CN105749909B - A kind of preparation method of the system supported hydrogenation catalyst of palladium-lead - Google Patents
A kind of preparation method of the system supported hydrogenation catalyst of palladium-lead Download PDFInfo
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Abstract
The present invention relates to the preparation method of the system supported hydrogenation catalyst of palladium-lead, palladium, lead are contained in catalyst, contains Al in carrier2O3, it is characterised in that: Al is impregnated in the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, is impregnated again with the mixed-cation solution of Pd, Pb after drying, dry roasting obtains Pd-Pb catalyst.Due to overcoming maceration extract surface tension and solvation effect in preparation method to the adverse effect of palladium-lead dispersion, it is more conducive to form palladium-metal, catalyst has excellent activity, selectivity and anticoking capability；Simultaneously because Pb has the function of preferably preventing Pd to be lost, it is suitably applied that MAPD content is higher, C4The selection hydrogenation process of the higher carbon two of ends content, the third fraction of carbon has good hydrogenation activity, excellent selectivity and preferable anticoking capability；When MAPD content is higher in hydrogenating materials, C4When ends content is higher, it may have excellent Hydrogenation.
Description
Technical field
The present invention relates to a kind of preparation methods of catalyst, and in particular to a kind of preparation side of palladium-lead system supported catalyst
Method.
Background technique
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 fraction 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, the presence of acetylene can also reduce polymerization catalyst when producing polyethylene, increase disappearing for catalyst
Consumption.So certain value must be dropped to the acetylene in ethylene hereinafter, could be as the monomer of synthetic high polymer.
Selection plus hydrogen are generallyd use in industry at present and dissolution extracting removes C2Acetylene in fraction.Dissolve extraction process
Smart ethylene, and recyclable product acetylene are obtained, but its process 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, it is before front-end hydrogenation, hydrogenator position that hydrogenator, which is located at domethanizing column,
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, and price adjustment co-catalyst silver and palladium act on, and 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 of wet reducing preparation silver and palladium catalyst, by be added in maceration extract it is organic or
Inorganic reducing agent, preparation 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
Have the disadvantage in that (1) is influenced by carrier hole structure, active component dispersion cannot be controlled accurately, 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
With the key factor for being raising catalyst choice, the catalyst of conventional method preparation, 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 unobvious, it is necessary to promote it by increasing the amount of Ag
A possibility that thus performance of promoter effect causes the transmitting of hydrogen to be hindered, 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, guarantees 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 aluminium oxide hydroxyl quantity；Macromolecule by functionalization with
The complexing of Pd is not strong, and activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is caused
Catalyst cost improves；Preparing C2 hydrogenation catalyst using this method, there is also the disadvantages of process flow 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, to influence the activity of catalyst, catalyst inactivation can be caused when serious, so that device be brought to leak alkynes risk.
Summary of the invention
In view of the above circumstances, the present invention proposes a kind of preparation method of system supported hydrogenation catalyst of palladium-lead.
The scheme of the invention is: Al is impregnated with the organic solution of hydroxyl dipyridyl derivatives2O3It is carrier, through drying
It is impregnated again with the mixed-cation solution of Pd, Pb afterwards, dry roasting obtains Pd-Pb catalyst.
In the present invention, after forming strong absorption containing hydroxyl dipyridyl derivatives and aluminium oxide, then with active component Pd,
Pb forms organic polymer complex compound, finally obtains the Pd-Pb catalyst of high dispersive.Best hydroxyl dipyridyl derivatives/
(Pd+Pb) the ratio between molal quantity is 1~50.
The process can be divided into the progress of 3 steps:
(1) Al is impregnated with the organic solution of hydroxyl dipyridyl derivatives first2O3It is carrier, forms hydroxyl-after dry
Bipyridyl/Al2O3Precursor；
(2) hydroxyl-bipyridyl/Al is impregnated with the mixed-cation solution containing Pd, Pb2O3Precursor is formed after dry
PdPb- hydroxyl-bipyridyl/Al2O3Precursor；
(3) PdPb- hydroxyl-bipyridyl/Al is roasted2O3Precursor obtains Pd-Pb catalyst.
In the present invention, drying is preferably carried out at 60 DEG C~150 DEG C.
