; when the content of MAPD in the hydrogenation raw material is higher, C4When the fraction content is higher, the hydrogenation performance is also excellent.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts, and in particular to a kind of system supported hydrogenation catalyst of palladium-lead.
Background technology
Ethylene is one of most important basic material of petro chemical industry, as the monomer-ethylene for synthesizing various polymer,
The overwhelming majority is made by petroleum hydrocarbon (such as ethane, propane, butane, naphtha and light diesel fuel) steam cracking.It is obtained through this method
To the C2 fractions based on ethylene in also contain 0.5%~2.5% (molar fraction) acetylene.The presence of acetylene can make ethylene
Polymerization process complicate, deteriorate polymer performance.When producing polyethylene with high-pressure process, due to the accumulation of acetylene, have quick-fried
Fried danger；In addition, when producing polyethylene, the presence of acetylene can also reduce polymerization catalyst, increase disappearing for catalyst
Consumption.So must certain value be dropped to the acetylene in ethylene hereinafter, could be as the monomer of synthetic high polymer.
Generally use selection plus hydrogen and dissolving extracting remove the acetylene in C2 fractions in industry at present.Dissolve extraction process
Smart ethylene, and recyclable product acetylene are obtained, but its flow is complicated, operation difficulty is larger.Currently, catalysis selective hydrogenation is acetylene
It is converted into the most economical and most generally accepted method of ethylene.
Catalysis selective hydrogenation is divided into front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene adds
For hydrogen reactor is with respect to domethanizing column position, hydrogenation reactor is located at before domethanizing column for front-end hydrogenation, hydrogenation reactor position
It is back end hydrogenation after domethanizing column.Currently, respectively being accounted in ethylene industry using front-end hydrogenation and the commercial plant of back end hydrogenation technique
Half or so.
US4404124 is prepared for the selective hydrogenation catalyst of active component shell distribution by step impregnation method, can apply
Add hydrogen in the selection of carbon two, C3 fraction, to eliminate the propine allene in acetylene and propylene in ethylene.US5587348 with
Aluminium oxide is carrier, adjusts co-catalyst silver and is acted on palladium, alkali metal is added, the fluorine of chemical bonding is prepared for the carbon of function admirable
Two hydrogenation catalysts.The catalyst, which has, reduces green oil generation, improves ethylene selectivity, reduces the spy of oxygenatedchemicals production quantity
Point.US5519566 discloses a kind of method that wet reducing prepares silver and palladium catalyst, by be added in maceration extract it is organic or
Inorganic reducing agent prepares silver and palladium bi-component selective hydrogenation catalyst.
Above traditional C2 hydrogenation catalyst is all made of infusion process preparation, and activity is mutually Pd, Ag bimetallic.The method
It has the following disadvantages：(1) it is influenced by carrier hole structure, active component dispersion cannot accurately control, and randomness is stronger.(2) by
The influence of maceration extract surface tension, solvation effect, metal active constituent presoma are deposited on carrier surface with aggregate form,
It cannot be formed and be uniformly distributed.(3) C2 hydrogenation is more demanding to catalyst choice, the phase interaction of auxiliary agent A g and active component Pd
The catalyst prepared with the key factor for being raising catalyst choice, conventional method, due to the different surface of Pd, Ag solution
Power, can not form the distribution of Pd, Ag same layer, and the promoter effect of Ag shows to obtain unobvious, it is necessary to promote it by increasing the amount of Ag
Thus the performance of promoter effect causes the transmission of hydrogen hindered, the possibility that oligomerisation reaction occurs increases, and green oil generating amount increases
It is more, influence the service life of catalyst.Three of the above phenomenon is easy to cause the bad dispersibility of metal active constituent, the choosing of reaction
Selecting property is low, and then influences the performance of catalyst.
