CN105749909A - Preparation method of palladium-lead based loaded hydrogenation catalyst - Google Patents
Preparation method of palladium-lead based loaded hydrogenation catalyst Download PDFInfo
- Publication number
- CN105749909A CN105749909A CN201410804175.8A CN201410804175A CN105749909A CN 105749909 A CN105749909 A CN 105749909A CN 201410804175 A CN201410804175 A CN 201410804175A CN 105749909 A CN105749909 A CN 105749909A
- Authority
- CN
- China
- Prior art keywords
- hydroxyl
- preparation
- catalyst
- bipyridyl
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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 preparation method of a palladium-lead based loaded hydrogenation catalyst.The catalyst contains palladium and lead, and a carrier contains Al2O3.The preparation method is characterized by including: soaking the Al2O3 based carrier in an organic solution of a dipyridine derivative with hydroxyl; drying, and using a mixed cationic solution of Pd and Pb for soaking; drying, and baking to obtain the Pd-Pb catalyst.Unfavorable influence on dispersion of palladium-lead caused by impregnation liquid surface tension and solvation effect is overcome in the preparation method, so that the catalyst prepared is more conducive to forming a palladium-lead alloy and has excellent activity, selectivity and coking resistance; Pb has good effect on stopping Pd loss, so that the catalyst is more suitable for being used in the selective hydrogenation process of fractions like C2 and C3 high in MAPD content and C4 fraction content, and has good hydrogenation activity, excellent selectivity and good coking resistance; when hydrogenation materials are high in MAPD content and C4 fraction content, the catalyst also has excellent hydrogenation performance.
Description
Technical field
The preparation method that the present invention relates to a kind of catalyst, the preparation method being specifically related to a kind of palladium-lead system supported catalyst.
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 C2Acetylene in 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, price modification 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.Adopting this patented method, the specific macromolecular compound of carrier adsorption carries out chemisorbed by the hydroxyl of aluminium oxide and macromolecule, and the amount of carrier adsorption macromolecular compound is subjected to aluminium oxide hydroxyl value quantitative limitation；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.
Carbon two, carbon three select in hydrogenation plant hydrogenating materials possibly together with a certain amount of C-4-fraction and propine, allene (MAPD), C-4-fraction, MAPD are in the easy coking of catalyst surface, solvable complex compound can be formed with palladium and cause palladium to run off simultaneously, thus affecting the activity of catalyst, catalysqt deactivation can be caused, thus bringing device leakage alkynes risk time serious.
Summary of the invention
In view of the above circumstances, the preparation method that the present invention proposes a kind of palladium-plumbous system supported hydrogenation catalyst.
The solution of the present invention is: impregnate Al by the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, after drying again by the mixed-cation solution impregnation of Pd, Pb, dry roasting, obtains Pd-Pb catalyst.
In the present invention, after forming strong absorption containing hydroxyl dipyridyl derivatives and aluminium oxide, then define organic polymer complex with active component Pd, Pb, finally obtain the Pd-Pb catalyst of high dispersive.The ratio of the molal quantity of best hydroxyl dipyridyl derivatives/(Pd+Pb) is 1～50.
This process can be divided into 3 steps to carry out:
(1) first Al is impregnated by the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, forms hydroxyl-bipyridyl/Al after drying2O3Precursor；
(2) with the mixed-cation solution impregnation hydroxyl-bipyridyl/Al containing Pd, Pb2O3Precursor, dried formation PdPb-hydroxyl-bipyridyl/Al2O3Precursor；
(3) roasting PdPb-hydroxyl-bipyridyl/Al2O3Precursor obtains Pd-Pb catalyst.
In the present invention, dry best carry out at 60 DEG C～150 DEG C.
Roasting preferably carries out at 300～600 DEG C, roasting 2～12h.
Palladium prepared by method provided by the invention-plumbous system supported hydrogenation catalyst has palladium-scattered structure of lead high uniformity.
Carrier of the present invention is alumina series carrier, it is possible to be Al2O3, it is also possible to it is mainly contain Al2O3, and doped with other hopcalite, other oxide can be silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide etc..Described Al2O3Can be γ, δ, θ, α or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation Al2O3。
In the present invention, carrier can be spherical, cylindrical, annular, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc..
Hydroxyl dipyridyl derivatives, it is preferred to hydroxyl 2,2,-dipyridyl derivatives, hydroxyl 3,3,-dipyridyl derivatives, it is preferred to hydroxyl 2,2,-dipyridyl derivatives.
