CN105732269B - The selection method of hydrotreating of C-2-fraction in a kind of sequence separation process - Google Patents
The selection method of hydrotreating of C-2-fraction in a kind of sequence separation process Download PDFInfo
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Abstract
The present invention relates to carbon two in a kind of sequence separation process to select method of hydrotreating, for adding the fixed bed reactors of hydrogen to be located at after domethanizing column, by two material of carbon in ethylene unit from front-end deethanization tower, it is pressurized with after hydrogen, selection plus hydrogen are carried out into adiabatic reactor reactor, it is characterized by: being equipped with Pd-Au series catalysts in fixed bed reactors, the catalyst is during the preparation process, through alumina series carrier in conjunction with hydroxyl dipyridyl derivatives, the hydroxyl bipyridyl and active component being incorporated on carrier form metal complex；Using method of the invention, the activity and selectivity of hydrogenation reaction are significantly better than traditional method of hydrotreating, and ethylene increment significantly improves, and the production quantity of green oil is also greatly lowered in hydrogenation process.The reduction of green oil simultaneously, so that the activated centre of catalyst is not covered by by-product, catalyst activity and selectivity are kept well.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, carbon two selects method of hydrotreating in especially a kind of sequence separation process.
Background technique
Polymer grade ethylene production is the faucet of petrochemical industry, and polymer grade ethylene and propylene are the most bases of downstream polymerisation device
This raw material.Wherein the selection of acetylene adds hydrogen to have extremely important influence to ethylene processing industry, in addition to guaranteeing going out for hydrogenator
Mouth acetylene content is up to standard outer, and the selectivity of catalyst is excellent, can make the generation ethane that ethylene is as few as possible, to the entire work of raising
It is significant to improve device economic benefit for the yield of ethene of skill process.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%-2.5%, when producing polyethylene, lacking in ethylene
Amount acetylene can reduce the activity of polymerization catalyst, and make the deterioration in physical properties of polymer, so must be by the acetylene in ethylene
Content drops to certain limit, could be as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are in ethylene unit process
One of important process.
Catalysis selective hydrogenation includes being divided into front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to second
For alkynes hydrogenator for domethanizing column position, it is before front-end hydrogenation that hydrogenator, which is located at domethanizing column, adds hydrogen anti-
It is back end hydrogenation after answering device to be located at domethanizing column.The advantages of back end hydrogenation is sequence separation process, technique is hydrogenation process control
Means are more, are not easy temperature runaway, easy to operate, but the disadvantage is that the easy coking of catalyst, the regeneration of catalyst are more frequent.The reason is that
In hydrogenation process, since the amount of allocating of hydrogen is few, be easy to happen acetylene adds hydrogen dimerization reaction, generates 1,3-butadiene, goes forward side by side
One step generates the wider oligomer of molecular weight, is commonly called as " green oil ".Green oil is adsorbed on catalyst surface, and is further formed coking,
Block catalyst duct, makes catalyst activity and selectivity decline.
Two back end hydrogenation of carbon mainly uses two sections or three sections of reactor tandem process, the dress that air speed is lower or alkynes content is low at present
It sets, can be connected using two reactor.Commercial plant at present, mainly based on three sections of reactor tandem process.
Back end hydrogenation material generally forms are as follows: 1.0~2.2% (v) acetylene, 65~85% ethylene, remaining is ethane, hydrogen
Gas after metering by being incorporated.
The reaction is exothermic reaction, but temperature rise is relatively low, and according to air speed size, single reactor maximum temperature rise is from 30~60
It DEG C differs, so using adiabatic reactor substantially.
To two reactor, first segment reactor requires the acetylene of 70% or more conversion, and second segment reactor will be remaining
Acetylene is converted to its content less than 1 μ L/L.
Or acetylene content higher device higher to air speed generally uses three sections of reactor process, first segment conversion 50%
Left and right, remaining the two sections remaining acetylene of conversion, three sections of reactor outlet acetylene contents are less than 1 μ L/L.
