CN105732286B - A kind of selection method of hydrotreating of C3 fraction - Google Patents
A kind of selection method of hydrotreating of C3 fraction Download PDFInfo
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Abstract
The present invention relates to a kind of selective hydrogenation method of C 3 fractions, C3 fraction enters adiabatic reactor reactor and carries out selection plus hydrogen, to remove propine and allene therein, it is characterized in that being equipped with Pd Au series catalysts in adiabatic reactor reactor, the catalyst is in preparation process, it is combined with hydroxyl dipyridyl derivatives by alumina series carrier, the hydroxyl dipyridyl derivatives being incorporated on carrier form metal complex with active component；Method using the present invention, since catalytic reaction activity and selectivity improve, the space velocity range of reaction also extends significantly, minimum air speed can arrive 3/h, range up to 120/h, the safety that device operation can be increased substantially is suitably applied the C_3 hydrogenation device more demanding to propylene increment since propylene increment significantly improves.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, especially a kind of C 3 fraction selective hydrogenation is except propine, allene
Method.
Background technology
The acquisition of high-purity propylene is the premise of polypropylene production, and the key of high-purity propylene production is to remove carbon three to evaporate
Propine (MA) in point and allene (PD), the general method for adding hydrogen using selection.
Current hydrogenation technique mainly use liquid-phase hydrogenatin, due to the MAPD (propine and allene) in three component of carbon have compared with
Strong polymerization tendency, easily forms coking in catalyst surface.Thus lead to catalyst activity reduction, hydrogenated products quality is made not conform to
The service life of lattice, catalyst shortens.
Add hydrogen flow process method in the sequence of the C3 fraction hydrogenation technique flow of no pre-add hydrogen, i.e. C3 fraction
In, cracking gas is after the separation of washing, oil wash, alkali cleaning and carbon four, and first by methane tower, tower top is one fraction of carbon and hydrogen
Gas, tower reactor are carbon two and C3 fraction, and using ethane tower, the ingredient of separation of carbon two and C3 fraction, tower reactor is carbon three
Hydrogenating materials, most of ingredient are propylene, remaining is a small amount of propane, propine and allene, and C3 fraction enters fixed thermal insulation
Bed reactor carries out liquid-phase hydrogenatin removing alkynes and alkadienes, and propylene is 70~90% (mol), propane 10 in reactor inlet raw material
~30% (mol).Propine (PD)+allene (MA) is 0.2~8.0% (mol).The usual process conditions of the technique hydrogenation reaction
For：10~50 DEG C, 2.5~3.5MPa of reaction pressure of reactor inlet temperature, 5~60h of liquid phase volume air speed-1, hydrogen/(MA+PD)
(mol)=1~2.
In the C3 fraction hydrogenation technique flow for having pre-add hydrogen, i.e., in the technological process of predepropanization front-end hydrogenation, cracking gas warp
After crossing oil wash, washing and alkali cleaning, first by predepropanization tower, the fraction of tower top includes carbon one and hydrogen, C-2-fraction
And C3 fraction, tower reactor are attached most importance to C3 fraction, the fraction of tower top enters Acetylene converter, wherein one fraction of carbon and hydrogen
For product content 35~50%, the Acetylene converter of C-2-fraction 35~50%, C3 fraction 10~20%, the technique is general
Be three sections, one, second-stage hydrogenation reactor be mainly used for the removing of acetylene, third section reactor carries out the removing of propine, allene.
The unit generally uses gas phase hydrogenation technique, and propine, allene removal efficiency are in 50% or more, after the flow, reaction mass
Using the separation of C3 fraction and one C-2-fraction of carbon, the liquid phase that the C3 fraction after separation enters carbon three after cooling adds
Hydrogen.Since most of propine allene has been converted, add hydrogen load relatively low, has higher want to the selectivity of catalyst
It asks.
In general, in C3During fraction selective hydrogenation, there are following reactions：
Main reaction
MAPD+H2→CH3CH=CH2 (1)
Side reaction
MAPD+2H2→CH3CH―CH3 (2)
2C3H4+H2→C6H8 (3)
CO+R*H+nH2→RCOHn (4)
At the initial stage of catalyst operation, the activity of catalyst is preferable, but when the selectivity of catalyst is undesirable, due to
Reaction temperature rising is excessively high, and local reaction is excessively violent, it is easy to cause temperature runaway, seriously affect the safe operation of device.
It is with Al that traditional C_3 hydrogenation catalyst, which uses catalyst,2O3For carrier, using Pd as active component, Ag, which is added, is
Active component is helped, the specific surface area of catalyst is 20~100m2/g.The preparation method of catalyst is to use infusion process.It is being catalyzed
It is influenced to be especially apparent by maceration extract surface tension and solvation effect in the dipping and drying process process of agent, metal active
Component presoma is deposited on carrier surface with aggregate form.In addition, the distribution between Pd and Ag is undesirable, catalyst is lived
Property it is not easy to control, the selectivity of catalyst relies primarily on the dispersity of catalyst aperture and active component to control, due to urging
In agent preparation process, the dispersion of active component is influenced by the quantity of carrier surface group and solvation, catalyst activity
The randomness of component dispersion is big, prepares poor repeatability, therefore the effect for being catalyzed reaction is undesirable.
