CN105732282B - Carbon two selects method of hydrotreating in sequence separation process - Google Patents
Carbon two selects method of hydrotreating in 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 from front-end deethanization tower in ethylene unit, it is pressurized with after hydrogen, selection plus hydrogen are carried out into adiabatic reactor reactor, Pd Cu series catalysts are housed in fixed bed reactors, the catalyst is in preparation process, it is combined with hydroxyl dipyridyl derivatives by alumina series carrier, the hydroxyl bipyridyl being incorporated on carrier forms metal complex with active component；Method using the present invention, the activity of hydrogenation reaction and selectivity 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, and catalyst activity and selectivity are kept well；Catalyst used in the present invention is particularly suitable for the C2 hydrogenation device more demanding to catalyst activity.
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 technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the most bases of downstream polymerisation device
This raw material.The selection of wherein acetylene adds hydrogen to have extremely important influence to ethylene processing industry, in addition to ensureing going out for hydrogenation reactor
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 improving entire work
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 flow
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 domethanizing column position, hydrogenation reactor is located at before domethanizing column for front-end hydrogenation alkynes hydrogenation reactor, 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, catalyst activity and selectivity is made to decline.
Two back end hydrogenation of carbon mainly uses two sections or three sections of reactor tandem process, the dress that air speed is relatively low or alkynes content is low at present
It sets, two reactor series connection may be used.Commercial plant at present, mainly based on three sections of reactor tandem process.
General group of back end hydrogenation material becomes：The acetylene of 1.0~2.2% (v), 65~85% ethylene, remaining is ethane, hydrogen
Gas after metering by being incorporated.
The reaction is exothermic reaction, but temperature rises 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, which is converted to its content, is 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：
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 is to generate the General reactions formula of green oil to generating green oil to have important contribution, reaction (5).
In these reactions, only reacts (1) and be desirable to the reaction occurred, remaining is undesirable reaction.
US5856262 is reported using the modified silica of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) 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 acts on US4404124 with palladium, is 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 prepared using infusion process, limited by 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 bimetallics 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 partly form alloy
Structure.It is often selectively preferable in initial reaction stage when this catalyst is applied to C 2 fraction selective hydrogenation, with run time
Extend, selectivity constantly declines, and 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, ensures 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 of aluminium oxide with macromolecule
Absorption, the amount of carrier adsorption high-molecular compound will be limited by the hydroxyl quantity of 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 technological process complexity.
Higher in air speed, alkynes and the higher carbon two of diene content, carbon three select in hydrogenation plant, add hydrogen operating mode to urging
Agent Active pharmaceutical is higher, and the bimetal supported catalyst using Pd as active component, Ag for auxiliary agent is used for the type device,
The shortcomings that it is high that there are reaction temperatures, and activity cannot preferably meet device requirement needs that more suitable auxiliary agent is selected to prepare catalysis
Agent, to meet the hydrogenation requirements of device.
Invention content
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 activearm
Divide high degree of dispersion, the Pd-Cu catalyst with height alloy structure, improve hydrogenation selectivity, improve ethylene increment, improves device
Operation stability and economic benefit.
Inventor has found, is separated by Cu when using catalyst prepared by preparation method of the present invention, the Pd in catalyst 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
Production quantity significantly declines, and therefore the surface coking rate of catalyst is greatly reduced, catalyst on-stream cycle time extends, economy effect
It is beneficial apparent.
The present invention provides carbon two in a kind of sequence separation process to select method of hydrotreating, the adiabatic reactor reactor for adding hydrogen
It is pressurized with after hydrogen by the C2 hydrogenation material from front-end deethanization in ethylene unit after domethanizing column, into thermal insulation
Bed reactor carries out selection plus hydrogen, it is characterised in that：Pd-Cu series catalysts are housed, with Al in adiabatic reactor reactor2O3Or Al2O3
It is carrier with other hopcalites, is wherein palladium content 0.020~0.055% in terms of 100% by the quality of catalyst,
Cu contents are 0.03~0.2%, and the specific surface area of catalyst is 20~60m2/ g, pore volume are 0.15~0.70mL/g；This is urged
Agent is combined in preparation process, by carrier with hydroxyl-bipyridyl, and hydroxyl bipyridyl forms metal complex with active component
Object；Reaction condition is：30~70 DEG C, 1.5~2.5MPa of reaction pressure of adiabatic reactor reactor inlet temperature, gas space velocity 5000~
10000h-1。
The characteristics of Pd-Cu series catalysts used in the present invention is：The catalyst is PdCu- hydroxyls-using the present invention
Bipyridyl/Al2O3Prepared by the method for precursor.