The amount of allocating of hydrogen is related with acetylene content and using technique.To three sections of reactor process, general first segment reaction
Device hydrogen/acetylene is 0.8~1.2, and second segment reactor hydrogen/acetylene is 1~1.5, and third section reactor hydrogen/acetylene is
1.5~3.
To two reactor technique, general first segment reactor hydrogen/acetylene is 1~1.5, second segment reactor hydrogen/
Acetylene is 2~4.
The reaction mechanism is as follows for this:
Main reaction C2H2+H2→C2H4Δ H=-175.7kJ/mol (1)
Side reaction
C2H4+H2→C2H6Δ H=-138.1kJ/mol (2)
C2H2+2H2→C2H6 (3)
2C2H2+H2→C4H6 (4)
C2H2+nC2H2+H2→C2n+2H2n+4 (5)
In these are answered, reaction (1) is acetylene hydrogenation, and reaction (2) and (3) is ethylene hydrogenation.Reaction (4) is that acetylene adds
Hydrogen dimerization has important contribution to green oil is generated, and reaction (5) is to generate the General reactions formula of green oil.
In these reactions, only reaction (1) is desirable to the reaction occurred, remaining is undesirable reaction.
US5856262 is reported using potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) modified silica as carrier,
The method for preparing low in acidity palladium catalyst, in air speed 3000h-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction 0.71%, hydrogen
Under conditions of alkynes molar ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
Using aluminium oxide as carrier, addition co-catalyst silver and palladium act on US4404124, are prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst, which has, reduces ethane production quantity, inhibits the acetylene being adsorbed on catalyst surface to carry out partial hydrogenation dimerization anti-
It answers, 1,3-butadiene is inhibited to generate, reduce the characteristics of green oil generates, improves ethylene selectivity, reduce oxygenatedchemicals production quantity,
It is applied widely in ethylene industry.However, above-mentioned catalyst is using prepared by infusion process, by the limit of preparation method
System, metal dispersity is only 30% or so, and there is also many deficiencies for catalyst performance, still there is further improved necessity.
Traditional Pd-Ag bimetallic selective hydrogenation catalyst is prepared using aqueous solution infusion process.Using sub-dip method
When, a kind of group of branch it is more be enriched in carrier surface, and another component is enriched in outer surface, only part metals atom phase
Mutually infiltration, forms alloy structure.Meanwhile using total immersion method, due to two metal ion species presoma and carrier it is mutual
Effect difference and surface tension and solvation, are hardly formed the uniform load of two kinds of components, also can only partially form alloy
Structure.It is often selectively preferable in initial reaction stage when this catalyst is applied to C 2 fraction selective hydrogenation, with runing time
Extend, selectivity constantly decline generally runs 3~6 months and just needs to regenerate, economic loss is larger.
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 are limited the hydroxyl quantity by aluminium oxide；By the macromolecule of functionalization
Not strong with the complexing of Pd, activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is made
It is improved at catalyst cost；Preparing C2 hydrogenation catalyst using this method, there is also the disadvantages of process flow complexity.
In recent years, requirement of the ethylene unit to C2 hydrogenation catalyst increasingly improves, it is desirable that catalyst is compared with low reaction temperature
Under degree, there is excellent activity and selectivity, to reach energy-saving, device ethylene increment is improved, to reach raising device
The purpose of economic benefit.
Summary of the invention
The purpose of the present invention is to provide carbon two in a kind of sequence separation process to select method of hydrotreating, by selecting active group
Divide high degree of dispersion, the Pd-Au catalyst with height alloy structure, improve hydrogenation selectivity, improve ethylene increment, improves device
Operation stability and economic benefit.
Inventors have found that Pd in catalyst is separated by Au when using catalyst prepared by preparation method of the present invention, so that
The spacing in activated centre widens, and two acetylene molecules occur hydrodimerized probability when adding hydrogen and are greatly reduced.1,3- butadiene
Therefore the surface coking rate of production quantity sharp fall, catalyst is greatly reduced, catalyst on-stream cycle time extends, economy effect
It is beneficial obvious.