CN201110086174.0 on carrier by adsorbing specific high-molecular compound, in carrier surface certain thickness
Macromolecule wrapped layer is formed, with compound and high molecular weight reactive with functional base, with can be complexed with active component
Function base, complex reaction is occurred on carrier surface function base by active component, ensures active component orderly and height point
It dissipates.Using the patented method, the specific high-molecular compound of carrier adsorption carries out chemistry by the hydroxyl and macromolecule of aluminium oxide
Absorption, the amount of carrier adsorption high-molecular compound will be limited by the hydroxyl quantity of aluminium oxide；By the macromolecule of functionalization
Not strong with the complexing of Pd, activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is made
It is improved at catalyst cost；Preparing C2 hydrogenation catalyst using this method, there is also the disadvantages of technological process complexity.
Carbon two, carbon three select also to contain a certain amount of C-4-fraction and propine, allene in hydrogenation plant hydrogenating materials
(MAPD), C-4-fraction, MAPD are easy coking in catalyst surface, while can form soluble complex compound with palladium and cause
Palladium is lost in, and to influence the activity of catalyst, catalyst inactivation can be caused when serious, to bring device to leak alkynes risk.
Invention content
In view of the above circumstances, the present invention proposes a kind of better hydrogenation catalyst of selectivity.
The system supported hydrogenation catalyst of palladium-lead provided by the invention contains palladium, lead, Al in catalyst2O3It is carrier, it is special
Sign is：It is in terms of 100% by the quality of catalyst, wherein Pd contents are 0.01~0.8%, preferably 0.02~0.50%；Pb
Content is 0.04~3%；Specific surface area of catalyst is 2~100m2/ g, pore volume be 0.15~0.8mL/g, preferably 0.2~
0.6mL/g；Heap density is 0.5~1.2g/cm3,Preferably 0.6~1.1g/cm3；The catalyst is spread out with hydroxyl bipyridyl
The organic solution of biology impregnates Al2O3It is carrier, is impregnated again with the mixed-cation solution containing Pd, Pb after drying, is roasted after dry
It burns, obtains Pd-Pb series catalysts.
The method for preparing catalyst of recommendation is：With hydroxyl dipyridyl derivatives organic solution, Al is impregnated2O3It is carrier,
Hydroxyl-bipyridyl/Al is obtained after drying2O3Precursor, prepare Pd, Pb mixed-cation solution dipping hydroxyl-bipyridyl/
Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyls-bipyridyl/Al2O3Precursor.At 300~600 DEG C
2~12h of roasting temperature obtains required catalyst.
Al in carrier2O3The hydroxyl dipyridyl derivatives of absorption are hydroxyl 2,2 ,-dipyridyl derivatives, band hydroxyl
The 3 of base, 3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, it can be ensured that Al2O3It is generated by force
While chemisorption, nitrogen base and active component Pd, Pb of extra hydroxyl and bipyridyl are combined.
The acquisition of catalyst preferably includes following steps：
A. by the organic solution and Al of hydroxyl dipyridyl derivatives2O3It is carrier mixing, so that solution is absorbed, 20
DEG C~60 DEG C at a temperature of reaction 2~for 24 hours, take out solid particle, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/
Al2O3Precursor.
B. prepare Pd, Pb mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl obtained by step A-connection pyrrole
Pyridine/Al2O3Precursor reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyls-connection pyrrole
Pyridine/Al2O3Precursor.The volume of the mixed-cation solution of Pd, Pb is preferably hydroxyl-bipyridyl/Al2O3Precursor total volume
60%~200%, Pb molal quantity and Pd the ratio between molal quantity preferably 0.4~5；It is 1.0~4.0 preferably to adjust pH value.
C. the PdPb- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor 300~600 DEG C of roasting temperatures 2~
12h so that PdPb- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
Carrier of the present invention is alumina series carrier, can be Al2O3, or mainly contain Al2O3, wherein also doped with other
Hopcalite, other oxides are silica, titanium oxide, magnesia and/or calcium oxide.The Al2O3For γ, δ,
θ, alpha-crystal form or in which several mixing crystal form Al2O3, preferably θ, α or its mix crystal form.
Carrier can be spherical in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Palladium and lead form organic polymer complex compound in the presoma of catalyst in the present invention.
Complex reaction is the in-situ chemical reaction of complex-metal ion in the present invention, and metal ion is by chemical anti-
It answers rather than physical absorption is attached on macromolecule, therefore it is in uniform sequential distribution that the atom of palladium, lead is on macromolecule, is being roasted
During burning, palladium-lead atom can carry out oxidation reaction in situ, during oxidation reaction, form the oxide of palladium, lead
Eutectic.