CN98810096 discloses a kind of method of catalytic distillation, is that will be catalyzed to add to remove the PDMA in C3 fraction
Hydrogen and rectifying separation process are combined into one, and since heat exchange is abundant in this process, are not susceptible to temperature runaway, while in the process
A small amount of oligomer of middle generation, is also easy to be carried over, and can be reduced much in the coking degree of catalyst surface.This method is to catalysis
The filling of destilling tower is more demanding, and the distribution of fluid can have a significant impact to separating effect.This method also increases simultaneously
The difficulty of operation.
CN103801293A discloses a kind of selective hydrogenation catalyst comprising carrier and the main activity being carried on carrier
Component Pd and help active component A g, Bi, it is characterised in that：Using XPS analysis, catalyst surface Pd and O atom number percentage composition
The ratio between be 4 × 10-4~30 × 10-4, the ratio between Ag and O atom number percentage composition are 15 × 10-4~60 × 10-4；Help active component Bi
Weight ratio with main active component Pd is 0.01~5.When the catalyst is used for selective hydrogenation, while having and urging well
Change active and good selectivity.
CN103785484A discloses a kind of hydrogenation catalyst, the hydrogenation catalyst include tooth spherical alumina support and
The VI B races metal component and VIII race's metal component being supported on the tooth spherical alumina support, wherein the tooth spherical shape oxidation
The Kong Rongwei 0.4-0.7mL/g of alumina supporter, specific surface area 180-280m2/g.The present invention also provides the hydrogenation catalysts
Preparation method and a kind of method of light oil hydrofinishing.Hydrogenation catalyst provided by the invention is used for Hydrogenation of Coker Gasoline
Refining plant can give full play to the Hydrogenation of catalyst, and the pressure drop of hydrogenation plant system is effectively maintained to stablize, and extend
The operation cycle of hydrogenation plant.
CN103657671A is related to a kind of diolefin hydrogenate catalyst and preparation method and application.It is by a kind of VIII race gold
Belong to, one kind+trivalent metal, a kind of IA races metal, a kind of Group IVB metal, a kind of Group IIB metal, two kinds of group vib metals and flat
The SiO of measurement2-Al2O3The mixed metal oxide catalyst of composition, which is characterized in that counted using oxide and using catalyst as base
Standard, VIII race's metal containing 10-40 weight % in the catalyst, 5-30 weight %+trivalent metal, 0.1-8 weight % IA races
Two kind of VI B races metal of metal, the IV B races metal of 0.1-8 weight %, the II B races metal of 0.1-30 weight %, 5-50 weight %
With the SiO of 10-30 weight %2-Al2O3Composition.Catalyst provided by the invention is not easy coking, and anti-poisoning capability is strong, catalyst
Operation cycle is long.
CN103769158A discloses a kind of preparation method of hydrogenation catalyst.The catalyst is catalyzed for Cu-Al-Zn-M-O
Agent, wherein M are one or more in Ba, Mn, Mg, Ti, Cr.The method of the present invention contains Cu, Al using two step parallel flow precipitations
Solution and precipitating reagent are carried out containing Cu, Zn, M solution and precipitating reagent made from parallel-flow precipitation at different conditions.Gained catalyst is suitable
For dimethyl maleate Hydrogenation for 1,4-butanediol during, improve the reactivity and selectivity and steady of catalyst
It is qualitative.
CN103623874A discloses a kind of preparation method of two selective hydrogenation catalyst of carbon.Including：1) in a water bath, water
Cellulose of solubleness ether is dissolved in deionized water, is mixed with catalyst activity component salting liquid, and it is neutrality to adjust pH value, is stirred
It mixes；Wherein deionized water, catalyst activity component, the weight ratio of water-soluble cellulose ether are=1：(0.0001~0.001)：
(0.0001~0.005)；2) it loads；3) dry, roasting.Water-soluble cellulose ethers can be used as effective stablize in the present invention
Agent forms monodispersed Pd nano particle in the solution, is loaded on carrier by infusion process and forms more activated centres.This
Inventive method improves the activity of catalyst and the selectivity of hydrogenation products, enhances the dispersibility and utilization rate of palladium, reduces
The load capacity of palladium.