The present invention provides a kind of selection method of hydrotreating of C-2-fraction in sequence separation process, for adding the adiabatic reactor of hydrogen
Reactor is located at after domethanizing column, pressurized with after hydrogen by the C2 hydrogenation material in ethylene unit from front-end deethanization, into
Enter adiabatic reactor reactor and carry out selection plus hydrogen, it is characterised in that: Pd-Au series catalysts is housed, with Al in adiabatic reactor reactor2O3
Or Al2O3With other hopcalites be carrier, by the quality of catalyst be 100% in terms of, wherein Pd content 0.01~
0.05%, Au content are 0.03~0.5%, and the specific surface area of catalyst is 20~60m2/ g, pore volume are 0.15~0.70mL/
g；During the preparation process, through carrier in conjunction with hydroxyl-bipyridyl, hydroxyl bipyridyl and active component form metal to the catalyst
Complex compound；Reaction condition are as follows: 30~80 DEG C of adiabatic reactor reactor inlet temperature, 1.5~3.0MPa of reaction pressure, gas space velocity
2000~15000h-1。
The characteristics of Pd-Au series catalysts used in the present invention is: the catalyst is using PdAu- hydroxyl-of the invention
Bipyridyl/Al2O3The method preparation of precursor.
The catalyst preparation process of recommendation, includes at least: hydroxyl dipyridyl derivatives being loaded on carrier, then are led to
The cation for crossing the extra hydroxyl of hydroxyl dipyridyl derivatives and/or adjacent nitrogen base and Pd, Au forms complex ion.
Hydroxyl dipyridyl derivatives of the invention, preferably hydroxyl 2,2, it is-dipyridyl derivatives, hydroxyl
3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.Because its in conjunction with aluminium oxide rear extra hydroxyl
With Pd, Au preferable complex reaction can occur for base and two nitrogen bases at ortho position.
The present invention is that carbon two selects method of hydrotreating in sequence separation process, and composition is mainly C-2-fraction in entrance raw material,
Wherein acetylene 1.0~2.5% (molar fraction), ethane 11.2~30.3% (molar fraction), ethylene 68.8~88.9% (mole
Score).The present invention is not specially limited the hydrogen alkynes ratio of each reactor, using common hydrogen alkynes ratio, generally 0.8~4.It is right
Three sections of reactor process, general first segment reactor hydrogen/acetylene be 0.8~1.2, second segment reactor hydrogen/acetylene be 1~
1.5, third section reactor hydrogen/acetylene is 1.5~3.To two reactor technique, general first segment reactor hydrogen/acetylene
It is 1~1.5, second segment reactor hydrogen/acetylene is 2~4.
The catalyst type used is defined in the present invention, such catalyst choice and traditional catalyst have larger area
Not.
The principle of the present invention is: in selective hydrogenation reaction, closing as used catalyst activity component Pd, Au is formed
The quantity of gold, the mutually adsorbed hydrogen of caltalyst is greatly reduced, and the trend that deep hydrogenation occurs for acetylene substantially reduces, catalyst
Selectivity significantly improves.
The acquisition of the catalyst preferably includes following steps: with hydroxyl dipyridyl derivatives organic solution, dipping is carried
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- hydroxyl-bipyridyl/Al2O3Precursor.At 300~600 DEG C
2~12h of roasting temperature obtains required catalyst.
Carrier of the present invention for alumina support or can mainly contain Al2O3, wherein the mixing also doped with other oxides
Object, other oxides are silica, titanium oxide, magnesia and/or calcium oxide.The aluminium oxide can be γ, δ, θ, α or its
In several mixing crystal form, preferably θ, α or its mix crystal form.
Carrier can be spherical shape in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Catalyst preparation of the present invention can be implemented using following procedure, and the preparation method of the catalyst includes such as
Lower step:
A. the organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, is absorbed solution, 20 DEG C~60
Reaction 2 at a temperature of DEG C~for 24 hours, takes out solid particle after cooling, dry at 60 DEG C~150 DEG C, obtain hydroxyl bipyridyl/
Al2O3Precursor.Hydroxyl-bipyridyl/(Pd+Au) molal quantity is preferably 1~100；The volume of organic solution is preferably equal to or greater than
The 80% of carrier total volume.