Roasting preferably carries out at 300~600 DEG C, roasts 2~12h.
The system supported hydrogenation catalyst of palladium-lead of method preparation provided by the invention has palladium-lead high uniformity dispersion
Structure.
Carrier of the present invention is alumina series carrier, can be Al2O3, it is also possible to mainly contain Al2O3, and doped with it
Its hopcalite, other oxides can be silica, titanium oxide, magnesia and/or calcium oxide etc..The Al2O3
It can be γ, δ, θ, α or in which several mixing crystal forms, preferably θ, α or its mixing crystal form Al2O3。
Carrier can be spherical shape in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Hydroxyl dipyridyl derivatives, preferably hydroxyl 2,2,Dipyridyl derivatives, hydroxyl 3,3,Join pyrrole
Piperidine derivatives, preferably hydroxyl 2,2,Dipyridyl derivatives.
The preparation method for the catalyst that the present invention recommends is rapid:
The step of recommendation (1): hydroxyl-bipyridyl/Al2O3The preparation of precursor:
By the organic solution and Al of hydroxyl dipyridyl derivatives2O3It is carrier mixing, it is anti-at a temperature of 20 DEG C~60 DEG C
Answer 2~for 24 hours, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；The volume of organic solution is preferably big
In equal to the 80% of carrier total volume.
The step of recommendation (2): PdPb- hydroxyl-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Pb mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with step (1) obtained by hydroxyl-connection pyrrole
Pyridine/Al2O3Precursor reaction 2~for 24 hours, it is 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 of recommendation (3): the preparation of catalyst
PdPb- hydroxyl-bipyridyl/Al prepared by step 22O3Precursor in 300~600 DEG C of 2~12h of roasting temperature,
So that PdPb- hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains Pd-Pb catalyst.
In catalyst in use, H can be used in the reactor2Reduction treatment is carried out, reduction-state catalyst is obtained.
In step 1, the hydroxyl dipyridyl derivatives, preferably hydroxyl 2,2 '-dipyridyl derivatives,
Make Al2O3While generating stronger chemisorption to it, the extra hydroxyl two nitrogen bases adjacent with bipyridyl and active component
Pd, Pb are combined.
It needing that solvent is added in step 1, this is to make hydroxyl 2, and 2 '-dipyridyl derivatives can be completely dissolved, with
Be conducive to absorption of the macromolecule on carrier, be usual organic solvent, such as can be ethyl alcohol and ether.The additional amount of solvent is more
Few, mainly to control institute's solubilizer can be such that macromolecule is completely dissolved.
In step 2, palladium-lead solution can be the soluble salt solutions of palladium, lead, such as can be Pd (NO3)2、PbNO3
Mixed solution.Palladium, lead salt dosage are in the mixed solution can make Pd, Pb content of final catalyst, according to catalyst
Purposes can choose different Pd, Pb contents, the ratio between molal quantity and the molal quantity of Pd of best Pb are 1.0~10.
In step 3, roasting preferably carries out in aerobic atmosphere, and maturing temperature of the present invention is preferably 350 DEG C~500
℃。
Complex reaction is complex-metal ion in-situ chemical reaction in the present invention, and metal ion is by chemical anti-
It answers rather than physical absorption is integrated on macromolecule, therefore the atom of palladium, lead is to roast on macromolecule in uniform sequential distribution
During burning, palladium-lead atom can carry out oxidation reaction in situ, during oxidation reaction, form the oxide of palladium, lead
Eutectic.
The influence of maceration extract surface tension and solvation effect to the dispersion of palladium-lead can be overcome using this method, preparation is urged
Agent is alloy-type bimetallic catalyst, therefore has superior selectivity.
Due to Al in the present invention2O3The Al-O key for being carrier will be to the strong absorption of hydroxyl generation in hydroxyl-bipyridyl, therefore
It can effectively ensure Al2O3Carrier avoids hydroxyl-bipyridyl loss in solution to high molecular adsorbance.Simultaneously as inhaling
It is attached to Al2O3Hydroxyl-bipyridyl hydroxyl and nitrogen base on carrier and active component Pd, help the complexing power of active component Pb compared with
By force, it can be ensured that active component Pd in solution, help active component Pb by hydroxyl-bipyridyl/Al2O3It is adsorbed, is avoided molten completely
Active component Pd in liquid, the loss for helping active component Pb reduce production cost.