CN103418396A discloses a kind of hydrogenation catalyst and its preparation and application, and the catalyst contains containing alcohol molding
Aqua oxidation alumina supporter, load at least one non-noble metal metal salt for being selected from VIII race on this carrier and at least one choosing
From the metal salt of VI B races metal, is counted by oxide and on the basis of catalyst, VIII race's tenor is 2 weights of weight %~10
% is measured, VI B races tenor is 15 weight of weight %~45 %.The preparation method of the catalyst includes preparing containing alcohol molding hydration
Alumina support simultaneously loads at least one non-noble metal metal salt for being selected from VIII race and at least one selected from VI B on this carrier
The metal salt of race's metal, is dried later.Compared with existing technical method, hydrogenation catalyst provided by the invention not only has
There is excellent hydrocarbon oil hydrogenation to refine performance, while preparation method is simple, production cost is low.
Patent CN201110086151.X discloses a kind of method of C 3 fraction selective hydrogenation, the catalysis that this method uses
Agent, with Pd for main active component, using aluminium oxide as carrier, addition co-catalyst silver.By adsorbing specific high score on carrier
Sub- compound forms macromolecule wrapped layer in carrier surface certain thickness, with compound and high molecular weight reactive with functional base,
With the function base that can be complexed with active component, complexing is occurred instead on carrier surface function base by active component
Answer, ensure active component orderly and high degree of dispersion.Using the patented method, the specific high-molecular compound of carrier adsorption passes through oxygen
The hydroxyl and macromolecule for changing aluminium carry out chemisorption, and the amount of carrier adsorption high-molecular compound will be by the hydroxyl quantity of aluminium oxide
Limitation；The complexing of macromolecule and Pd by functionalization is not strong, and sometimes up to activity component load quantity does not reach requirement,
Residual fraction active component is gone back in maceration extract, and catalyst cost is caused to improve；C_3 hydrogenation catalyst is prepared also using this method
Haves the shortcomings that technological process complexity.
In recent years, requirement of the C_3 hydrogenation device to catalyst increasingly improves, it is desirable that catalyst at a lower reaction temperature,
With excellent activity and selectivity, to reach energy-saving, device propylene increment is improved, device economy effect is improved to reach
The purpose of benefit.
Invention content
The purpose of the present invention is to provide a kind of selection method of hydrotreating of C3 fraction, C3 fraction enters adiabatic reactor reaction
Device carries out selection plus hydrogen, to remove propine and allene therein, it is characterised in that urged equipped with Pd-Au systems in adiabatic reactor reactor
Agent refers to Al2O3It is carrier, is in terms of 100% by the quality of catalyst, wherein Pd contents are that 0.15~0.4%, Au contents are
0.01~0.2%, the specific surface area of catalyst is 15~100m2/ g, pore volume are 0.3~0.6ml/g；It is prepared by the catalyst
In the process, it is combined with hydroxyl-bipyridyl by alumina series carrier, active component forms metal complex with hydroxyl-bipyridyl；
Its hydrogenation process conditions is：30~60 DEG C, 2.5~3.5MPa of reaction pressure of adiabatic reactor reactor inlet temperature, liquid phase volume are empty
5~100h of speed-1, hydrogen/(propine and allene) molar ratio is 1~5:1.The characteristics of Pd-Au series catalysts used in the present invention
It is：The catalyst is PdAu- hydroxyls-bipyridyl/Al using the present invention2O3Prepared by the method for precursor.
The catalyst preparation process of recommendation, includes at least：Hydroxyl dipyridyl derivatives are loaded to alumina series to carry
On body, then by the cation of the extra hydroxyl of hydroxyl dipyridyl derivatives and/or nitrogen base and Pd, Au formed complexing from
Son.
The hydroxyl dipyridyl derivatives of the present invention, preferably hydroxyl 2,2, it is-dipyridyl derivatives, hydroxyl
3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, because it is combined rear extra hydroxyl with aluminium oxide
With Pd, Au preferable complex reaction can occur for base and two nitrogen bases at ortho position.
The catalyst type used is defined in the present invention, such catalyst choice has larger area with traditional catalyst
Not.
The principle of the present invention is：In selective hydrogenation reaction, closed as used catalyst activity component Pd, Au is formed
The quantity of gold, the hydrogen that caltalyst phase is adsorbed is greatly reduced, and the trend that deep hydrogenation occurs for propine, allene drops significantly
Low, catalyst choice significantly improves.
The acquisition of the catalyst preferably includes following steps：With hydroxyl bipyridyl organic solution, Al is impregnated2O3System carries
Body obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, prepare Pd, Au mixed solution dipping hydroxyl-bipyridyl/
Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyls-bipyridyl/Al2O3Precursor.At 300~600 DEG C
2~12h of roasting temperature obtains required catalyst.
Carrier of the present invention is alumina series carrier, preferably aluminium oxide, or mainly contains Al2O3,Wherein doped with other oxygen
The mixture of compound, other oxides are silica, titanium oxide, magnesia and/or calcium oxide.The aluminium oxide be γ, δ,
θ, α or in which several mixing crystal forms, preferably θ, α or its mixing crystal form.