Maceration extract surface tension and solvation effect can be overcome to prepare catalysis to the influence of palladium-lead dispersion using this method
Agent is alloy-type bimetallic catalyst, therefore has superior selectivity.
Due to Al in the present invention2O3The Al-O keys for being carrier will be to the strong suction of hydroxyl generation in hydroxyl-dipyridyl derivatives
It is attached, therefore can effectively ensure Al2O3It is carrier to high molecular adsorbance, avoids the damage of hydroxyl-dipyridyl derivatives in solution
It loses.Simultaneously as being adsorbed on Al2O3It is the hydroxyl and adjacent nitrogen base and active component of hydroxyl-dipyridyl derivatives on carrier
Pd, help the complexing power of active component Pb stronger, it can be ensured that active component Pd in solution, to help active component Pb by hydroxyl-
Bipyridyl/Al2O3Absorption completely, the loss for avoiding active component Pd in solution, helping active component Pb reduce production cost.
Hydroxyl-the dipyridyl derivatives introduced in the present invention can be such that metallic atom reaches because of the presence of polymer effect
The effect of high uniformity dispersion, hydroxyl-bipyridyl of the present invention can be hydroxyl 2,2 ,-dipyridyl derivatives, band hydroxyl
The 3 of base, 3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.
Hydrogenation catalyst of the present invention, what roasting preferably carried out in having oxygen atmosphere, calcination temperature of the present invention is preferably 350
DEG C~500 DEG C.
In catalyst in use, can H be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
The molal quantity of hydroxyl-dipyridyl derivatives/(Pd+Pb) is 20~120.Solvent is added in step in order to make hydroxyl
Base-bipyridyl is completely dissolved, and to be conducive to absorption of the macromolecule on carrier, solvent can be ethyl alcohol and ether.Solvent adds
How much enter amount, mainly controlling institute's solubilizer can be such that macromolecule is completely dissolved.
In stepb, it is described configuration palladium-lead solution in palladium, lead dosage, Pd, Pb of final catalyst can be made
Content, wherein Pd are preferably preferably 0.04~3% in 0.02~0.5%, Pb contents.
The solution of palladium-lead can be the soluble salt solutions of palladium, lead, such as can be Pd (NO3)2、Pb(NO3)2Mixing it is molten
Liquid.
Using plasma emission spectrometer or atomic absorption spectrum can measure catalyst Pd contents and Pb content (standards
GB/T 15337-94), the existing forms of Pd-Pb on catalyst can be measured using XRD.
In the present invention, hydroxyl-dipyridyl derivatives are loaded on alumina series carrier, then passes through hydroxyl-bipyridyl
The cation of extra hydroxyl and/or adjacent nitrogen base and Pd, Pb forms complex ion.The solution for configuring palladium-lead, has official by load
The high molecular predecessor of energyization is impregnated into the palladium-lead solution prepared, and is reacted under certain conditions, make palladium, lead from
Son is complexed on the macromolecular chain loaded simultaneously.The ion of palladium-lead is attached on macromolecule by chemical reaction, each
The palladium combined on macromolecule-lead atom number is proportional to hydroxyl, the quantity of nitrogen base on macromolecule, the hydroxyl-bipyridyl
Quantity is preferably 50~200 times of (palladium+lead) molal quantity.During the reaction, what palladium, lead button were orderly is distributed in macromolecule
On.In roasting process, palladium-lead atom can carry out oxidation reaction in situ, and catalyst prepared by this method is that alloy-type is double
Metallic catalyst overcomes the unfavorable shadow of maceration extract surface tension and solvation effect to palladium-lead dispersion using the preparation method
It rings, the catalyst of preparation is more conducive to form palladium-metal, and catalyst has excellent selectivity.
Catalyst of the present invention can be used for the selection hydrogenation process of the third fraction of carbon two, carbon, have good hydrogenation activity, excellent
Different selectivity and preferable anticoking capability.