Hydroxyl-the bipyridyl introduced in the present invention can make metallic atom reach height because of the presence of polymer effect
The effect of even dispersion.
In the present invention, hydroxyl-bipyridyl is loaded on alumina series carrier, then extra by hydroxyl-bipyridyl
The cation of hydroxyl and/or nitrogen base and Pd, Pb forms complex ion.Palladium-lead solution is configured, load is had into functionalization macromolecule
Predecessor be impregnated into the palladium-lead solution prepared, reacted under certain conditions, make palladium, lead ion while being complexed
Onto the macromolecular chain loaded.Palladium-lead ion is integrated on macromolecule by chemical reaction, is tied on each macromolecule
The palladium of conjunction-lead atom number is proportional to hydroxyl, the quantity of nitrogen base on macromolecule, and hydroxyl-bipyridyl quantity is preferably
1~50 times of (palladium+lead) amount of ions.During the reaction, palladium, lead button are sub orderly is distributed on macromolecule.It was roasting
Cheng Zhong, palladium-lead atom can carry out oxidation reaction in situ, and catalyst prepared by this method is alloy-type bimetallic catalyst,
Maceration extract surface tension and solvation effect are overcome to the adverse effect of palladium-lead dispersion using the preparation method, preparation
Catalyst is more conducive to form palladium-metal, has the function that improve catalyst activity and selectivity.
Using plasma emission spectrometer or atomic absorption spectrum can measure catalyst Pd content and Pb content (standard
GB/T 15337-94), the existing forms of Pd-Pb on catalyst can be measured using XRD.
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 content
Two, carbon three selects hydrogenation plant.Catalyst composition has and C-4-fraction, MAPD and palladium is hindered to form soluble complicated chemical combination
Object and the effect being lost still have excellent hydrogenation activity and stabilization under C-4-fraction, the higher working condition of MAPD content
Property.
Specific embodiment
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 content and Pb content.
Standard GB/T 1537-94
Ethylene selectivity=△ ethylene/△ acetylene
Embodiment 1
Weigh Φ 4.2mm, length 4.2mm, specific surface 3.0m2/ g, hole hold the column α-Al of 0.24mL/g2O3Carrier
500g。
By 10.34g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, make 4,4 '-dihydroxy -2 after standing 2h, after 2 '-bipyridyls load on alumina support completely, 60 DEG C of dryings
10h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.30g Pd (NO3)2、0.52g Pb(NO3)2It is dissolved in 600mL deionized water, adjusting pH is 2.0, is made into mixed
Solution is closed, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out residual
Liquid obtains Pd Pb- hydroxyl-bipyridyl/Al2O3Precursor, the ratio between hydroxyl-bipyridyl and (Pd+Pb) molal quantity are 20.120℃
2h is roasted in air atmosphere at a temperature of 550 DEG C after dry 4h, obtains (Pd-Pd)/Al2O3Catalyst.Fixation is placed in front of use
It is N with molar ratio in bed reaction device2:H2The mixed gas of=1:1 obtains load type palladium-lead catalysis at a temperature of 120 DEG C
Agent S-1.It is 0.06% that measure catalyst Pd content, which be 0.025%, Pb content,.
Comparative example 1:
Weigh Φ 4.5mm, length 4.5mm, specific surface area 17m2Column α-the Al of/g, Kong Rongwei 0.22ml/g2O3It carries
Body 500g.
A, it is functionalized PVC/Al2O3Preparation
PVC8.9g is dissolved completely in 800ml tetrahydrofuran (THF), by the carrier impregnation weighed up to above-mentioned solution
Middle 1h makes PVC be deposited on Al2O3Surface pours out raffinate, is dried to obtain PVC/Al2O3Product.
119.28g dicyandiamide and 2.0gNa is added2CO3, above-mentioned PVC/Al is added2O3Reflux 4 hours, is cooled to room temperature,
It is washed with deionized to neutrality, drying for standby.Obtain functionalization PVC/Al2O3.Complexing agent dicyandiamide molal quantity/macromolecular chain
Molal quantity=10 upper reactive group Cl.