B. prepare Pd, Au mixed solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl-bipyridyl/Al obtained by step A2O3
Precursor reaction 2~for 24 hours, takes out solid particle after cooling, dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyl-bipyridyl/
Al2O3Precursor.
The ratio between molal quantity and the molal quantity of Pd of Au are preferably 2~10, and preferably adjusting pH value is 1.5~4.0；Pd, Au's
The volume of mixed solution is preferably hydroxyl-bipyridyl/Al2O3The 60%~200% of precursor total volume.
C. the PdAu- hydroxyl-bipyridyl/Al prepared by step B2O3Precursor 300~600 DEG C of roasting temperatures 2~
12h, so that PdAu- hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
In catalyst in use, H can be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
Reactor refers to adiabatic reactor reactor in the present invention.It can be single or more, preferably 2~3.
Inventor also found, when carrying out selective hydrogenation reaction using this method, the active of catalyst reaction, selectivity are
It is significantly improved, ethylene increment increases, and green oil generating amount reduces, anticoking capability enhancing.
Meanwhile the method for the present invention prepares palladium-gold catalyst, since its alloy structure is obvious, alloy effect is stronger, is more suitable for
After requiring higher two back end hydrogenation device of carbon, the alloy catalyst to be applied to carbon two catalyst activity, selectivity
Hydrogenation plant has excellent activity and selectivity at a lower reaction temperature.
Detailed description of the invention
Attached drawing 1 is using a kind of C 2 fraction selective hydrogenation process flow chart using sequence separation process of the invention.
1-oil scrubber；2-water scrubbers；3-caustic wash towers；4-driers；5-domethanizing columns；6-front-end deethanization towers；7—
Acetylene converter；8-compressors.
Specific embodiment
Embodiment 1
Weigh Φ 3.5, specific surface area 20.0m2Spherical α-the Al of/g, Kong Rong 0.31mL/g, heap density 0.82g/ml2O3
Carrier 500g.
By 23.88g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 2h 4,4- dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 60 DEG C of dry 10h,
Obtain hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium chloride, gold chloride are dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, are configured to mix
Solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out residual
Liquid obtains PdAu- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=30).120 DEG C of dry 4h
3h is roasted in air atmosphere at a temperature of 550 DEG C afterwards, obtains (Pd-Au)/Al2O3Catalyst.Fixed bed reaction is placed in front of use
It is 99.9% with hydrogen purity in device, air speed 200h-1Gas obtain load type palladium-Jin Cuihua at a temperature of 120 DEG C
Agent S-1.It is 0.21% that measure catalyst Pd content, which be 0.018%, Au content,.
Comparative example 1
Weigh Φ 3.5, specific surface area 20.0m2Spherical α-the Al of/g, Kong Rong 0.31mL/g, heap density 0.82g/ml2O3
Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC 8.9g is dissolved completely in 800mlTHF (tetrahydrofuran), by above-mentioned carrier impregnation into above-mentioned solution,
PVC is set to be adsorbed in Al after standing 2h2O3Surface, drying for standby.Obtain PVC/Al2O3。
119.28g dicyandiamide and 4.0gNa is added2CO3, the PVC/Al being prepared is added2O3Flow back 1h, is cooled to room
Temperature is washed with deionized to neutrality, drying for standby.Obtain functionalization PVC/Al2O3。
B, Pd-Au- high-molecular complex/Al2O3The preparation of presoma
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, is made into mixed
Close solution.Take the functionalization-PVC/Al prepared2O3Presoma adds it in the mixed solution prepared, stirring
30min pours out raffinate, and above-mentioned product is washed with deionized to neutrality, and 120 DEG C of dry 4h obtain (Pd-Au)-PVC/Al2O3
Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h, obtain oxidation state (Pd-Au)/Al in air atmosphere2O3Catalysis
Agent.It is placed in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas, at 120 DEG C
At a temperature of, obtain support type palladium-gold catalyst D-1.It is 0.21% that measure catalyst Pd content, which be 0.018%, Au content,.It adopts
With back end hydrogenation technique, process flow chart is as shown in Fig. 1, raw material composition are as follows:
C2H2: 1.6% (Φ), C2H475.3% (Φ), C2H623.1% (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: 2000h-1, operating pressure: 1.7MPa, each reactor catalyst loadings: 450ml.One section anti-
Answer device H2/C2H2=1.5:1 (molar ratio)；Second stage reactor H2/C2H2=3:1 (molar ratio), the result after examination in 500 hours
As shown in table 1.