Meanwhile the method for the present invention prepares palladium-lead catalyst, is more suitably applied to C-4-fraction, the higher carbon of MAPD contents
Two, carbon three selects hydrogenation plant.The catalyst forms, and has and C-4-fraction, MAPD and palladium is hindered to form soluble complicated chemical combination
Object and the effect being lost in still have excellent hydrogenation activity and stabilization under C-4-fraction, the higher working condition of MAPD contents
Property.
Specific implementation mode
Analysis test method：
Specific surface area：GB/T-5816
Kong Rong：GB/T-5816
Heap density：Q/SY142-2006
Catalyst Pd, Pb assay：Using plasma emission spectrometer measures catalyst Pd contents and Pb contents.
Standard GB/T 1537-94
Ethylene selectivity=△ ethylene/△ acetylene
Embodiment 1
Weigh Φ 4.5mm, length 4.5mm, specific surface 3.2m2/ g, hole hold the column α-Al of 0.24mL/g2O3Carrier
500g。
By 92.28g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 2h 4,4- dihydroxy -2,2- bipyridyls being loaded on alumina support completely, 80 DEG C of dry 6h,
Obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.24g Pd (NO3)2、1.05g Pb(NO3)2, it is added in 500mL deionized waters, is slowly added to concentrated nitric acid
10mL is heated to being completely dissolved, and it is 2.0 to adjust pH value.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor, which is added to, have been prepared
Solution stirs 15min, stands 3h, pours out raffinate, obtain Pd/Pb- hydroxyls-bipyridyl/Al2O3(hydroxyl-bipyridyl rubs precursor
That number：(Pd+Pb)=120).Roast 4h in air atmosphere at a temperature of 550 DEG C after 120 DEG C of dry 4h, obtain (Pd-Pb)/
Al2O3Catalyst.It is positioned in fixed-bed reactor before use, is N with molar ratio2:H2=1:1 mixed gas, 120
It is restored at a temperature of DEG C, obtains load type palladium-lead catalyst S-1.It is that 0.020%, Pb contents are to measure catalyst Pd contents
0.13%.
Comparative example 1：
Weigh Φ 4.5mm, length 4.5mm, specific surface 3.2m2/ g, hole hold the column α-Al of 0.24mL/g2O3Carrier
500g。
Weigh appropriate Pd (NO3)2、Pb(NO3)2It is dissolved in the 500mL deionized waters containing appropriate nitric acid, is heated to completely molten
Solution, it is 2.1 to adjust pH value.Above-mentioned carrier is added to the solution prepared, stirs 10min, raffinate is poured out, 550 after drying
6h is roasted at a temperature of DEG C in air atmosphere, obtains (Pd-Pb)/Al2O3Catalyst.It is positioned in fixed-bed reactor before use,
It is N with molar ratio2:H2=1:1 mixed gas obtains load type palladium-lead comparative catalyst D-1 at a temperature of 120 DEG C.It measures
Catalyst Pd contents are that 0.020%, Pb contents are 0.13%.
Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 1.
1 hydrogenating materials of table composition is as shown in the table
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | C3H6 | C3H8 | MAPD | CO | C4 + |
| Content (Φ %) | 18.6 | 0.7 | 35 | 6 | 23 | 13.1 | 2.5 | 1.2 | 0.18 | 0.50 |
Reaction condition：
Operating pressure：3.5MPa,；Loaded catalyst：500ml.Initial reaction stage (50h) material air speed：4000h-1, then
Air speed is promoted to 6000h-1, every one group of 10h sampling analyses.
Adiabatic reactor reactor, two sections of tandem process carry out hydrogenation reaction.Second stage reactor is tied after examination in 200 hours
Fruit is as shown in table 2.
2 two sections of the table result of appraisal of adiabatic reactor reactor 200 hours
Embodiment 2
Weigh Φ 2.4mm, specific surface area 45m2The ball type carrier 500g of/g, Kong Rongwei 0.24ml/g, wherein containing θ-
Al2O3Carrier 440g, titanium oxide 60g.
By 15.75g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 600mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 8h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 100 DEG C of dry 5h are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.73gPd (NO3)2,5.20g Pb(NO3)2, it is added in 600mL deionized waters, is slowly added to concentrated nitric acid
10mL is heated to being completely dissolved, and it is 2.5 to adjust pH, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added
To the solution prepared, 60min is stirred, 3h is stood, pours out raffinate, obtain PdPb- hydroxyls-bipyridyl/Al2O3Precursor.
