CN105732265B - Carbon two selects method of hydrotreating in a kind of sequence separation process - Google Patents
Carbon two selects method of hydrotreating in a kind of sequence separation process Download PDFInfo
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- CN105732265B CN105732265B CN201410766754.8A CN201410766754A CN105732265B CN 105732265 B CN105732265 B CN 105732265B CN 201410766754 A CN201410766754 A CN 201410766754A CN 105732265 B CN105732265 B CN 105732265B
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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 dethanizer, it is pressurized with after hydrogen, selection plus hydrogen are carried out into adiabatic reactor reactor, it is characterized by: being equipped with Pd-Ag 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 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→C2H4△ H=-175.7kJ/mol (1)
Side reaction
C2H4+H2→C2H6△ 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.
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-Ag 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 Ag 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 carbon two in a kind of sequence separation process to select method of hydrotreating, for adding the adiabatic reactor reactor of hydrogen
It is pressurized with after hydrogen by the C2 hydrogenation material in ethylene unit from front-end deethanization after domethanizing column, into insulation
Bed reactor carries out selection plus hydrogen, it is characterised in that: Pd-Ag series catalysts is housed, with Al in adiabatic reactor reactor2O3Or Al2O3
It is carrier with other hopcalites, is wherein palladium content 0.025~0.055% in terms of 100% by the quality of catalyst,
Ag content is 0.05~0.3%, and the specific surface area of catalyst is 20~60m2/ g, pore volume are 0.15~0.70mL/g；This is urged
During the preparation process, through carrier in conjunction with hydroxyl-bipyridyl, hydroxyl bipyridyl and active component form metal complex to agent
Object；Reaction condition are as follows: 40~100 DEG C of adiabatic reactor reactor inlet temperature, 1.5~2.5MPa of reaction pressure, gas space velocity 2000
~10000h-1。
The characteristics of Pd-Ag series catalysts used in the present invention is: the catalyst is using PdAg- 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, Ag 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, Ag 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, Ag 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, the mixed-cation solution for preparing Pd, Ag impregnate hydroxyl-connection pyrrole
Pyridine/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdAg- hydroxyl-bipyridyl/Al2O3Precursor.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, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl bipyridyl/Al2O3Before
Body.Hydroxyl-bipyridyl/(Pd+Ag) molal quantity is preferably 1~100；The body of hydroxyl dipyridyl derivatives organic solution
Product is preferably equal to or greater than the 80% of carrier total volume.
B. prepare Pd, Ag mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl obtained by step A-connection pyrrole
Pyridine/Al2O3Precursor reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdAg- hydroxyl-connection pyrrole
Pyridine/Al2O3Precursor.
The ratio between molal quantity and the molal quantity of Pd of Ag are preferably 0.4~5, and preferably adjusting pH value is 2.0~4.0；Pd, Ag's
The volume of mixed-cation solution is preferably hydroxyl-bipyridyl/Al2O3The 80%~120% of precursor total volume.
C. the PdAg- hydroxyl-bipyridyl/Al prepared by step B2O3Precursor 300~600 DEG C of roasting temperatures 2~
12h, so that PdAg- 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.
Detailed description of the invention
Attached drawing 1 is to select hydrogenation technique flow chart using a kind of carbon two of sequence separation process of the invention.1-oil wash
Tower；2-water scrubbers；3-caustic wash towers；4-driers；5-domethanizing columns；6-dethanizers；7-Acetylene converters；
8-heat exchangers.
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 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.
Weigh 0.37g Pd (NO3)2、0.79g AgNO3, be dissolved in 600mL deionized water, be added 10ml nitric acid stir to
It is completely dissolved, adjusting pH value is 3.5, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor, which is added to, have been prepared
Solution, stir 10min, stand 2h, pour out raffinate, obtain PdAg- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl
Molal quantity: (Pd+Ag)=30).Roast 3h in air atmosphere at a temperature of 550 DEG C after 120 DEG C of dry 4h, obtain (Pd-Ag)/
Al2O3Catalyst.It is placed in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas
Body obtains load type palladium-silver catalyst S-1 at a temperature of 120 DEG C.Measuring catalyst Pd content is 0.030%, Ag content
It is 0.10%.