Carrier can be spherical in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Following procedure may be used to implement in catalyst preparation of the present invention, which can be divided into the progress of 3 steps.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By hydroxyl bipyridyl organic solution, with Al2O3It is carrier mixing, so that solution is absorbed, in 20 DEG C~60 DEG C temperature
The lower reaction of degree 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor.Hydroxyl
The molal quantity of base-bipyridyl/(Pd+Au) is preferably 1~100；The volume of organic solution be preferably carrier total volume 80%~
120%.
B.PdAu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Au mixed solution, at a temperature of 30 DEG C~100 DEG C with bipyridyl/Al hydroxyl obtained by step A2O3
Precursor reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyls-bipyridyl/Al2O3Before
Body.
The ratio between the molal quantity of Au and the molal quantity of Pd are preferably 0.5~4, and it is preferably 1.5~4.0 to adjust pH value；Pd, Au's
The volume of mixed solution is preferably hydroxyl-bipyridyl/Al2O3The 60%~200% of precursor total volume.
C. the preparation of catalyst
PdAu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature,
Make PdAu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
Solvent is added in step in order to make hydroxyl-bipyridyl be completely dissolved, to be conducive to suction of the macromolecule on carrier
Attached, solvent can be ethyl alcohol and ether.How much is the addition of solvent, and mainly to control institute's solubilizer can make macromolecule completely molten
Solution.
In stepb, the solution of palladium-gold can be the soluble salt solutions of palladium, gold, such as can be palladium bichloride and gold chloride
Mixed solution.Palladium, gold salt dosage are can make Pd, Au content of final catalyst in the mixed solution.
In step C, what roasting preferably carried out in having oxygen atmosphere, calcination temperature of the present invention is preferably 350 DEG C~500
℃。
In catalyst in use, can H be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
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 to be on the atom macromolecule of palladium, gold, is being roasted
During, palladium-gold atom can carry out oxidation reaction in situ, and during oxidation reaction, it is total to form palladium, the oxide of gold
It is brilliant.
The influence of the dispersion of maceration extract surface tension and solvation effect to palladium-gold, preparation can be overcome to urge using this method
Agent is alloy-type bimetallic catalyst, therefore has superior selectivity.
Due to Al in the present invention2O3The Al-O keys of carrier will generate strong absorption to the hydroxyl in hydroxyl-bipyridyl, therefore can
Effectively to ensure Al2O3Carrier avoids the loss of hydroxyl-bipyridyl in solution to high molecular adsorbance.Simultaneously as absorption
In Al2O3The hydroxyl and nitrogen base of hydroxyl-bipyridyl on carrier and active component Pd, help the complexing power of active component A u stronger,
It may insure the active component Pd in solution, help active component A u by hydroxyl-bipyridyl/Al2O3It is adsorbed completely, avoids solution
Middle active component Pd, the loss for helping active component A u 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
Hydroxyl and/or nitrogen base and the cation of Pd, Au form complex ion.The solution for configuring palladium-gold, has functionalization macromolecule by load
Predecessor be impregnated into the palladium-gold solution prepared, reacted under certain conditions, make palladium, gold ion while being complexed
Onto the macromolecular chain loaded.The ion of palladium-gold is attached on macromolecule by chemical reaction, is tied on each macromolecule
Palladium-atomic number of Au of conjunction is proportional to hydroxyl, the quantity of nitrogen base on macromolecule, and the quantity of the hydroxyl-bipyridyl is preferably
1~100 times of (palladium+gold) amount of ions.During the reaction, palladium, gold particle are orderly is distributed on macromolecule.It was roasting
Cheng Zhong, palladium-gold atom can carry out oxidation reaction in situ, and catalyst prepared by this method is alloy-type bimetallic catalyst,
The adverse effect of the dispersion of maceration extract surface tension and solvation effect to palladium-gold is overcome using the preparation method, preparation
Catalyst is more conducive to form palladium-billon, has the function that improve catalyst activity and selectivity.
In the present invention, the C3 fraction as hydrogenating materials can be respectively from two kinds of flows, and one kind adding hydrogen flow for sequence,
Another kind is Front-end depropanization and front-end hydrogenation, and hydrogenation process conditions of the present invention are preferably：Adiabatic reactor reactor inlet temperature 30~
60 DEG C, 2.5~3.5MPa of reaction pressure, 5~100h of liquid phase volume air speed-1, hydrogen/(propine and allene) molar ratio is 1~5:
1, hydrogen/(MA+PD) (mol)=1~5:1.In reactor inlet raw material general propylene be 70~90% (mol), propane 10~
30% (mol), propine (MA) are 0.05~0.2% (mol), and allene (PD) is 0.05~0.2% (mol).The reaction used
Device is generally first stage reactor.