B、Pd-Pb-polymer/Al2O3The preparation of presoma
Take 0.30g Pd (NO3)2、0.52g Pb(NO3)2It is dissolved in the 500mL deionized water containing appropriate nitric acid, is heated to
It is completely dissolved, adjusting pH value is 1.6.Take the functionalization-PVC/Al prepared in step A2O3Presoma adds it to Pd
(NO3)2、Pb(NO3)2Mixed solution in, stir 30min, pour out raffinate, above-mentioned product be washed with deionized to neutrality,
Obtain (Pd-Pb)-PVC/Al2O3Presoma.
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 placed in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 300h-1Gas, at 100 DEG C
At a temperature of restore 4h, obtain catalyst D-1.It is 0.06% that measure catalyst Pd content, which be 0.025%, Pb content,.
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 | 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；Operating pressure: 3.5MPa,；Loaded catalyst: 500ml.
Adiabatic reactor reactor, two sections of tandem process carry out hydrogenation reaction.Three sections of reactors are 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 2.7mm, specific surface area 50m2The ball type carrier 500g of/g, Kong Rongwei 0.75ml/g, wherein containing θ-
Al2O3Carrier 440g, titanium oxide 60g.
By 4,4 '-dihydroxy -2 174.5g, 2 '-bipyridyls are dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation upper
It states in solution, makes 4,4 '-dihydroxy -2 after standing 8h, after 2 '-bipyridyls load on alumina support completely, 90 DEG C of dryings
8h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.61gPd (NO3)2,5.20gPb(NO3)2It is dissolved in 600mL deionized water, adjusting pH is 2.5, is made into mixing
Solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 8h, pours out residual
Liquid, remaining solid dry 6h at 110 DEG C obtain 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, obtain catalyst S-2 in air atmosphere.Measure the catalyst
Pd content is that 0.060%, Pb content is 0.63%.
Comparative example 2:
Weigh Φ 4.5mm, length 4.5mm, specific surface 2.0m2/ g, hole hold the column α-Al of 0.20mL/g2O3Carrier
500g。
Weigh appropriate Pd (NO3)2、Pb(NO3)2It is dissolved in the 600mL deionized water containing appropriate nitric acid, is heated to completely molten
Solution, adjusting pH value is 1.5.Above-mentioned carrier is added to the solution prepared, stirs 10min, raffinate is poured out, 550 after drying
2h is roasted at a temperature of DEG C in air atmosphere, obtains (Pd-Pb)/Al2O3Catalyst.It is placed in fixed-bed reactor before use,
It is N with molar ratio2:H2The mixed gas of=1:1 obtains load type palladium-lead comparative catalyst D-2 at a temperature of 120 DEG C.It measures
Catalyst Pd content is that 0.025%, Pb content is 0.63%.
Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 3.
3 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 %) | 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；Operating pressure: 3.5MPa,；Loaded catalyst: 500ml.
Adiabatic reactor reactor, two sections of tandem process carry out hydrogenation reaction.Three sections of reactors are tied after examination in 200 hours
Fruit is as shown in table 4.
4 two sections of the table result of appraisal of adiabatic reactor reactor 200 hours
Embodiment 3:
Weigh 4.3*4.3mm, specific surface area 17m2The cylindric carrier 500g of/g, Kong Rongwei 0.34ml/g, wherein α-
Al2O3400g, magnesia 100g.
By 6.51g 6,6'- dihydroxy -3,3'- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyl being loaded on alumina support completely, 120 DEG C of dryings
4h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.37g Pd (NO3)2, 1.82g Pb (NO3)2It is dissolved in 600mL deionized water, concentrated nitric acid is slowly added dropwise, stir
It mixes to solid and is completely dissolved, adjusting pH is 3.2, mixed solution is made into, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to
The solution of preparation stirs 60min, stands 8h, pours out raffinate, and remaining solid dry 8h at 100 DEG C obtains PdPb- hydroxyl-connection
Pyridine/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Pb)=5).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h, obtain comparative catalyst S-3 in air atmosphere.This is measured to urge
Agent Pd content is that 0.030%, Pb content is 0.22%.
Comparative example 3:
A is functionalized SAN/Al2O3Preparation
Weigh Φ 2.5mm, specific surface area 50m2The ball type carrier 500g of/g, Kong Rongwei 0.75ml/g, wherein containing θ-
Al2O3Carrier 440g, titanium oxide 60g.