By the presoma of above-mentioned preparation, 550 DEG C of roasting 6h, obtain catalyst S-2 in air atmosphere.Measure the catalyst
Pd contents are that 0.060%, Pb contents are 0.62%.
Comparative example 2：
A is functionalized SAN/Al2O3Preparation
Weigh Φ 2.4mm, specific surface area 45m2The ball type carrier 500g of/g, Kong Rongwei 0.24ml/g, wherein containing θ-
Al2O3Carrier 440g, titanium oxide 60g.
SAN resin 3.3g are weighed, are dissolved in 600ml DMF solvents, stirring at room temperature makes SAN resins be completely dissolved,
Be added in this solution it is above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred, detach dry after solvent, obtain SAN/ θ-Al2O3
Presoma.
By functionalization-SAN/ θ-Al obtained above2O3Presoma is added in 1000ml deionized waters, and 85.2g is added
Ethylenediamine, flow back 60min, and product is taken out after cooling, washs to neutrality, is dried to obtain functionalization-SAN/Al2O3Presoma.
B(Pd-Pb)-SAN/Al2O3The preparation of precursor
Weigh 0.73gPd (NO3)2,5.20g Pb(NO3)2It is dissolved in the 1200mL deionized waters containing appropriate nitric acid, heats
To being completely dissolved, it is 2.7 to adjust pH value.Functionalization-the SAN/Al for taking step A to prepare2O3Presoma is added to Pd (NO3)2、Pb
(NO3)2Mixed solution in, stir 120min, pour out raffinate, above-mentioned product be washed with deionized to neutrality, (Pd- is obtained
Pb)-SAN/Al2O3Precursor.
The preparation of C catalyst
By the presoma of above-mentioned preparation, 380 DEG C of roasting 2h, obtain comparative catalyst D-2 in air atmosphere.This is measured to urge
Agent Pd contents are that 0.06%, Pb contents are 0.62%.
Using back end hydrogenation technique, raw material group becomes：
C2H2：1.7% (Φ), C2H4：74.3% (Φ), C2H6：24.0% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade reactions, i.e. first stage reactor outlet material enter second stage reactor.
Every section of reactor has independent air distribution system.
Material gas space velocity：10000h-1, operating pressure：1.7MPa, each reactor catalyst loadings：500ml.One section
Reactor H2/C2H2=1.6：1 (molar ratio)；Second stage reactor H2/C2H2=2.8：1 (molar ratio), after examination in 150 hours
The results are shown in Table 3.
3 catalyst 200h performance average values of table
Embodiment 3：
Weigh diameter 4.2mm, length 4.2mm, specific surface area 18m2The cylindric carrier of/g, Kong Rongwei 0.31ml/g
500g, wherein Al2O3400g, magnesia 100g, Al2O3For α-Al2O3。
By 69.5g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 120 DEG C of dryings
4h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.49g Pd (NO3)2, 1.82g Pb (NO3)2, it is dissolved in 600mL deionized waters, is slowly added to concentrated nitric acid
10mL is heated to being completely dissolved, and it is 3.3 to adjust pH value, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor, which is added to, have been prepared
Solution, stir 60min, stand 10h, pour out raffinate, obtain PdPb- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl
Molal quantity：(Pd+Pb)=50).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 8h, obtain catalyst S-3 in air atmosphere.Measure the catalyst
Pd contents are that 0.040%, Pb contents are 0.23%.