The catalyst preparation process of recommendation, includes at least：Hydroxyl dipyridyl derivatives are loaded on carrier, then are led to
It crosses the extra hydroxyl of hydroxyl dipyridyl derivatives and/or adjacent nitrogen base and the cation of Pd, Cu forms complex ion.
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, Cu 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 it is mainly C-2-fraction to be formed 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 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, Cu is formed
The quantity of gold, the hydrogen that caltalyst phase is adsorbed 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 carries
Body obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution for preparing Pd, Cu impregnate hydroxyl-connection pyrrole
Pyridine/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor.300~600
DEG C 2~12h of roasting temperature, obtains required catalyst.
Carrier of the present invention can be alumina support or 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 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, and the preparation method of the catalyst includes such as
Lower step：
A. the organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, solution is made to be absorbed, 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.The molal quantity of hydroxyl-bipyridyl/(Pd+Cu) is preferably 1~100；It is total that its volume of organic solution is preferably equal to or greater than carrier
The 80% of volume.
B. prepare Pd, Cu 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 PdCu- hydroxyls-connection pyrrole
Pyridine/Al2O3Precursor；Liquor capacity is preferably hydroxyl-bipyridyl/Al2O3The 60%~200% of precursor total volume.
The ratio between the molal quantity of Cu and the molal quantity of Pd are preferably 0.4~5, and it is 1.0~4.0 preferably to adjust pH value.
C. the PdCu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor 300~600 DEG C of roasting temperatures 2~
12h so that PdCu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
In catalyst in use, can H 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.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-copper catalyst, alloy structure is more suitably applied to catalyst activity requirement
Higher working condition.Higher in air speed, alkynes and the higher carbon two of diene content select in hydrogenation process, have reaction temperature
Spend low, the good advantage of hydrogenation activity.
Description of the drawings
Attached drawing 1 is that a kind of carbon two of sequence separation process using the present invention selects hydrogenation technique flow chart.1- oil scrubbers；
2-water scrubbers；3-caustic wash towers；4-driers；5-domethanizing columns；6-front-end deethanization towers；7-Acetylene converters；8—
Compressor.
Specific implementation mode
Embodiment 1
Weigh Φ 3.4, specific surface area 21.0m2/ g, hole hold 0.31mL/g, the spherical α-Al of heap density 0.81g/mL2O3
Carrier 500g.
By 55.87g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 2h 4,4- dihydroxy -2,2- bipyridyls being loaded on alumina support completely, 60 DEG C of dry 10h,
Obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.30g Pd (NO3)2、1.18g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, pH value is adjusted
It is 2.2, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, stirring
10min stands 2h, pours out raffinate, obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+
Cu)=40).3h is roasted in air atmosphere at a temperature of 550 DEG C after 120 DEG C of dry 4h, obtains (Pd-Cu)/Al2O3Catalyst.Make
It is 99.9% with hydrogen purity with being preceding positioned in fixed-bed reactor, air speed 200h-1Gas, in 120 DEG C of temperature
Under, obtain loaded catalyst S-1.It is 0.08% that measure catalyst Pd contents, which be 0.024%, Cu contents,.
Comparative example 1
Weigh Φ 3.4mm, specific surface area 21.0m2/ g, hole hold 0.31mL/g, the spherical α-of heap density 0.81g/mL
Al2O3Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC 8.9g are dissolved completely in 800mLTHF (tetrahydrofuran), by above-mentioned carrier impregnation to above-mentioned solution,
PVC is set to be adsorbed in Al after standing 2h2O3Surface, drying for standby.Obtain PVC/Al2O3。
119.28g dicyandiamides 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-Cu- high-molecular complexes/Al2O3The preparation of presoma
Weigh 0.30g Pd (NO3)2、1.18g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, pH value is adjusted
It is 2.2, is made into mixed solution.Take the functionalization-PVC/Al prepared2O3Presoma adds it to Pd (NO3)2、AgNO3's
In mixed solution, 30min is stirred, raffinate is poured out, above-mentioned product is washed with deionized to neutrality, 120 DEG C of dry 4h are obtained
(Pd-Cu)-PVC/Al2O3Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h, obtain oxidation state (Pd-Cu)/Al in air atmosphere2O3Catalysis
Agent.It is positioned 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 loaded catalyst D-1.It is 0.08% that measure catalyst Pd contents, which be 0.024%, Cu contents,.