1 catalyst 500h performance average value of table
Embodiment 2
Weigh Φ 4.0mm, high 4.0mm, specific surface area 55.0m2/ g, Kong Rongwei 0.45ml/g, heap density are 0.68g/
Cylindrical θ-the Al of ml2O3Carrier 500g.
By 1.5g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 600mL ethanol solution, by above-mentioned carrier impregnation above-mentioned molten
In liquid, after after standing 8h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 90 DEG C of dry 8h obtain hydroxyl
Base-bipyridyl/Al2O3Precursor.
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.5, is made into mixed
Close solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 8h, pours out residual
Liquid, dry 6h, obtains PdAu- hydroxyl-bipyridyl/Al at 110 DEG C of remaining solid2O3Precursor (hydroxyl-bipyridyl molal quantity:
(Pd+Au)=1.5).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Fixed-bed reactor is placed in front of use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain support type palladium-gold catalyst S- at a temperature of 120 DEG C
2.It is 0.036% that measure catalyst Pd content, which be 0.038%, Au content,.
Comparative example 2
Catalyst preparation
Weigh Φ 4.0mm, high 4.0mm, specific surface area 55.0m2/ g, Kong Rongwei 0.45ml/g, heap density are 0.68g/
Cylindrical θ-the Al of ml2O3Carrier 500g.
A, functionalized polystyrene acrylonitrile (SAN)/Al2O3Preparation
SAN resin 2.2g is weighed, is dissolved in 600ml DMF (dimethylformamide) solvent, stirring makes SAN tree at room temperature
Rouge is completely dissolved, be added in this solution it is above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred, separate dry after solvent, obtain
To SAN/Al2O3。
By SAN/Al obtained above2O3, it is added in 500ml deionized water, 57.6g ethylenediamine is added, flows back 4h, cold
But product is taken out afterwards, is washed to neutrality, is dried to obtain functionalization-SAN/Al2O3。
B、(Pd-Au)-SAN/Al2O3The preparation of presoma
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 1200mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.5, is made into
Mixed solution.Take the functionalization-SAN/Al prepared2O3Presoma, by functionalization-SAN/Al2O3It is added to the mixing prepared
In solution, 5min is stirred, raffinate is poured out, above-mentioned product is washed with deionized to neutrality, obtains (Pd-Au)-after dry
SAN/Al2O3Presoma.
C, the preparation of catalyst
The presoma of above-mentioned preparation is obtained into Pd-Au/Al in 500 DEG C of roasting 4h of air atmosphere2O3Catalyst.Before use
It is placed in fixed-bed reactor, is 99.9% with hydrogen purity, air speed 200h-1Gas obtained at a temperature of 120 DEG C
To support type palladium-gold catalyst D-2.It is 0.036% that measure catalyst Pd content, which be 0.038%, Au content,.
Using back end hydrogenation technique, process flow chart is as shown in Fig. 1, raw material composition are as follows:
C2H2: 1.4% (Φ), C2H480.0% (Φ), C2H618.6% (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: 6000h-1, operating pressure: 1.5MPa, each reactor catalyst loadings: 450ml.One section anti-
Answer device H2/C2H2=1.5:1 (molar ratio)；Second stage reactor H2/C2H2=4:1 (molar ratio), the result after examination in 500 hours
As shown in table 2.