Comparative example 3：
Weigh diameter 4.2mm, length 4.2mm, specific surface area 18m2The cylindric carrier of/g, Kong Rongwei 0.31ml/g
500g, wherein Al2O3400g, magnesia 100g, Al2O3For α-Al2O3。
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC 8.9g are dissolved completely in 800mlTHF (tetrahydrofuran), by above-mentioned carrier impregnation to above-mentioned solution,
PVC is set to be adsorbed in Al after standing 2h2O3Surface, drying for standby.Obtain PVC/Al2O3。
119.28g dicyandiamides and 4.0gNa is added2CO3, above-mentioned PVC/Al is added2O3Flow back 1h, is cooled to room temperature, spends
Ion water washing to neutrality, drying for standby obtains functionalization PVC/Al2O3。
B、Pd-Pb-polymer/Al2O3The preparation of presoma
Weigh 0.49g Pd (NO3)2, 1.82g Pb (NO3)2, 2400mL deionized waters are dissolved in, the dense nitre of 10mL is slowly added to
For acid to being completely dissolved, it is 2.1 to adjust pH value, is made into mixed solution, takes the functionalization-PVC/Al prepared2O3Presoma, by itself plus
Enter to Pd (NO3)2、Pb(NO3)2Mixed solution in, stir 30min, pour out raffinate, above-mentioned product be washed with deionized
To neutrality, (Pd-Pb)-PVC/Al is obtained after dry 4h at 120 DEG C2O3Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h, obtain oxidation state (Pd-Pb)/Al in air atmosphere2O3Catalysis
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas, at 120 DEG C
At a temperature of, obtain load type palladium-lead catalyst D-3.It is 0.23% that measure catalyst Pd contents, which be 0.040%, Pb contents,.
Reaction mass comes from front-end deethanization column overhead, and composition is as shown in table 4.
4 hydrogenating materials of table form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | CO | C4 + |
| Content (v/v%) | 29 | 0.5 | 32.3 | 6.88 | 31 | 0.005 | 0.515 |
Reaction condition 1：Using front-end deethanization front-end hydrogenation technique, the hotbeds reactor such as single hop, material air speed is 18000h-1,
Operating pressure 4.0MPa, loaded catalyst 500ml.
The hotbeds reactors such as 5 single hop of table were through 200 hours reaction results
Embodiment 4
Weigh Φ 2.4mm, specific surface 18.0m2/ g, hole hold the ball-type α-Al of 0.16mL/g2O3Carrier 500g.
By 53.26g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 600mL ethanol solutions, by carrier impregnation in above-mentioned solution
In, after after standing 16h 4,4- dihydroxy -2,2- bipyridyls being loaded on alumina support completely, 120 DEG C of dry 5h are obtained
To hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.61g Pd (NO3)2、3.90g Pb(NO3)2, it is added in 600mL deionized waters, is slowly added to concentrated nitric acid
10mL is heated to being completely dissolved, and it is 3.5 to adjust pH value.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor, which is added to, have been prepared
Solution stirs 10min, stands 12h, pours out raffinate, obtain PdPb- hydroxyls-bipyridyl/Al2O3(hydroxyl-bipyridyl rubs precursor
That number：(Pd+Pb)=20).8h is roasted in air atmosphere at a temperature of 450 DEG C after 90 DEG C of dry 8h, obtains (Pd-Pb)/Al2O3
Catalyst.It is positioned in fixed-bed reactor before use, is N with molar ratio2:H2=1:1 mixed gas, in 115 DEG C of temperature
Lower reduction obtains load type palladium-lead catalyst S-4.It is 0.050%, Pb contents 0.48% to measure catalyst Pd contents.
Comparative example 4
Weigh Φ 2.4mm, specific surface 18.0m2/ g, hole hold the ball-type α-Al of 0.16mL/g2O3Carrier 500g.
By 53.26g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 600mL ethanol solutions, by carrier impregnation in above-mentioned solution
In, after after standing 16h 4,4- dihydroxy -2,2- bipyridyls being loaded on alumina support completely, 120 DEG C of dry 5h are obtained
To hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate 0.61g Pd (NO3)2、1.95g AgNO3It is dissolved in the 600mL deionized waters containing appropriate nitric acid, heats
To being completely dissolved, it is 3.5 to adjust pH value.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, stirring
10min stands 12h, pours out raffinate, obtain PdAg- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+
Ag)=20).8h is roasted in air atmosphere at a temperature of 450 DEG C after 90 DEG C of dry 8h, obtains (Pd-Ag)/Al2O3Catalyst.Make
It is N with molar ratio with being preceding positioned in fixed-bed reactor2:H2=1:1 mixed gas is restored at a temperature of 115 DEG C, is obtained
To load type palladium-silver catalyst D-4.It is 0.050%, Ag contents 0.24% to measure catalyst Pd contents.