The preparation method of this catalyst that the present invention recommends is rapid:
The step (1) recommended: hydroxyl-bipyridyl/Al2O3The preparation of precursor:
By the organic solution of hydroxyl dipyridyl derivatives and Al2O3It is carrier mixing, at 20 DEG C～60 DEG C temperature, reacts 2～24h, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；The volume of organic solution is preferably equal to or greater than the 80% of carrier cumulative volume.
The step (2) recommended: PdPb-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Pb, with step (1) gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, dry at 60 DEG C～150 DEG C, obtain PdPb-hydroxyl-bipyridyl/Al2O3Precursor.
Mixed-cation solution ph is preferably adjusted to 1.5～4.0.
The step (3) recommended: the preparation of catalyst
PdPb-hydroxyl-bipyridyl/Al prepared by step 22O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdPb-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains Pd-Pb catalyst.
When catalyst uses, H can be used in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
In step 1, described hydroxyl dipyridyl derivatives, it is preferred to hydroxyl 2,2 '-dipyridyl derivatives, makes Al2O3While it is produced higher chemisorbed, two nitrilo that unnecessary hydroxyl is adjacent with bipyridyl combine with active component Pd, Pb.
Needing in step 1 to add solvent, this is that 2 '-dipyridyl derivatives can be completely dissolved in order to make hydroxyl 2, to be conducive to macromolecule absorption on carrier, for usual organic solvent, as being ethanol and ether.The addition of solvent is how many, mainly to control institute's solubilizer and macromolecule can be made to be completely dissolved.
In step 2, the solution of palladium-lead can be palladium, plumbous soluble salt solutions, as being Pd (NO3)2、PbNO3Mixed solution.In described mixed solution, palladium, lead salt consumption are can make Pd, Pb content of final catalyst, can select different Pd, Pb content according to the purposes of catalyst, it is desirable to the ratio of the molal quantity of Pb and the molal quantity of Pd is 1.0～10.
In step 3, roasting preferably carries out in aerobic atmosphere, sintering temperature of the present invention preferably 350 DEG C～500 DEG C.
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, plumbous atom are in uniform sequential distribution on macromolecule, in the process of roasting, palladium-lead atom can carry out oxidation reaction in position, in the process of oxidation reaction, form palladium, plumbous oxide eutectic.
Adopting the method can overcome the scattered impact on palladium-lead of impregnation liquid surface tension and solvation effect, 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-bipyridyl being produced strong absorption, therefore can effectively guarantee Al2O3Carrier is to high molecular adsorbance, it is to avoid the loss of hydroxyl-bipyridyl in solution.Simultaneously as be adsorbed on Al2O3The hydroxyl of the hydroxyl-bipyridyl on carrier and nitrilo and active component Pd, the complexing power helping active component Pb are stronger, it can be ensured that active component Pd in solution, help active component Pb by hydroxyl-bipyridyl/Al2O3Adsorbed completely, it is to avoid active component Pd in solution, help the loss of active component Pb, reduced production cost.
Hydroxyl-the bipyridyl introduced in the present invention, because the existence of polymer effect, can make metallic atom reach the scattered effect of high uniformity.
In the present invention, being loaded to by hydroxyl-bipyridyl on alumina series carrier, the cation of the hydroxyl unnecessary again through hydroxyl-bipyridyl and/or nitrilo and Pd, Pb forms complex ion.The solution of configuration palladium-lead, is impregnated into being loaded with functionalized high molecular predecessor in the palladium-lead solution prepared, reacts under certain conditions, make palladium, lead ion be complexed on the macromolecular chain of load simultaneously.The ion of palladium-lead is attached on macromolecule by chemical reaction, palladium-lead 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 1～50 times of (palladium+lead) amount of ions.In course of reaction, orderly being distributed on macromolecule of son of palladium, lead button.In roasting process, palladium-lead 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 the solvation effect scattered adverse effect to palladium-lead, the catalyst of preparation, it is more conducive to form palladium-metal, reaches to improve the effect of catalyst activity and selectivity.
Using plasma emission spectrometer or atomic absorption spectrum can record this catalyst Pd content and Pb content (standard GB/T15337-94), adopt XRD can measure the existing forms of Pd-Pb on catalyst.