Inventor has found, after method of hydrotreating using the present invention, the selectivity of reaction improves, and reactor inlet temperature also may be used
To properly increase, so as to improve liquid phase volume air speed, from the 60h of traditional method of hydrotreating-1It is increased to 100h-1, it is possible to reduce
Reactor size reduces the energy loss of heat transfer process.The method of the present invention can improve the selectivity of reaction, reduce catalysis reaction
The risk of device temperature runaway, the safety to improving device operation have important meaning.
Meanwhile the method for the present invention prepares palladium-gold catalyst, since its alloy structure is apparent, alloy effect is stronger, is more suitable for
Higher C_3 hydrogenation device, the alloy catalyst is required to be applied to C_3 hydrogenation applied to catalyst activity, selectivity
Device has excellent activity and selectivity at a lower reaction temperature.
Description of the drawings
Fig. 1 is to use the C_3 hydrogenation flow chart without pre- hydrogenation technique using a kind of of the present invention.
Fig. 2 is a kind of C_3 hydrogenation flow chart using pre- hydrogenation technique using the present invention.
In figure：1-oil scrubber；2-water scrubbers；3-heat exchangers；4-caustic wash towers；5-domethanizing columns；6-dethanizers；
7-depropanizing towers；8-C_3 hydrogenation reactors；9-predepropanization towers；10-Acetylene converters；11-compressors.
Specific implementation mode
Analysis test method：
Specific surface area：GB/T-5816
Kong Rong：GB/T-5816
Heap density：Q/SY142-2006
Catalyst Pd, Au assay：Using plasma emission spectrometer measures catalyst Pd contents and Au contents.
Standard GB/T 1537-94
Selective computational methods：
Propylene Selectivity S=1- △ propane/△ (propine+allene)
Embodiment 1
Weigh Φ 4.0mm, length 4.0mm, specific surface area 80m2Column δ-the Al of/g, Kong Rongwei 0.60ml/g2O3It carries
Body 500g.
By 30.77g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 2h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 60 DEG C of dry 10h are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, and it is 1.5 to adjust pH value, is configured to
Mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out
Raffinate obtains PdAu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Au)=10).120 DEG C of dryings
2h is roasted in air atmosphere at a temperature of 550 DEG C after 4h, obtains (Pd-Au)/Al2O3Catalyst.It is anti-that fixed bed is positioned over before use
It answers in device, uses H2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h obtains support type palladium-gold catalyst S-1.Measure this
Catalyst Pd contents are that 0.21%, Au contents are 0.14%.
Comparative example 1
The preparation of catalyst
Weigh Φ 4.0mm, length 4.0mm, specific surface area 80m2Column δ-the Al of/g, Kong Rongwei 0.60ml/g2O3It carries
Body 500g.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, and it is 1.5 to adjust pH value, is configured to
Mixed solution.Above-mentioned carrier is added in the solution prepared, stirs 30min, it is dry after in 550 DEG C of roasting temperature 2h,
Obtain Pd-Au/Al2O3Catalyst.It is positioned in fixed-bed reactor before use, uses H2In air speed 400h-1, 120 DEG C of temperature,
Reduction treatment 8h obtains support type palladium-gold catalyst D-1.It is that 0.21%, Au contents are to measure catalyst Pd contents
0.14%.
Comparative example 2
The preparation of catalyst
Weigh Φ 4.0mm, length 4.0mm, specific surface area 80m2Column δ-the Al of/g, Kong Rongwei 0.60ml/g2O3It carries
Body 500g.
It weighs appropriate palladium nitrate and silver nitrate is dissolved in 600mL deionized waters, it is 1.5 to adjust pH value, is configured to mixed solution.It will
Above-mentioned carrier is added in the solution prepared, and is stirred 30min and is obtained Pd-Ag/ in 550 DEG C of roasting temperature 2h after drying
Al2O3Catalyst.It is positioned in fixed-bed reactor before use, uses H2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h,
Obtain load type palladium-silver catalyst D-1.It is 0.26% that measure catalyst Pd contents, which be 0.21%, Ag contents,.
Its C3 fraction is from sequence plus hydrogen flow, and as shown in Fig. 1, but adiabatic reactor reactor reaction bed is two sections,
Raw material composition is as shown in table 1.
1 hydrogenating materials of table form
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 |
| Content (V/V%) | 4.5 | 3.6 | 82.0 | 9.9 |
Reaction condition：
Two sections of adiabatic reactor reactor hydrogenation techniques, liquid phase feed volume space velocity：8h-1, operating pressure：2.3MPa, reactor
Loaded catalyst：500ml, hydrogen/(MA+PD) (mol)=1.4:1.After examination in 800 hours shown in reaction result table 2.