Using back end hydrogenation technique, process flow chart is as shown in Fig. 1, and raw material group becomes：
C2H2：1.8% (Φ), C2H475.1% (Φ), C2H623.1% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade 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：5000h-1, operating pressure：1.8MPa, each reactor catalyst loadings：450mL.One section anti-
Answer device H2/C2H2=1.5：1 (molar ratio)；Second stage reactor H2/C2H2=2.5：1 (molar ratio), is tied after examination in 500 hours
Fruit is as shown in table 1.
1 catalyst 500h performance average values of table
Embodiment 2
Weigh Φ 3.8mm, high 3.8mm, specific surface area 54.0m2/ g, Kong Rongwei 0.46mL/g, heap density are 0.69g/
Cylindrical θ-the Al of mL2O3Carrier 500g.
By 8.04g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 650mL ethanol solutions, 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 0.59gPd (NO3)2、2.94gCu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH value is
2.7 being made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, quiet
8h is set, raffinate is poured out, dries 6h at 110 DEG C of remaining solid, obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-connection pyrrole
Pyridine molal quantity：(Pd+Cu)=5).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst S-2 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.048%, Cu contents are 0.20%.
Comparative example 2
Catalyst preparation
Weigh Φ 3.8mm, high 3.8mm, specific surface area 54.0m2/ g, Kong Rongwei 0.46mL/g, heap density are 0.69g/
Cylindrical θ-the Al of mL2O3Carrier 500g.
A, functionalized polystyrene acrylonitrile (SAN)/Al2O3Preparation
SAN resin 2.2g are weighed, are dissolved in 600mL DMF (dimethylformamide) solvent, stirring at room temperature makes SAN trees
Fat is completely dissolved, be added in this solution it is above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred, detach dry after solvent, obtain
To SAN/Al2O3。
By SAN/Al obtained above2O3, it is added in 500mL deionized waters, 57.6g ethylenediamines 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-Cu)-SAN/Al2O3The preparation of presoma
Weigh 0.59gPd (NO3)2、2.94gCu(NO3)2The 1200mL deionized waters containing appropriate nitric acid are dissolved in, tune pH value is
2.7, it is made into mixed solution.Take the functionalization-SAN/Al prepared2O3Presoma, by functionalization-SAN/Al2O3It is added to Pd
(NO3)2、Cu(NO3)2Mixed solution in, stir 5min, pour out raffinate, above-mentioned product be washed with deionized to neutrality,
(Pd-Cu)-SAN/Al is obtained after drying2O3Presoma.
C, the preparation of catalyst
The presoma of above-mentioned preparation is obtained into Pd-Cu/Al in 500 DEG C of roasting 4h of air atmosphere2O3Catalyst.Before use
It is positioned in fixed-bed reactor, is 99.9% with hydrogen purity, air speed 200h-1Gas, at a temperature of 120 DEG C also
Original obtains loaded catalyst D-2.It is 0.20% that measure catalyst Pd contents, which be 0.048%, Cu contents,.
Using back end hydrogenation technique, process flow chart is as shown in Fig. 1, and raw material group becomes：
C2H2：1.7% (Φ), C2H480.0% (Φ), C2H618.3% (Φ).
Reaction condition：Two sections of adiabatic reactor reactor cascade 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：8000h-1, operating pressure：1.8MPa, 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 2.
2 500 hours catalyst performance average value of table
Embodiment 3
Weigh Φ 3.0mm, specific surface area 34.0m2/ g, Kong Rongwei 0.25mL/g, heap are more spherical than the tooth for 0.76g/mL
Carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
By 70.01g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation upper
It states in solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 120 DEG C dry
Dry 4h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.39gPd (NO3)2,0.59g Cu(NO3)2The 650mL deionized waters containing appropriate nitric acid are dissolved in, tune pH value is
3.2, it is made into mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, quiet
12h is set, raffinate is poured out, 100 DEG C of dry 8h obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：
(Pd+Cu)=80).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst S-3 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.032%, Cu contents are 0.04%.