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-lead catalyst, is more suitably applied to C-4-fraction, carbon two that MAPD content is higher, carbon three select hydrogenation plant.This catalyst forms, and has the effect hindering C-4-fraction, MAPD and palladium to form solvable complex compound and run off, and under the working condition that C-4-fraction, MAPD content are higher, still has excellent hydrogenation activity and stability.
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, Pb assay: using plasma emission spectrometer records this catalyst Pd content and Pb content.Standard GB/T1537-94
Ethylene selectivity=△ ethylene/△ acetylene
Embodiment 1
Weighing Φ 4.2mm, length is 4.2mm, specific surface 3.0m2Column α-the Al of/g, pore volume 0.24mL/g2O3Carrier 500g.
By 10.34g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, make 4 after standing 2h, 4 '-dihydroxy-2,2 '-bipyridyl loads to after on alumina support completely, 60 DEG C of dry 10h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.30gPd (NO3)2、0.52gPb(NO3)2Being dissolved in 600mL deionized water, adjusting pH is 2.0, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdPb-hydroxyl-bipyridyl/Al2O3The ratio of precursor, hydroxyl-bipyridyl and (Pd+Pb) molal quantity is 20.After 120 DEG C of dry 4h at 550 DEG C of temperature roasting 2h in air atmosphere, obtain (Pd-Pd)/Al2O3Catalyst.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 load type palladium-lead catalyst S-1.Recording this catalyst Pd content is 0.025%, and Pb content is 0.06%.
Comparative example 1:
Weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 17m2/ g, pore volume is the column α-Al of 0.22ml/g2O3Carrier 500g.
A, functionalized PVC/Al2O3Preparation
PVC8.9g is dissolved completely in 800ml oxolane (THF), makes PVC be deposited on Al 1h in the carrier impregnation weighed up to above-mentioned solution2O3Surface, pours out residual liquid, dries and obtains PVC/Al2O3Product.
Add 119.28g dicyandiamide and 2.0gNa2CO3, add above-mentioned PVC/Al2O3Reflux 4 hours, be cooled to room temperature, with deionized water wash to neutral, drying for standby.Obtain functionalized PVC/Al2O3.Reactive group Cl molal quantity=10 on chelating agent dicyandiamide molal quantity/macromolecular chain.
B、Pd-Pb-polymer/Al2O3The preparation of presoma
Take 0.30gPd (NO3)2、0.52gPb(NO3)2Being dissolved in the 500mL deionized water containing appropriate nitric acid, heating is to being completely dissolved, and regulating pH value is 1.6.Take the functionalized-PVC/Al of preparation in step A2O3Presoma, adds it to Pd (NO3)2、Pb(NO3)2Mixed solution in, stir 30min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, obtain (Pd-Pb)-PVC/Al2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, in air atmosphere, 550 DEG C of roasting 2h, obtain oxidation state Pd-Pb/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 300h-1Gas, at 100 DEG C of temperature reduce 4h, obtain catalyst D-1.Recording this catalyst Pd content is 0.025%, and Pb content is 0.06%.
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 %) | 20.0 | 0.6 | 36.1 | 4.3 | 24.0 | 12 | 2.0 | 0.75 | 0.2 | 0.5 |
Reaction condition: material air speed: 4500h-1；Operation pressure: 3.5MPa,；Loaded catalyst: 500ml.
Adiabatic reactor reactor, two-stage nitration tandem process, carry out hydrogenation reaction.Three sections of reactor results after the examination of 200 hours are as shown in table 2.
Table 2 200 hours result of appraisal of two-stage nitration adiabatic reactor reactor
Embodiment 2
Weighing Φ 2.7mm, specific surface area is 50m2/ g, pore volume is the ball type carrier 500g of 0.75ml/g, wherein containing θ-Al2O3Carrier 440g, titanium oxide 60g.
By 174.5g4,4 '-dihydroxy-2,2 '-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, make 4 after standing 8h, 4 '-dihydroxy-2,2 '-bipyridyl loads to after on alumina support completely, 90 DEG C of dry 8h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.61gPd (NO3)2,5.20gPb(NO3)2Being dissolved in 600mL deionized water, adjusting pH is 2.5, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid dry 6h at 110 DEG C obtains PdPb-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Pb) molal quantity=50).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere, obtain catalyst S-2.Recording this catalyst Pd content is 0.060%, and Pb content is 0.63%.