Reaction result after table examination in 2 800 hours
| Condition | 1 catalyst of embodiment | 1 catalyst of comparative example | 2 catalyst of comparative example |
| One section of inlet temperature (DEG C) | 45 | 45 | 45 |
| One section of Wen Sheng (DEG C) | 35 | 32 | 34 |
| One section of C3H4Residual volume (V/V%) | 0.55 | 1.50 | 0.62 |
| One-stage hydrogenation selectivity (%) | 92 | 68 | 69 |
| Two sections of inlet temperatures (DEG C) | 55 | 55 | 55 |
| Two sections of Wen Sheng (DEG C) | 9 | 17 | 16 |
| Two sections of C3H4Residual volume (V/V%) | 0.04 | 0.23 | 0.002 |
| Secondary hydrogenation selectivity (%) | 73 | 45 | 38 |
| Propylene increment % | 7.2 | 4.6 | 4.0 |
Comparative example 3
Catalyst preparation：
Weigh Φ 2.5mm, specific surface area 45m2/ g, Kong Rongwei 0.40ml/g, the tooth that heap density is 0.68g/ml are spherical
θ-Al2O3Carrier 500g.
A, function polystyrene acrylonitrile (SAN)/Al2O3Preparation
SAN resin 2.2g are weighed, are dissolved in 600ml dimethylformamides (DMF) solvent, stirring at room temperature makes SAN trees
Fat is completely dissolved, be added in this solution it is above-mentioned weighed carrier, stand 60min after being sufficiently stirred, detach dry after solvent, obtain
To SAN/Al2O3。
By SAN/Al obtained above2O3, it is added in 1000ml deionized waters, 57.6g ethylenediamines is added, flows back 5h, cold
But product is taken out afterwards, and washing to neutrality is dried to obtain functionalization SAN/Al2O3.In terms of molal quantity, complexing agent ethylenediamine molal quantity/
Molal quantity=23.96 reactive group CN in macromolecule.
B, (Pd-Au)-high-molecular complex/Al2O3The preparation of presoma
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, and it is 2.5 to adjust pH value, is configured to
Mixed solution.Take the functionalization-SAN/Al prepared2O3Presoma is added in the mixed solution of Pd-Au, is stirred 60min, is inclined
Go out raffinate, product will be obtained and be washed with deionized to neutrality, (Pd-Au)-polymer/Al is obtained after dry2O3Presoma.It is high
Reactive group CN molal quantitys/molal quantity=1.33 (Pd+Au) in molecule.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h, obtain (Pd-Au)/Al in air atmosphere2O3Catalyst.Make
With being preceding positioned in fixed-bed reactor, H is used2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h obtains load type palladium-
Au catalyst D-2.It is 0.035% that measure catalyst Pd contents, which be 0.2%, Au contents,.Using technological process shown in FIG. 1,
Its C3 fraction raw material composition is as shown in table 3.
3 hydrogenating materials of table form
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 |
| Content (V/V%) | 0.8 | 0.6 | 69.0 | 29.6 |
Single hop reactor hydrogenation technique, liquid phase feed volume space velocity：40h-1, operating pressure：3.0MPa
Reactor catalyst loadings：500ml, hydrogen/(MA+PD) (mol)=3:1,35 DEG C of reactor inlet temperature.Through
Reaction result is as shown in table 4 after examination in 800 hours.
Reaction result after 4 catalyst of table adds hydrogen to examine for 1000 hours applied to C3 fraction
Embodiment 3：
Weigh Φ 4.5mm × 4.5mm, specific surface area 17.0m2/ g, Kong Rongwei 0.22ml/g, heap density are 0.85g/
ML, column α-Al2O3Carrier 500g.
By 92.4g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 650mL 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.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, and it is 3.0 to adjust pH value, is configured to
Mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out
Raffinate obtains PdAu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Au)=10).120 DEG C of dryings
2h is roasted in air atmosphere at a temperature of 550 DEG C after 4h, obtains (Pd-Au)/Al2O3Catalyst.It is anti-that fixed bed is positioned over before use
It answers in device, uses H2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h obtains support type palladium-gold catalyst S-3.Measure this
Catalyst Pd contents are that 0.20%, Au contents are 0.07%.
Embodiment 4
Weigh Φ 3.0mm, specific surface area 40m2/ g, Kong Rongwei 0.42ml/g, the tooth that heap density is 0.73g/ml are spherical
θ-Al2O3Carrier 500g.
By 12.31g 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 6h are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, and it is 2.0 to adjust pH value, is configured to
Mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out
Raffinate obtains PdAu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Au)=21.5).120 DEG C dry
2h is roasted in air atmosphere at a temperature of 550 DEG C after dry 4h, obtains (Pd-Au)/Al2O3Catalyst.Fixed bed is positioned over before use
In reaction unit, H is used2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h obtains support type palladium-gold catalyst S-4.It measures
Catalyst Pd contents are that 0.20%, Au contents are 0.07%.
Comparative example 4：
The preparation of catalyst：
Weigh Φ 4.5mm × 4.5mm, specific surface area 17.0m2/ g, Kong Rongwei 0.22ml/g, the column that heap density is 0.85
Shape α-Al2O3Carrier 500g.