SAN resin 2.2g is weighed, is dissolved in 600ml DMF solvent, stirring is completely dissolved SAN resin at room temperature,
Be added in this solution it is above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred, separate dry after solvent, obtain SAN/ θ-Al2O3
Presoma.
By functionalization-SAN/ θ-Al obtained above2O3Presoma is added in 1000ml deionized water, and 57.6g is added
Ethylenediamine, flow back 30min, and product is taken out after cooling, washs to neutrality, is dried to obtain functionalization-SAN/Al2O3Presoma (complexing
Reactive group CN base molal quantity=22.85 on agent ethylenediamine molal quantity/macromolecule).
B(Pd-Pb)-SAN/Al2O3The preparation of precursor
Weigh appropriate Pd (NO3)2、Pb(NO3)2It is dissolved in the 1200mL deionized water containing appropriate nitric acid, is heated to completely molten
Solution, adjusting pH value is 2.5.Take the functionalization-SAN/Al prepared2O3Presoma is added to Pd (NO3)2、Pb(NO3)2Mixing
In solution, 60min is stirred, raffinate is poured out, above-mentioned product is washed with deionized to neutrality, it is dry at 110 DEG C of remaining solid
6h obtains (Pd-Pb)-SAN/Al2O3Precursor (reactive group CN base molal quantity/molal quantity=1 (Pd+Pb) on macromolecule).
The preparation of C catalyst
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h, obtain catalyst D-3 in air atmosphere.Measure the catalyst
Pd content is that 0.03%, Pb content is 0.22%.
Using two back end hydrogenation technique of carbon, raw material composition are as follows:
C2H2: 1.5% (Φ), C2H480.0% (Φ), C2H618.5% (Φ).
Reaction condition: two sections of adiabatic reactor reactor tandem 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: 6500h-1, operating pressure: 1.8MPa, each reactor catalyst loadings: 500ml.One section anti-
Answer device H2/C2H2=2:1 (molar ratio)；Second stage reactor H2/C2H2=4:1 (molar ratio), result is such as after examination in 200 hours
Shown in table 5.
5 200 hours catalyst performance average value of table
Embodiment 4
Weigh Φ 4.0mm, length 4.0mm, specific surface 30.0m2/ g, hole hold the column α-Al of 0.50mL/g2O3Carrier
500g。
By 78.56g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, make 4,4 '-dihydroxy -2 after standing 10h, after 2 '-bipyridyls load on alumina support completely, 100 DEG C of dryings
6h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.55g Pd (NO3)2、3.90g Pb(NO3)2It is dissolved in 600mL deionized water, adjusting pH is 2.7, is made into mixed
Solution is closed, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 10h, pours out
Raffinate obtains Pd-Pb- hydroxyl-bipyridyl/Al2O3Precursor, the ratio between hydroxyl-bipyridyl and (Pd+Pb) molal quantity are 30.100
2h is roasted in air atmosphere at a temperature of 550 DEG C after DEG C dry 6h, obtains (Pd-Pb)/Al2O3Catalyst.It is placed in front of use solid
It is N with molar ratio in fixed bed reaction unit2:H2The mixed gas of=1:1, reduction treatment at a temperature of 120 DEG C, obtains support type
Palladium-lead catalyst S-4.It is 0.48% that measure catalyst Pd content, which be 0.045%, Pb content,.
Comparative example 4:
Weigh Φ 4.0mm, length 4.0mm, specific surface 30.0m2/ g, hole hold the column α-Al of 0.50mL/g2O3Carrier
500g。
By 78.56g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, make 4,4 '-dihydroxy -2 after standing 10h, after 2 '-bipyridyls load on alumina support completely, 100 DEG C of dryings
6h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.55g Pd (NO3)2、1.18g AgNO3It is dissolved in 600mL deionized water, adjusting pH is 2.7, and it is molten to be made into mixing
Liquid, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 10h, pours out raffinate,
Obtain PdAg- hydroxyl-bipyridyl/Al2O3Precursor, the ratio between hydroxyl-bipyridyl and (Pd+Ag) molal quantity are 30.100 DEG C of dryings
2h is roasted in air atmosphere at a temperature of 550 DEG C after 6h, obtains (Pd-Ag)/Al2O3Catalyst.It is anti-that fixed bed is placed in front of use
It answers in device, is N with molar ratio2:H2The mixed gas of=1:1, reduction treatment at a temperature of 120 DEG C, obtains load type palladium-silver
Catalyst D-4.It is 0.13% that measure catalyst Pd content, which be 0.042%, Ag content,.
Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 6.
6 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 %) | 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；Operating pressure: 3.7MPa；Loaded catalyst: 500ml.
Adiabatic reactor reactor, two sections of tandem process carry out hydrogenation reaction.Three sections of reactors are tied after examination in 200 hours
Fruit is as shown in table 7.
7 two sections of the table result of appraisal of adiabatic reactor reactor 200 hours
Claims (15)
1. a kind of preparation method of the system supported hydrogenation catalyst of palladium-lead, it is characterised in that with hydroxyl dipyridyl derivatives
Organic solution impregnate Al2O3It is carrier, is impregnated again with the mixed-cation solution of Pd, Pb after drying, dry roasting obtains
To Pd-Pb catalyst.
2. preparation method according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives/(Pd+Pb) rubs
The ratio between your number is 1~50:1.
3. preparation method according to claim 1, it is characterised in that roasting carries out at 300~600 DEG C；Roasting 2~
12h。
4. preparation method according to claim 3, it is characterised in that roasting carries out at 350 DEG C~500 DEG C；Roasting 2~
12h。
5. preparation method according to claim 1, it is characterised in that alumina series carrier is Al2O3, or mainly contain Al2O3
And doped with other hopcalites.
6. preparation method according to claim 5, it is characterised in that other oxides are silica, titanium oxide, magnesia
And/or calcium oxide.
7. preparation method according to claim 1, it is characterised in that Al2O3For γ, δ, θ, α or more than several mix-crystal
Type.
8. preparation method according to claim 1, it is characterised in that Al2O3For θ, α or its mixing crystal form.
9. preparation method according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives are hydroxyl 2,
2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives.
10. any preparation method according to claim 1~9, it is characterised in that catalyst preparation is divided into the progress of 3 steps:
(1) Al is impregnated with the organic solution of hydroxyl dipyridyl derivatives first2O3It is carrier, forms hydroxyl-connection pyrrole after dry
Pyridine/Al2O3Presoma；
(2) hydroxyl-bipyridyl/Al is impregnated with the mixed-cation solution containing Pd, Pb2O3Presoma forms PdPb- hydroxyl after dry
Base-bipyridyl/Al2O3Presoma；
(3) PdPb- hydroxyl-bipyridyl/Al is roasted2O3Presoma obtains Pd-Pb catalyst.
11. preparation method according to claim 10, it is characterised in that hydroxyl-bipyridyl/Al in step (1)2O3Presoma
Preparation are as follows:
By the organic solution and Al of hydroxyl dipyridyl derivatives2O3It is carrier mixing, reacts 2 at a temperature of 20 DEG C~60 DEG C
~for 24 hours, and it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Presoma.
12. preparation method according to claim 10, it is characterised in that PdPb- hydroxyl-bipyridyl/Al in step (2)2O3
The preparation of presoma are as follows:
Prepare Pd, Pb mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with step (1) obtained by hydroxyl-bipyridyl/
Al2O3Forerunner's precursor reactant 2~for 24 hours, it is dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyl-bipyridyl/Al2O3Presoma.
13. preparation method according to claim 12, it is characterised in that the ratio between molal quantity and the molal quantity of Pd of Pb are 1.0
~10:1.
14. preparation method according to claim 12, it is characterised in that adjust Pd, Pb mixed-cation solution ph be
1.5~4.0.
15. preparation method according to claim 10, it is characterised in that the preparation of catalyst in step (3) are as follows:
PdPb- hydroxyl-bipyridyl/Al prepared by step (2)2O3Presoma makes in 300~600 DEG C of 2~12h of roasting temperature
Obtain PdPb- hydroxyl-bipyridyl/Al2O3Presoma is changed into corresponding metal composite oxide, obtains Pd-Pb catalyst.
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| 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 |
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| 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 |
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| 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54页表4及其最后一段 |
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