2 500 hours catalyst performance average value of table
Embodiment 3
Weigh Φ 3.0mm, specific surface area 35.0m2/ g, Kong Rongwei 0.20ml/g, heap are more spherical than the tooth for 0.75g/ml
Carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.By dihydroxy -3 49.75g 6,6'-,
3'- bipyridyl is dissolved in 650mL ethanol solution, in the above solution by above-mentioned carrier impregnation, makes 6,6'- dihydroxy after standing 12h
After base -3,3'- bipyridyl loads on alumina support completely, 120 DEG C of dry 4h obtain hydroxyl-bipyridyl/Al2O3Preceding body
Body.
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 650mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3, is made into mixing
Solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 12h, pours out residual
Liquid, 100 DEG C of dry 8h obtain PdAu- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=90).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.Fixed-bed reactor is placed in front of use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain support type palladium-gold catalyst S- at a temperature of 120 DEG C
3.It is 0.20% that measure catalyst Pd content, which be 0.037%, Au content,.
Comparative example 3
Catalyst preparation
Weigh Φ 3.0mm, specific surface area 35.0m2/ g, Kong Rongwei 0.20ml/g, heap are more spherical than the tooth for 0.75g/ml
Carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 200mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3, is made into mixing
Solution will shake 0.5 hour after the solution spraying to above-mentioned carrier, after 100 DEG C of dry 8h, 500 DEG C of roastings in air atmosphere
4h obtains (Pd-Au)/Al2O3Catalyst.It is placed in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed
For 200h-1Gas obtain support type palladium-gold catalyst D-3 at a temperature of 120 DEG C.Measuring catalyst Pd content is
0.037%, Au content are 0.20%.
Using back end hydrogenation technique, reaction raw materials are as follows:
C2H2: 2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition: three sections of bed adiabatic reactor reactor tandem process, i.e. first stage reactor outlet material enter second-stage reaction
Device, second stage reactor outlet material enter three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 15000h-1, operating pressure: 2.0MPa, each reactor catalyst loadings: 450ml.One section
Reactor H2/C2H2=1:1 (molar ratio)；Second stage reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=
3:1 (molar ratio)；The results are shown in Table 3 after examination in 500 hours.
3 catalyst 500h performance average value of table
Embodiment 4
Weigh Φ 4.0mm, high 4.0mm, specific surface area 50.0m2/ g, Kong Rongwei 0.50ml/g, heap ratio are 0.65g/ml
Tooth ball type carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
By 219g 6,6'- dihydroxy -3,3'- bipyridyl is dissolved in 600mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 8h 6,6'- dihydroxy -3,3'- bipyridyl being loaded on alumina support completely, 90 DEG C of dryings
10h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 650mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3.5, is made into mixed
Close solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 10h, pours out
Raffinate, 90 DEG C of dry 10h obtain PdAu- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=
100)。
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Fixed-bed reactor is placed in front of use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain support type palladium-gold catalyst S- at a temperature of 120 DEG C
4.It is 0.38% that measure catalyst Pd content, which be 0.015%, Au content,.
Comparative example 4
Catalyst preparation
Weigh Φ 4.0mm, high 4.0mm, specific surface area 50.0m2/ g, Kong Rongwei 0.50ml/g, heap ratio are 0.65g/ml
Tooth ball type carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 200mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 3.5, is made into mixed
Solution is closed, will be shaken after the solution spraying to above-mentioned carrier 0.5 hour, after 90 DEG C of dry 10h, 600 DEG C of roastings in air atmosphere
It burns 2h and obtains (Pd-Au)/Al2O3Catalyst.It is placed in fixed-bed reactor before use, is 99.9% with hydrogen purity, it is empty
Speed is 200h-1Gas obtain support type palladium-gold catalyst D-4 at a temperature of 120 DEG C.Measuring catalyst Pd content is
0.015%, Au content are 0.38%.
Using back end hydrogenation technique, reaction raw materials are as follows:
C2H2: 2.2 (v%) C2H479.3 (v%), C2H618.5 (v%).
Reaction condition: three sections of bed adiabatic reactor tandem process, i.e. first stage reactor outlet material enter second stage reactor,
Second stage reactor outlet material enters three sections of reactors, and every section of reactor has independent air distribution system.