Comparative example 2:
Weighing Φ 4.5mm, length is 4.5mm, specific surface 2.0m2Column α-the Al of/g, pore volume 0.20mL/g2O3Carrier 500g.
Weigh appropriate Pd (NO3)2、Pb(NO3)2Being dissolved in the 600mL deionized water containing appropriate nitric acid, heating is to being completely dissolved, and regulating pH value is 1.5.Above-mentioned carrier joining the solution prepared, stirs 10min, pour out residual liquid, roasting 2h in air atmosphere at 550 DEG C of temperature, obtains (Pd-Pb)/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 load type palladium-lead comparative catalyst D-2.Recording this catalyst Pd content is 0.025%, and Pb content is 0.63%.
Adopting the front-end hydrogenation technique of predepropanization, reaction raw materials is from predepropanization column overhead, and composition is as shown in table 3.
Shown in table 3 hydrogenating materials table composed as follows
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (Φ %) | 20.0 | 0.6 | 36.1 | 4.3 | 24.0 | 12 | 2.0 | 0.78 | 0.2 | 0.56 |
Reaction condition: material air speed: 4500h-1；Operation pressure: 3.5MPa,；Loaded catalyst: 500ml.
Adiabatic reactor reactor, two-stage nitration tandem process, carry out hydrogenation reaction.Three sections of reactor results after the examination of 200 hours are as shown in table 4.
Table 4 200 hours result of appraisal of two-stage nitration adiabatic reactor reactor
Embodiment 3:
Weighing 4.3*4.3mm, specific surface area is 17m2/ g, pore volume is the cylindric carrier 500g, wherein α-Al of 0.34ml/g2O3400g, magnesium oxide 100g.
By 6.51g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 12h, make 6,6'-dihydroxy-3,3'-bipyridyl loads to after on alumina support completely, 120 DEG C of dry 4h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.37gPd (NO3)2, 1.82gPb (NO3)2Being dissolved in 600mL deionized water, be slowly added dropwise concentrated nitric acid, stir and be completely dissolved to solid, adjusting pH is 3.2, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid dry 8h at 100 DEG C obtains PdPb-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Pb)=5).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere, obtain comparative catalyst S-3.Recording this catalyst Pd content is 0.030%, and Pb content is 0.22%.
Comparative example 3:
The functionalized SAN/Al of A2O3Preparation
Weighing Φ 2.5mm, specific surface area is 50m2/ g, pore volume is the ball type carrier 500g of 0.75ml/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 30min, takes out product after cooling, and washing, to neutral, dry and obtains functionalized-SAN/Al2O3Presoma (on chelating agent ethylenediamine molal quantity/macromolecule reactive group CN base molal quantity=22.85).
B(Pd-Pb)-SAN/Al2O3The preparation of precursor
Weigh appropriate Pd (NO3)2、Pb(NO3)2Being dissolved in the 1200mL deionized water containing appropriate nitric acid, heating is to being completely dissolved, and regulating pH value is 2.5.Take the functionalized-SAN/Al prepared2O3Presoma joins Pd (NO3)2、Pb(NO3)2Mixed solution in, stir 60min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, at remaining solid 110 DEG C, dry 6h, obtains (Pd-Pb)-SAN/Al2O3Precursor (on macromolecule reactive group CN base molal quantity/(Pd+Pb) molal quantity=1).
The preparation of C catalyst
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere, obtain catalyst D-3.Recording this catalyst Pd content is 0.03%, and Pb content is 0.22%.
Adopting carbon two back end hydrogenation technique, raw material consists of:
C2H2: 1.5% (Φ), C2H480.0% (Φ), C2H618.5% (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: 6500h-1, operate pressure: 1.8MPa, each reactor catalyst loadings: 500ml.First stage reactor H2/C2H2=2:1 (mol ratio)；Second stage reactor H2/C2H2=4:1 (mol ratio), after the examination of 200 hours, result is as shown in table 5.
5200 hours catalyst performance meansigma methodss of table
Embodiment 4
Weighing Φ 4.0mm, length is 4.0mm, specific surface 30.0m2Column α-the Al of/g, pore volume 0.50mL/g2O3Carrier 500g.