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-Ag- high-molecular complex/Al2O3The preparation of presoma
Weigh 0.37gPd (NO3)、0.79gAgNO3, it is dissolved in 600mL deionized water, 10ml nitric acid is added and stirs to complete
Dissolution, adjusting pH value is 3.5, is made into mixed solution.Take the functionalization-PVC/Al prepared2O3Presoma adds it to Pd
(NO3)2、AgNO3Mixed solution in, stir 30min, pour out raffinate, above-mentioned product be washed with deionized to neutrality, 120
DEG C dry 4h obtains (Pd-Ag)-PVC/Al2O3Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h, obtain oxidation state (Pd-Ag)/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 load type palladium-silver catalyst D-1.It is 0.10% that measure catalyst Pd content, which be 0.030%, 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 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 1.4g 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.
Weigh 0.73gPd (NO3)2、2.37gAgNO3, it is dissolved in 600mL deionized water, 10ml nitric acid is added and stirs to complete
Fully dissolved, adjusting pH value is 2.5, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor be added to prepared it is molten
Liquid stirs 60min, stands 8h, pours out raffinate, and dry 6h at 110 DEG C of remaining solid obtains PdAg- hydroxyl-bipyridyl/Al2O3
Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ag)=1).
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 load type palladium-silver catalyst S- at a temperature of 120 DEG C
2.It is 0.30% that measure catalyst Pd content, which be 0.060%, Ag 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-Ag)-SAN/Al2O3The preparation of presoma
Weigh 0.73gPd (NO3)2、2.37gAgNO3, it is dissolved in 1200mL deionized water, 10ml nitric acid is added and stirs to complete
Fully dissolved, adjusting pH value is 2.5, is made into mixed solution.Take the functionalization-SAN/Al prepared2O3Presoma, by functionalization-SAN/
Al2O3It is added to Pd (NO3)2、AgNO3Mixed solution in, stir 5min, pour out raffinate, above-mentioned product be washed with deionized water
It washs to neutrality, obtains (Pd-Ag)-SAN/Al after dry2O3Presoma.
C, the preparation of catalyst
The presoma of above-mentioned preparation is obtained into Pd-Ag/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 load type palladium-silver catalyst D-2.It is 0.26% that measure catalyst Pd content, which be 0.054%, Ag 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: 2.0MPa, each reactor catalyst loadings:
450ml.First stage reactor H2/C2H2=1.5:1 (molar ratio)；Second stage reactor H2/C2H2=4:1 (molar ratio),
The results are shown in Table 2 after examination in 500 hours.
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 71.07g 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.
Weigh 0.40gPd (NO3)2,0.39gAgNO3, it is dissolved in 550mL deionized water, 10ml nitric acid is added and stirs to complete
Fully dissolved, adjusting pH value is 3, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared,
60min is stirred, 12h is stood, pours out raffinate, 100 DEG C of dry 8h obtain PdAg- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-connection
Pyridine molal quantity: (Pd+Ag)=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 load type palladium-silver catalyst S- at a temperature of 120 DEG C
3.It is 0.050% that measure catalyst Pd content, which be 0.040%, Ag 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.
Weigh 0.40gPd (NO3)2,0.39gAgNO3, it is dissolved in 300mL deionized water, is dissolved in 550mL deionized water, adds
Enter 10ml nitric acid to stir to being completely dissolved, adjusting pH value is 3, will be shaken 0.5 hour, 100 DEG C after the solution spraying to above-mentioned carrier
After dry 8h, 500 DEG C of roasting 4h obtain (Pd-Ag)/Al in air atmosphere2O3Catalyst.Fixed bed reaction is placed in front of use
It is 99.9% with hydrogen purity in device, air speed 200h-1Gas obtain the catalysis of load type palladium-silver at a temperature of 120 DEG C
Agent D-3.It is 0.05% that measure catalyst Pd content, which be 0.04%, Ag content,.