Using the front-end hydrogenation technique of predepropanization, reaction raw materials are as shown in table 8 to form.
8 hydrogenating materials of table composition is as shown in the table
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (Φ %) | 18 | 0.6 | 33 | 6.2 | 26.2 | 13 | 2 | 0.8 | 0.2 | 0.47 |
Reaction condition：Material air speed：4000h-1；Operating pressure：3.5MPa；Loaded catalyst：500ml.
Adiabatic reactor reactor, two sections of tandem process carry out hydrogenation reaction.Second stage reactor is tied after examination in 200 hours
Fruit is as shown in table 9.
9 two sections of the table result of appraisal of adiabatic reactor reactor 200 hours
It can be seen that compared with using traditional preparation catalyst from above embodiment, side using the present invention
After method, the activity of C-2-fraction hydrogenation reaction, selectivity, anticoking capability increase substantially.
Claims (13)
1. a kind of system supported hydrogenation catalyst of palladium-lead, palladium, lead, Al are contained in catalyst2O3It is carrier, it is characterised in that：With
The quality of catalyst is 100% meter, and wherein Pd contents are 0.01~0.8%；Pb contents are 0.04~3%；Catalyst specific surface
Product is 2~100m2/ g, pore volume are 0.15~0.8mL/g, and heap density is 0.5~1.2g/cm3；The catalyst preparation process packet
It includes：Al is impregnated with the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, after drying again with the mixing sun containing Pd, Pb
Solion impregnates, dry roasting.
2. hydrogenation catalyst according to claim 1, it is characterised in that Al2O3Be carrier it is Al2O3Or mainly Al2O3,
Wherein also doped with other hopcalites, other oxides are silica, titanium oxide, magnesia and/or calcium oxide.
3. hydrogenation catalyst according to claim 1, it is characterized in that：The Al2O3For γ, δ, θ, alpha-crystal form or in which several
The mixing crystal form of kind.
4. hydrogenation catalyst according to claim 1, it is characterised in that catalyst Pd contents are that 0.02~0.5%, Pb contains
Amount is 0.04~3%.
5. hydrogenation catalyst according to claim 1, it is characterised in that the specific surface area of catalyst is 2~100m2/ g, hole
Volume is 0.20~0.60mL/g, and heap density is 0.60~1.1g/cm3。
6. hydrogenation catalyst according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives are hydroxyl
2,2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives.
7. according to the hydrogenation catalyst one of described in claim 1 to 6, it is characterised in that the preparation of catalyst includes following mistake
Journey：
A. by the organic solution and Al of hydroxyl dipyridyl derivatives2O3It is carrier mixing, is reacted at a temperature of 20 DEG C~60 DEG C
2~for 24 hours, and solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Presoma；
B. prepare Pd, Pb mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl-bipyridyl obtained by step A/
Al2O3Forerunner's precursor reactant 2~for 24 hours takes out solid particle, dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyls-bipyridyl/
Al2O3Presoma；
C. the PdPb- hydroxyls-bipyridyl/Al prepared by step B2O3Presoma in 300~600 DEG C of 2~12h of roasting temperature,
Make PdPb- hydroxyls-bipyridyl/Al2O3Presoma is changed into corresponding metal composite oxide, obtains catalyst.
8. hydrogenation catalyst according to claim 7, it is characterised in that the molar ratio of hydroxyl-bipyridyl/(Pd+Pb) is 20
~120：1.
9. hydrogenation catalyst according to claim 7, it is characterised in that in stepb, the mixed-cation solution of Pd, Pb
For the mixed solution of palladium nitrate and plumbi nitras.
10. hydrogenation catalyst according to claim 7, it is characterised in that in stepb, adjust Pd, Pb mixing sun from
Sub- solution ph is 1.5~4.0.
11. hydrogenation catalyst according to claim 7, it is characterised in that in stepb, the molal quantity of Pb and mole of Pd
The ratio between number is 1~10：1.
12. hydrogenation catalyst according to claim 1, it is characterised in that roasting refers in 300~600 DEG C of roasting temperatures
2~12h.