By 78.56g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, make 4 after standing 10h, 4 '-dihydroxy-2,2 '-bipyridyl loads to after on alumina support completely, 100 DEG C of dry 6h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.55gPd (NO3)2、3.90gPb(NO3)2Being dissolved in 600mL deionized water, adjusting pH is 2.7, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 10h, pours out residual liquid, obtain Pd-Pb-hydroxyl-bipyridyl/Al2O3The ratio of precursor, hydroxyl-bipyridyl and (Pd+Pb) molal quantity is 30.After 100 DEG C of dry 6h at 550 DEG C of temperature roasting 2h in air atmosphere, obtain (Pd-Pb)/Al2O3Catalyst.It is positioned over before using in fixed-bed reactor, is N by mol ratio2:H2The mixing gas of=1:1, reduction treatment at 120 DEG C of temperature, obtain load type palladium-lead catalyst S-4.Recording this catalyst Pd content is 0.045%, and Pb content is 0.48%.
Comparative example 4:
Weighing Φ 4.0mm, length is 4.0mm, specific surface 30.0m2Column α-the Al of/g, pore volume 0.50mL/g2O3Carrier 500g.
By 78.56g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, make 4 after standing 10h, 4 '-dihydroxy-2,2 '-bipyridyl loads to after on alumina support completely, 100 DEG C of dry 6h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.55gPd (NO3)2、1.18gAgNO3Being dissolved in 600mL deionized water, adjusting pH is 2.7, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 10h, pours out residual liquid, obtain PdAg-hydroxyl-bipyridyl/Al2O3The ratio of precursor, hydroxyl-bipyridyl and (Pd+Ag) molal quantity is 30.After 100 DEG C of dry 6h at 550 DEG C of temperature roasting 2h 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, reduction treatment at 120 DEG C of temperature, obtain load type palladium-silver catalyst D-4.Recording this catalyst Pd content is 0.042%, and Ag content is 0.13%.
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 %) | 19.5 | 0.6 | 34.1 | 5.0 | 25.8 | 11.0 | 3.0 | 0.76 | 0.2 | 0.54 |
Reaction condition: material air speed: 8500h-1；Operation pressure: 3.7MPa；Loaded catalyst: 500ml.
Adiabatic reactor reactor, two-stage nitration tandem process, carry out hydrogenation reaction.Three sections of reactor results after the examination of 200 hours are as shown in table 7.
Table 7 200 hours result of appraisal of two-stage nitration adiabatic reactor reactor
Claims (13)
1. the preparation method of palladium-plumbous system supported hydrogenation catalyst, it is characterised in that impregnate Al by the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, after drying again by the mixed-cation solution impregnation of Pd, Pb, dry roasting, obtains Pd-Pb catalyst.
2. preparation method according to claim 1, it is characterised in that the ratio of the molal quantity of hydroxyl dipyridyl derivatives/(Pd+Pb) is 1～50:1.
3. preparation method 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.
4. preparation method according to claim 1, it is characterised in that alumina series carrier, for Al2O3Or mainly contain Al2O3, and doped with other hopcalite.
5. preparation method according to claim 4, it is characterised in that other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.
6. preparation method according to claim 1, it is characterised in that Al2O3For γ, δ, θ, α or above several mixing crystal formation, it is desirable to Al2O3For θ, α or its mixing crystal formation.
7. preparation method according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives is hydroxyl 2,2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives.
8. according to the arbitrary described preparation method of claim 1～7, it is characterised in that catalyst preparing is divided into 3 steps to carry out:
(1) first Al is impregnated by the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, forms hydroxyl-bipyridyl/Al after drying2O3Precursor；
(2) with the mixed-cation solution impregnation hydroxyl-bipyridyl/Al containing Pd, Pb2O3Precursor, dried formation PdPb-hydroxyl-bipyridyl/Al2O3Precursor；
(3) roasting PdPb-hydroxyl-bipyridyl/Al2O3Precursor obtains Pd-Pb catalyst.
9. preparation method according to claim 8, it is characterised in that hydroxyl-bipyridyl in step (1)
/Al2O3The preparation of precursor is:
By the organic solution of hydroxyl dipyridyl derivatives and Al2O3It is carrier mixing, at 20 DEG C～60 DEG C temperature, reacts 2～24h, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor.
10. preparation method according to claim 8, it is characterised in that PdPb-hydroxyl-bipyridyl/Al in step (2)2O3The preparation of precursor is:
The mixed-cation solution of preparation Pd, Pb, with step (1) gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, dry at 60 DEG C～150 DEG C, obtain PdPb-hydroxyl-bipyridyl/Al2O3Precursor.