A, prepared by functionalized poly vinyl chloride (PVC)
It weighs PVC 10g to be dissolved completely in 800mlTHF, 80g dicyandiamides is added, flow back 120min, is cooled to room temperature,
It is spare that functionalization PVC is obtained after washing.In terms of molal quantity, reactivity CI groups rub in complexing agent dicyandiamide molal quantity/macromolecule
That number=5.94.
B, (Pd-Au)-high-molecular complex/Al2O3The preparation of presoma
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, it is added to above-mentioned functionalization
In PVC solution, 5min is stirred, (Pd-Au)-PVC is obtained.
By 500gAl2O3Carrier is added in mixed solution, after standing 1h after being sufficiently stirred, by above-mentioned product deionized water
It washs to neutrality.Obtain (Pd-Au)-polymer/Al2O3Presoma.Functional group's CN molal quantitys after functionalization on macromolecular chain/
(Pd+Au) molal quantity=9.5.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h, obtain oxidation state (Pd-Au)/Al in air atmosphere2O3Catalysis
Agent.It is positioned in fixed-bed reactor before use, uses H2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h loaded
Type palladium-gold catalyst D-3.It is 0.07% that measure catalyst Pd contents, which be 0.20%, Au contents,.Using technique shown in Fig. 2
Flow, C3 fraction raw material composition are as shown in table 5.
5 hydrogenating materials of table form
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 |
| Content (mol%) | 0.2 | 0.2 | 85.0 | 14.6 |
Reaction process condition：Single stage adiabatic bed reactor process, material air speed：120/h-1, operating pressure：2.8MPa is urged
Agent loadings：500ml.Hydrogen/(MA+PD) (mol)=1.5:1.Reaction result is as shown in table 6 after examination in 800 hours.
Reaction result after table examination in 6 600 hours
Embodiment 5
Weigh Φ 2.5mm, specific surface area 45m2/ g, Kong Rongwei 0.40ml/g, the tooth that heap density is 0.68g/ml are spherical
θ-Al2O3Carrier 500g.
By 123.1g 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, 90 DEG C of dry 8h are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 300mL deionized waters containing appropriate hydrochloric acid, and it is 2.5 to adjust pH value, is configured to
Mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out
Raffinate obtains PdAu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Au)=80).120 DEG C of dryings
2h is roasted in air atmosphere at a temperature of 550 DEG C after 4h, obtains (Pd-Au)/Al2O3Catalyst.It is anti-that fixed bed is positioned over before use
It answers in device, uses H2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h obtains support type palladium-gold catalyst S-2.Measure this
Catalyst Pd contents are that 0.22%, Au contents are 0.012%.
Comparative example 5
Catalyst preparation：
Weigh Φ 2.5mm, specific surface area 45m2/ g, Kong Rongwei 0.40ml/g, the tooth that heap density is 0.68g/ml are spherical
θ-Al2O3Carrier 500g.
A, function polystyrene acrylonitrile (SAN)/Al2O3Preparation
SAN resin 2.2g are weighed, are dissolved in 600ml dimethylformamides (DMF) solvent, stirring at room temperature makes SAN trees
Fat is completely dissolved, be added in this solution it is above-mentioned weighed carrier, stand 60min after being sufficiently stirred, detach dry after solvent, obtain
To SAN/Al2O3。
By SAN/Al obtained above2O3, it is added in 1000ml deionized waters, 57.6g ethylenediamines is added, flows back 5h, cold
But product is taken out afterwards, and washing to neutrality is dried to obtain functionalization SAN/Al2O3.In terms of molal quantity, complexing agent ethylenediamine molal quantity/
Molal quantity=23.96 reactive group CN in macromolecule.
B, (Pd-Au)-high-molecular complex/Al2O3The preparation of presoma
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 600mL deionized waters containing appropriate hydrochloric acid, and it is 2.5 to adjust pH value, is configured to
Mixed solution.Take the functionalization-SAN/Al prepared2O3Presoma is added in the mixed solution of Pd-Au, is stirred 60min, is inclined
Go out raffinate, product will be obtained and be washed with deionized to neutrality, (Pd-Au)-polymer/Al is obtained after dry2O3Presoma.It is high
Reactive group CN molal quantitys/molal quantity=1.33 (Pd+Au) in molecule.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h, obtain (Pd-Au)/Al in air atmosphere2O3Catalyst.Make
With being preceding positioned in fixed-bed reactor, H is used2In air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h obtains load type palladium-
Au catalyst D-2.It is 0.18% that measure catalyst Pd contents, which be 0.32%, Au contents,.
Using technological process shown in FIG. 1, C3 fraction raw material composition is as shown in table 7.
7 hydrogenating materials of table form
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 |
| Content (V/V%) | 0.8 | 0.6 | 69.0 | 29.6 |
Single hop reactor hydrogenation technique, liquid phase feed volume space velocity：65h-1, operating pressure：3.0MPa
Reactor catalyst loadings：500ml, hydrogen/(MA+PD) (mol)=3:1,35 DEG C of reactor inlet temperature.Through
Reaction result is as shown in table 8 after examination in 800 hours.