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: 10000h-1, operating pressure: 2.5MPa, each reactor catalyst loadings: 450ml.One section
40 DEG C of reactor inlet temperature, H2/C2H2=1:1 (molar ratio)；50 DEG C of second stage reactor inlet temperature, H2/C2H2=1.5:1
(molar ratio)；Three sections 80 DEG C of reactor inlet temperature, H2/C2H2=3:1 (molar ratio)；The result such as table after examination in 500 hours
Shown in 3.
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 21.9g 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.
Weigh 0.61gPd (NO3)2,1.57gAgNO3, it is dissolved in 650mL deionized water, 10ml nitric acid is added and stirs to complete
Fully dissolved, adjusting pH value is 2, is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared,
60min is stirred, 10h is stood, pours out raffinate, 90 DEG C of dry 10h obtain PdAg- hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-connection
Pyridine molal quantity: (Pd+Ag)=10).
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 load type palladium-silver catalyst S- at a temperature of 120 DEG C
4.It is 0.2% that measure catalyst Pd content, which be 0.05%, Ag 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.
Weigh 0.61gPd (NO3)2,1.57gAgNO3, it is dissolved in 650mL deionized water, 10ml nitric acid is added and stirs to complete
Fully dissolved, adjusting pH value is 2, is made into mixed solution, will shake after the solution spraying to above-mentioned carrier 0.5 hour, 90 DEG C of dry 10h
Afterwards, 600 DEG C of roasting 2h obtain (Pd-Ag)/Al in air atmosphere2O3Catalyst.Fixed-bed reactor is placed in front of use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain load type palladium-silver catalyst D- at a temperature of 120 DEG C
4.It is 0.2% that measure catalyst Pd content, which be 0.05%, Ag content,.
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
40 DEG C of reactor inlet temperature, H2/C2H2=1:1 (molar ratio)；50 DEG C of second stage reactor inlet temperature, H2/C2H2=1.5:1
(molar ratio)；Three sections 80 DEG C of reactor inlet temperature, H2/C2H2=3:1 (molar ratio)；The result such as table after examination in 500 hours
Shown in 4.
4 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, Ag 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 (16)
1. in a kind of sequence separation process carbon two select method of hydrotreating, for add the adiabatic reactor reactor of hydrogen be located at domethanizing column it
Afterwards, pressurized with after hydrogen by two material of carbon in ethylene unit from dethanizer, selection, which is carried out, into adiabatic reactor reactor adds
Hydrogen, it is characterised in that: Pd-Ag series catalysts are housed, with Al in adiabatic reactor reactor2O3Or Al2O3With the mixing of other oxides
Object is carrier, is in terms of 100% by the quality of catalyst, wherein Pd content be 0.025~0.5%, Ag content be 0.05~
0.3%, the specific surface area of catalyst is 20~60m2/ g, pore volume are 0.15~0.70mL/g；The catalyst is in preparation process
In, through carrier in conjunction with hydroxyl dipyridyl derivatives, hydroxyl bipyridyl and active component form metal complex；Reaction
Condition are as follows: 40~100 DEG C of adiabatic reactor reactor inlet temperature, 1.5~2.5MPa of reaction pressure, gas space velocity 2000~
10000h-1。
2. carbon two selects method of hydrotreating in sequence separation process according to claim 1, it is characterised in that catalyst preparation
Process includes at least: hydroxyl dipyridyl derivatives being loaded on carrier, then more by hydroxyl dipyridyl derivatives
The cation of remaining hydroxyl and/or nitrogen base and Pd, Ag forms complex ion.
3. carbon two selects method of hydrotreating in sequence separation process according to claim 2, it is characterised in that hydroxyl connection
Pyridine derivate is hydroxyl 2,2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives.