11. preparation method according to claim 10, it is characterised in that the ratio of the molal quantity of Pb and the molal quantity of Pd is 1.0～10:1.
12. preparation method according to claim 10, it is characterised in that the mixed-cation solution ph regulating Pd, Pb is 1.5～4.0.
13. preparation method according to claim 8, it is characterised in that in step (3), the preparation of catalyst is:
PdPb-hydroxyl-bipyridyl/Al prepared by step (2)2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdPb-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains Pd-Pb catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410804175.8A CN105749909B (en) | 2014-12-19 | 2014-12-19 | A kind of preparation method of the system supported hydrogenation catalyst of palladium-lead |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410804175.8A CN105749909B (en) | 2014-12-19 | 2014-12-19 | A kind of preparation method of the system supported hydrogenation catalyst of palladium-lead |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105749909A true CN105749909A (en) | 2016-07-13 |
| CN105749909B CN105749909B (en) | 2019-01-18 |
Family
ID=56341466
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410804175.8A Active CN105749909B (en) | 2014-12-19 | 2014-12-19 | A kind of preparation method of the system supported hydrogenation catalyst of palladium-lead |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105749909B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209964A (en) * | 2021-05-12 | 2021-08-06 | 中国科学技术大学 | Supported palladium-based catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN102199067A (en) * | 2011-04-07 | 2011-09-28 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
| CN102206130A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
-
2014
- 2014-12-19 CN CN201410804175.8A patent/CN105749909B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN102199067A (en) * | 2011-04-07 | 2011-09-28 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
| CN102206130A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
Non-Patent Citations (2)
| Title |
|---|
| 何炳林等: "高分子负载加氢催化剂中钯流失的研究 Ⅰ.高分子载体的影响", 《应用化学》 * |
| 金关泰主编: "《高分子化学的理论和应用进展》", 31 March 1995 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113209964A (en) * | 2021-05-12 | 2021-08-06 | 中国科学技术大学 | Supported palladium-based catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105749909B (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105727990A (en) | Preparation method of Pd-Cu-series supported hydrogenation catalyst | |
| CN102205243B (en) | Palladium-silver bimetallic hydrogenation catalyst | |
| CN105727991B (en) | A kind of palladium-copper system load hydrogenation catalyst | |
| CN105732285A (en) | Selective hydrogenation method for C3 fraction | |
| CN105727946A (en) | Preparation method of Pd/Ag-series supported hydrogenation catalyst | |
| CN105727989A (en) | Preparation method of Pd-Ni-series supported hydrogenation catalyst | |
| CN105727992B (en) | A kind of system supported hydrogenation catalyst of palladium-nickel | |
| Malibo et al. | Heterostructured Redox‐Active V2O5/SnO2 Oxide Nanocatalyst for Aqueous‐Phase Oxidation of Furfural to Renewable Maleic Acid | |
| CN105732264A (en) | Selective hydrogenation method of trace amount of acetylene in methanol to olefin (MTO) apparatus | |
| CN105732260B (en) | The method of C 2 fraction selective hydrogenation | |
| CN105732281B (en) | C-2-fraction predepropanization front-end hydrogenation method | |
| CN105749909A (en) | Preparation method of palladium-lead based loaded hydrogenation catalyst | |
| CN105732261A (en) | Selective hydrogenation method of trace amount of acetylene in methanol-to-olefin apparatus | |
| CN105732284B (en) | The selection method of hydrotreating of C3 fraction | |
| CN105727945B (en) | A kind of palladium-silver system supported hydrogenation catalyst of palladium- | |
| CN105727948B (en) | A kind of preparation method of the system supported hydrogenation catalyst of palladium-gold | |
| CN105749910A (en) | Palladium-lead based loaded hydrogenation catalyst | |
| CN105732267B (en) | The selection method of hydrotreating of C-2-fraction | |
| CN105732277A (en) | Front-depropanization front-hydrogenation method for C2 fraction | |
| CN105732276B (en) | The method of C-2-fraction front-end deethanization front-end hydrogenation | |
| CN108250020A (en) | A kind of selection method of hydrotreating of C3 fraction | |
| CN105727947B (en) | A kind of system supported hydrogenation catalyst of palladium-gold | |
| CN105753627A (en) | C3 fraction selective hydrogenation method | |
| CN105732279B (en) | C-2-fraction back end hydrogenation method | |
| CN105732280A (en) | Front-deethanization front-hydrogenation method for C2 fraction |
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 |