Material gas space velocity: 10000h-1, operating pressure: 2.5MPa, each reactor catalyst loadings: 450ml.One section
Reactor H2/C2H2=1:1 (molar ratio)；Second stage reactor H2/C2H2=1.5:1 (molar ratio)；Three sections of reactor H2/C2H2=
3:1 (molar ratio)；The results are shown in Table 4 after examination in 500 hours.
4 catalyst 500h performance average value of table
Embodiment 5
Weigh Φ 3.5, specific surface area 20.0m2Spherical α-the Al of/g, Kong Rong 0.31mL/g, heap density 0.82g/ml2O3
Carrier 500g.
By 34.12g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 2h 4,4- dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 60 DEG C of dry 10h,
Obtain hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium chloride is weighed, gold chloride is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, 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- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Au)=30).120 DEG C of dryings
3h 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 placed in front of use
It answers in device, is 99.9% with hydrogen purity, air speed 200h-1Gas obtain load type palladium-gold at a temperature of 120 DEG C and urge
Agent S-5.It is 0.30% that measure catalyst Pd content, which be 0.027%, Au content,.
Comparative example 5
Weigh Φ 3.5, specific surface area 20.0m2Spherical α-the Al of/g, Kong Rong 0.31mL/g, heap density 0.82g/ml2O3
Carrier 500g.
By 34.12g 4,4- dihydroxy -2,2- bipyridyl is dissolved in 650mL ethanol solution, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 2h 4,4- dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 60 DEG C of dry 10h,
Obtain hydroxyl-bipyridyl/Al2O3Precursor.
Claim appropriate palladium nitrate, silver nitrate is dissolved in the 600mL deionized water containing appropriate hydrochloric acid, and adjusting pH value is 2.0, is configured to mix
Close solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out residual
Liquid obtains PdAu- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ag)=30).120 DEG C of dry 4h
3h is roasted in air atmosphere at a temperature of 550 DEG C afterwards, obtains (Pd-Ag)/Al2O3Catalyst.Fixed bed reaction is placed in front of use
It is 99.9% with hydrogen purity in device, air speed 200h-1Gas obtain load type palladium-Jin Cuihua at a temperature of 120 DEG C
Agent D-5.It is 0.16% that measure catalyst Pd content, which be 0.027%, Ag content,.
Using back end hydrogenation technique, process flow chart is as shown in Fig. 1, raw material composition are as follows:
C2H2: 1.6% (Φ), C2H475.3% (Φ), C2H623.1% (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: 2000h-1, operating pressure: 1.7MPa, each reactor catalyst loadings: 450ml.One section anti-
Answer device H2/C2H2=1.5:1 (molar ratio)；Second stage reactor H2/C2H2=3:1 (molar ratio), the result after examination in 500 hours
As shown in table 5.
5 catalyst 500h performance average value of table
It is and organic and when active component content is identical as can be seen that compared with using traditional preparation catalyst
Macromolecular grafted functional group simultaneously loads on a catalyst support, then the solution of carrier impregnation activity Pd, Au is obtained organic high
The method of molecular metal complex compound prepares catalyst and compares, using method of hydrotreating of the invention, the activity and choosing of hydrogenation reaction
Selecting property is significantly better than traditional method of hydrotreating, and the production quantity of green oil is also greatly lowered in hydrogenation process.The reduction of green oil simultaneously,
So that the activated centre of catalyst is not covered by by-product, catalyst activity and selectivity are kept well.