4. carbon two selects method of hydrotreating in sequence separation process according to claim 1, it is characterised in that catalyst preparation
Process includes at least following steps: with hydroxyl dipyridyl derivatives organic solution, impregnated carrier obtains hydroxyl after drying
Base-bipyridyl/Al2O3Precursor, the mixed-cation solution for preparing Pd, Ag impregnate hydroxyl-bipyridyl/Al2O3Precursor, in
It is dry at 60 DEG C~150 DEG C, obtain PdAg- hydroxyl-bipyridyl/Al2O3Precursor；300~600 DEG C of roasting temperatures 2~
12h obtains required catalyst.
5. carbon two selects method of hydrotreating in sequence separation process according to claim 1, it is characterised in that carrier is oxidation
Aluminium, or mainly contain Al2O3, wherein other oxides are silica, titanium oxide, magnesia also doped with other oxides
And/or calcium oxide；The aluminium oxide is γ, δ, θ, α or in which several mixing crystal form Al2O3。
6. carbon two selects method of hydrotreating in sequence separation process according to claim 5, it is characterised in that the oxidation
Aluminium is θ, α or it mixes crystal form Al2O3。
7. carbon two selects method of hydrotreating in sequence separation process according to claim 1, it is characterised in that carrier is spherical shape,
Cylinder, circular ring shape, bar shaped, cloverleaf pattern or bunge bedstraw herb shape.
8. carbon two selects method of hydrotreating in -7 any sequence separation process according to claim 1, it is characterised in that catalysis
The preparation method of agent includes the following steps:
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.PdAg- hydroxyl-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Ag mixed-cation 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, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdAg- hydroxyl-bipyridyl/Al2O3Before
Body；
C. the preparation of catalyst
PdAg- hydroxyl-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature so that
PdAg- hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
9. carbon two selects method of hydrotreating in sequence separation process according to claim 8, it is characterised in that hydroxyl in step B
The ratio between molal quantity of base-bipyridyl and (Pd+Ag) is 1~100: 1.
10. carbon two selects method of hydrotreating in sequence separation process according to claim 8, it is characterised in that in stepb,
The mixed-cation solution of Pd, Ag are the mixed solution of palladium nitrate and silver nitrate.
11. carbon two selects method of hydrotreating in sequence separation process according to claim 8, it is characterised in that in stepb,
The ratio between molal quantity and the molal quantity of Pd of Ag are 0.4~5: 1.
12. carbon two selects method of hydrotreating in sequence separation process according to claim 8, it is characterised in that in stepb,
The mixed-cation solution ph for adjusting Pd, Ag is 2.0~4.0.
13. carbon two selects method of hydrotreating in sequence separation process according to claim 1, it is characterised in that hydrogen and acetylene
Volume ratio is 0.8~4: 1.
14. carbon two selects method of hydrotreating in sequence separation process according to claim 1, it is characterised in that adiabatic reactor reaction
The device reaction bed number of plies is two sections or three sections of beds.
15. carbon two selects method of hydrotreating in sequence separation process according to claim 14, it is characterised in that adiabatic reactor is anti-
Answer the device reaction bed number of plies be two sections when, first segment reactor hydrogen/acetylene volume ratio be 1~1.5, second segment reactor hydrogen with
Acetylene volume ratio is 2~4: 1.
16. carbon two selects method of hydrotreating in sequence separation process according to claim 14, it is characterised in that adiabatic reactor is anti-
When to answer the device reaction bed number of plies be 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, and third section reactor hydrogen and acetylene volume ratio are 1.5~3.0: 1.
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Citations (4)
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|---|---|---|---|---|
| US4484015A (en) * | 1981-05-06 | 1984-11-20 | Phillips Petroleum Company | Selective hydrogenation |
| US5856262A (en) * | 1995-09-23 | 1999-01-05 | Basf Aktiengesellschaft | Supported palladium catalyst for selective catalytic hydrogenation of acetylene in hydrocarbonaceous streams |
| 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 |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4484015A (en) * | 1981-05-06 | 1984-11-20 | Phillips Petroleum Company | Selective hydrogenation |
| US5856262A (en) * | 1995-09-23 | 1999-01-05 | Basf Aktiengesellschaft | Supported palladium catalyst for selective catalytic hydrogenation of acetylene in hydrocarbonaceous streams |
| 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 |
| 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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