Reaction result after 8 catalyst of table adds hydrogen to examine for 1000 hours applied to C3 fraction
After above embodiment can be seen that method using the present invention, the activity of C3 fraction hydrogenation reaction, selection
Property increase substantially so that hydrogenation reaction more easily operates, and is not susceptible to leakage alkynes and excessive hydrogenation.It is run in the long period
When, the activity of catalyst is also kept well.From embodiment it can further be seen that after adopting this method, being reacted due to being catalyzed
Activity and selectivity improve, and the space velocity range of reaction also extends significantly, and minimum air speed can arrive 5/h, range up to 100/h or more,
The safety and efficiency, the economic benefit of device that device operation can be increased substantially can increase substantially.
Claims (14)
1. a kind of selection method of hydrotreating of C3 fraction, C3 fraction enters adiabatic reactor reactor and carries out selection plus hydrogen, with removing
Propine and allene therein, it is characterised in that use Al equipped with Pd-Au series catalysts in adiabatic reactor reactor2O3It is carrier,
It is in terms of 100% by the quality of catalyst, it is 0.01~0.2% that wherein Pd contents, which are 0.15~0.40%, Au contents, catalyst
Specific surface area is 15~100m2/ g, pore volume are 0.3~0.6ml/g；The catalyst passes through alumina series in preparation process
Carrier is combined with hydroxyl-bipyridyl, and the hydroxyl bipyridyl being incorporated on carrier forms metal complex with active component；It adds hydrogen
Process conditions are：30~60 DEG C, 2.5~3.5MPa of reaction pressure of adiabatic reactor reactor inlet temperature, liquid phase volume air speed 5~
100h-1, hydrogen/(propine and allene) molar ratio is 1~5:1.
2. selection method of hydrotreating according to claim 1, it is characterised in that catalyst preparation process includes at least：By band
The dipyridyl derivatives of hydroxyl load on alumina series carrier, then pass through the extra hydroxyl of hydroxyl dipyridyl derivatives
And/or nitrogen base and the cation of Pd, Au form complex ion.
3. selection method of hydrotreating according to claim 1, it is characterised in that C3 fraction is from sequence plus hydrogen flow.
4. selection method of hydrotreating according to claim 1, it is characterised in that C3 fraction comes from predepropanization front-end hydrogenation stream
Journey.
5. selection method of hydrotreating according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives are hydroxyl
2,2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives.
6. selection method of hydrotreating according to claim 1, it is characterised in that the preparation process of catalyst includes the following steps：
With the organic solution of hydroxyl dipyridyl derivatives, Al is impregnated2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3
Precursor, the mixed solution for preparing Pd, Au impregnate hydroxyl-bipyridyl/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, it obtains
PdAu- hydroxyls-bipyridyl/Al2O3Precursor；In 300~600 DEG C of 2~12h of roasting temperature, required catalyst is obtained.
7. selection method of hydrotreating according to claim 1, it is characterised in that Al2O3Be carrier be Al2O3Or it mainly contains
Al2O3, wherein also doped with other hopcalites, other oxides are titanium oxide, magnesia and/or calcium oxide；It is described
Aluminium oxide be γ, δ, θ, α or in which several mixing crystal form Al2O3。
8. selection method of hydrotreating according to claim 7, it is characterised in that the aluminium oxide is θ, α or it mixes crystal form
Al2O3。
9. selection method of hydrotreating according to claim 1, it is characterised in that carrier is spherical shape, cylindrical, circular ring shape, item
Shape, cloverleaf pattern or bunge bedstraw herb shape.
10. according to any selection method of hydrotreating of claim 1-9, it is characterised in that the preparation process of catalyst include with
Lower step：
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
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 solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdAu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Au mixed solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl-bipyridyl/Al obtained by step A2O3Precursor
Reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyls-bipyridyl/Al2O3Precursor；
C. the preparation of catalyst
PdAu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor is in 300~600 DEG C of 2~12h of roasting temperature so that
PdAu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
11. selection method of hydrotreating according to claim 10, it is characterised in that hydroxyl-bipyridyl/(Pd+Au) in step A
Molal quantity be 1~100：1.
12. selection method of hydrotreating according to claim 10, it is characterised in that in stepb, the mixed solution of Pd, Au are
The mixed solution of palladium bichloride and gold chloride.
13. selection method of hydrotreating according to claim 10, it is characterised in that in stepb, the molal quantity of Au and Pd's
The ratio between molal quantity is 0.5~4：1.
14. selection method of hydrotreating according to claim 10, it is characterised in that the mixed solution pH of Pd, Au in stepb
Value is 1.5~4.0.
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| CN102206132A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C3 fraction |
| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
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| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
| CN102206132A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C3 fraction |
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