Claims (13)
1. the selection method of hydrotreating of C-2-fraction in a kind of sequence separation process, for adding the adiabatic reactor reactor of hydrogen to be located at piptonychia
It is pressurized with after hydrogen by two material of carbon in ethylene unit from front-end deethanization tower after alkane tower, into adiabatic reactor reactor into
Row selection plus hydrogen, it is characterised in that: Pd-Au series catalysts are housed, with Al in adiabatic reactor reactor2O3Or Al2O3With other oxidations
The mixture of object is carrier, is in terms of 100% by the quality of catalyst, wherein Pd content 0.01~0.05%, Au content are 0.03
~0.5%, the specific surface area of catalyst is 20~60m2/ g, pore volume are 0.15~0.70mL/g；It is prepared by the catalyst
Cheng Zhong, through carrier in conjunction with hydroxyl dipyridyl derivatives, hydroxyl bipyridyl and active component form metal complex；Instead
Answer condition are as follows: 30~80 DEG C of adiabatic reactor reactor inlet temperature, 1.5~3.0MPa of reaction pressure, gas space velocity 2000~
15000h-1；The acquisition of catalyst includes the following steps: with hydroxyl dipyridyl derivatives organic solution, impregnated carrier, through dry
Hydroxyl-bipyridyl/Al is obtained after dry2O3Precursor, the mixed solution for preparing Pd, Au impregnate hydroxyl-bipyridyl/Al2O3Preceding body
Body, it is dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyl-bipyridyl/Al2O3Precursor；In 300~600 DEG C of roasting temperatures
2~12h obtains required catalyst.
2. 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.
3. selection method of hydrotreating according to claim 1, it is characterised in that carrier is aluminium oxide, or is mainly contained
Al2O3, wherein other oxides are silica, titanium oxide, magnesia and/or calcium oxide also doped with other oxides；It is described
Aluminium oxide be γ, δ, θ, α or in which several mixing crystal form Al2O3。
4. selection method of hydrotreating according to claim 3, it is characterised in that the aluminium oxide is θ, α or it mixes crystal form
Al2O3。
5. selection method of hydrotreating according to claim 1, it is characterised in that carrier is spherical, cylindrical, circular ring shape, item
Shape, cloverleaf pattern or bunge bedstraw herb shape.
6. -5 any selection method of hydrotreating according to claim 1, it is characterised in that the preparation method of catalyst includes such as
Lower step:
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, at a temperature of 20 DEG C~60 DEG C react 2~for 24 hours,
Solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdAu- hydroxyl-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- hydroxyl-bipyridyl/Al2O3Precursor；
C. the preparation of catalyst
PdAu- hydroxyl-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature so that
PdAu- hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
7. selection method of hydrotreating according to claim 6, it is characterised in that hydroxyl-bipyridyl/(Pd+Au) in step A
Molal quantity is 1~100:1.
8. selection method of hydrotreating according to claim 6, it is characterised in that in stepb, the mixed solution of Pd, Au are chlorine
Change the mixed solution of palladium and gold chloride.
9. selection method of hydrotreating according to claim 6, it is characterised in that in stepb, the molal quantity of Au and rubbing for Pd
The ratio between your number is 2~10:1.
10. selection method of hydrotreating according to claim 6, it is characterised in that in stepb, the mixing for adjusting Pd, Au is molten
Liquid pH value is 1.5~4.0.
11. selection method of hydrotreating according to claim 1, it is characterised in that hydrogen is 0.8~4:1 with acetylene volume ratio.
12. selection method of hydrotreating according to claim 1, it is characterised in that adiabatic reactor reactor reaction bed number is two sections
Or three sections of beds.
13. selection method of hydrotreating according to claim 12, it is characterised in that adiabatic reactor reactor reaction bed number is two
Duan Shi, first segment reactor hydrogen and acetylene volume ratio are 1~1.5:1, second segment reactor hydrogen and acetylene volume ratio be 2~
4:1；When adiabatic reactor reactor reaction bed number is three sections, first segment reactor hydrogen and acetylene volume ratio are 0.8~1.2:1,
Second segment reactor hydrogen and acetylene volume ratio are 1~1.5:1, third section reactor hydrogen and acetylene volume ratio be 1.5~
3.0:1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4484015A (en) * | 1981-05-06 | 1984-11-20 | Phillips Petroleum Company | Selective hydrogenation |
| CN102206131A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4484015A (en) * | 1981-05-06 | 1984-11-20 | Phillips Petroleum Company | Selective hydrogenation |
| CN102206131A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
Non-Patent Citations (1)
| Title |
|---|
| 高分子负载加氢催化剂中钯流失的研究 Ⅰ.高分子载体的影响;何炳林 等;《应用化学》;19891231;第6卷(第2期);第54页表4及其最后一段 |
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