13. hydrogenation catalyst according to claim 1, it is characterised in that roasting refers to being roasted at a temperature of 350 DEG C~500 DEG C
Burn 2~12h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410806061.7A CN105749910B (en) | 2014-12-19 | 2014-12-19 | Palladium-lead supported hydrogenation catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410806061.7A CN105749910B (en) | 2014-12-19 | 2014-12-19 | Palladium-lead supported hydrogenation catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105749910A CN105749910A (en) | 2016-07-13 |
| CN105749910B true CN105749910B (en) | 2018-10-16 |
Family
ID=56341487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410806061.7A Active CN105749910B (en) | 2014-12-19 | 2014-12-19 | Palladium-lead supported hydrogenation catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105749910B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113694941B (en) * | 2020-05-20 | 2024-05-07 | 中国石油化工股份有限公司 | Supported metal catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157031A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | A recapitalization generating oil hydrogenation catalysts and its preparing method |
| CN101255358A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | A kind of selective hydrogenation catalyst and its preparation method |
| 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 |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7595410B2 (en) * | 2006-07-18 | 2009-09-29 | Lyondell Chemical Technology, L.P. | Direct epoxidation process using improved catalyst composition |
| CN102407118B (en) * | 2010-09-21 | 2013-06-05 | 中国石油化工股份有限公司 | Unsaturated hydrocarbon hydrogenation catalyst and application thereof |
-
2014
- 2014-12-19 CN CN201410806061.7A patent/CN105749910B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157031A (en) * | 2007-11-12 | 2008-04-09 | 中国海洋石油总公司 | A recapitalization generating oil hydrogenation catalysts and its preparing method |
| CN101255358A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | A kind of selective hydrogenation catalyst and its preparation method |
| 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 |
|---|
| 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;何炳林等;《应用化学》;19891231;第6卷(第2期);第52-55页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105749910A (en) | 2016-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105727991B (en) | Palladium-copper series supported hydrogenation catalyst | |
| CN102205243B (en) | Palladium-silver bimetallic hydrogenation catalyst | |
| CN105727992B (en) | Palladium-nickel series supported hydrogenation catalyst | |
| CN105727990B (en) | Preparation method of palladium-copper supported hydrogenation catalyst | |
| CN105732285B (en) | Carbon three-fraction selective hydrogenation method | |
| CN105727989B (en) | Preparation method of palladium-nickel-series supported hydrogenation catalyst | |
| CN105727946B (en) | Preparation method of palladium-silver supported hydrogenation catalyst | |
| CN105732260B (en) | Method for selective hydrogenation of carbon-containing distillate | |
| CN105749910B (en) | Palladium-lead supported hydrogenation catalyst | |
| CN105749909B (en) | Preparation method of palladium-lead supported hydrogenation catalyst | |
| CN105732284B (en) | Selective hydrogenation method of carbon three-fraction | |
| CN105732281B (en) | Pre-depropanization pre-hydrogenation method for carbon-dioxide fraction | |
| CN105727945B (en) | Palladium-silver series supported hydrogenation catalyst | |
| CN108250017A (en) | Method for selective hydrogenation of carbon three-fraction | |
| CN105732267B (en) | Process for the selective hydrogenation of a carbon-containing fraction | |
| CN105732276B (en) | Hydrogenation method before deethanization of carbon-containing fraction | |
| CN105727947B (en) | Palladium-gold series supported hydrogenation catalyst | |
| CN106928004B (en) | Carbon three-fraction selective hydrogenation method | |
| CN105732277B (en) | Method for pre-depropanizing and pre-hydrogenating carbon-containing fraction | |
| CN105753627B (en) | Carbon three-fraction selective hydrogenation method | |
| CN105727948B (en) | Preparation method of palladium-gold supported hydrogenation catalyst | |
| CN105732280B (en) | Hydrogenation method before deethanization of carbon-containing distillate | |
| CN105732265B (en) | Carbon two selective hydrogenation method in sequential separation process | |
| CN105732279B (en) | Method for post-hydrogenation of carbon-containing distillate | |
| CN105732259B (en) | Carbon three-fraction selective hydrogenation method |
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 |