Comparative example 3
Weigh Φ 3.0mm, specific surface area 34.0m2/ g, Kong Rongwei 0.25mL/g, heap are more spherical than the tooth for 0.76g/mL
Carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
Weigh 0.39gPd (NO3)2,0.59g Cu(NO3)2, the 200mL deionized waters containing appropriate nitric acid are dissolved in, pH value is adjusted
It is 3.2, is made into mixed solution, will be shaken after the solution spraying to above-mentioned carrier 0.5 hour, after 100 DEG C of dry 8h, in air gas
500 DEG C of roasting 4h obtain (Pd-Cu)/Al in atmosphere2O3Catalyst.It is positioned in fixed-bed reactor before use, uses hydrogen purity
It is 99.9%, air speed 200h-1Gas obtain loaded catalyst D-3 at a temperature of 120 DEG C.Catalyst Pd is measured to contain
It is 0.04% that amount, which is 0.032%, Cu contents,.
Using back end hydrogenation technique, reaction raw materials are：
C2H2：2.3 (v%) C2H479.2 (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=2：1 (rubs
That ratio)；Three sections of 80 DEG C of reactor inlet temperatures, H2/C2H2=3：1 (molar ratio)；Result such as 3 institute of table after examination in 500 hours
Show.
3 catalyst 500h performance average values of table
Embodiment 4
Weigh Φ 3.8mm, high 3.8mm, specific surface area 48.0m2/ g, Kong Rongwei 0.53mL/g, heap ratio are 0.66g/mL
Tooth ball type carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
By 54.45g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation upper
It states in solution, after after standing 8h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 90 DEG C of dryings
10h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.49gPd (NO3)2,2.35g Cu(NO3)2650mL deionized waters are dissolved in, it is 2.4 to adjust pH value, is made into mixing
Solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 10h, pours out residual
Liquid, 90 DEG C of dry 10h obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Cu)=20).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst S-4 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.04%, Cu contents are 0.16%.
Comparative example 4
Weigh Φ 3.8mm, high 3.8mm, specific surface area 48.0m2/ g, Kong Rongwei 0.53mL/g, heap ratio are 0.66g/mL
Tooth ball type carrier 500g, wherein Al2O3460g, titanium oxide 40g, Al2O3For the mixing crystal form of θ, α.
It weighs appropriate 6,6'- dihydroxy -3,3'- bipyridyl and is dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 8h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 90 DEG C of dryings
10h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2,AgNO3650mL deionized waters are dissolved in, it is 2.4 to adjust pH value, is made into mixed solution.It will be upper
State hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 10h, pours out raffinate, and 90 DEG C dry
Dry 10h obtains PdAg- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Ag)=20).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst D-4 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.04%, Ag contents are 0.16%.
Using back end hydrogenation technique, reaction raw materials are：
C2H2：2.4 (v%) C2H479.1 (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 of 80 DEG C of reactor inlet temperatures, H2/C2H2=3：1 (molar ratio)；The result such as table after examination in 500 hours
Shown in 4.
4 catalyst 500h performance average values 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, Cu is obtained organic high
The method of molecular metal complex compound prepares catalyst and compares, and uses the method for hydrotreating of the present invention, the activity of hydrogenation reaction and choosing
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 plus hydrogen adiabatic reactor reactor be located at domethanizing column it
Afterwards, pressurized with after hydrogen by two material of carbon from front-end deethanization tower in ethylene unit, it is selected into adiabatic reactor reactor
Add hydrogen, it is characterised in that：Pd-Cu series catalysts are housed, with Al in adiabatic reactor reactor2O3Or Al2O3With mixing for other oxides
Conjunction object is carrier, is wherein palladium content 0.020~0.055% in terms of 100% by the quality of catalyst, Cu contents are 0.03~
0.2%, 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, it is combined with hydroxyl dipyridyl derivatives by carrier, hydroxyl bipyridyl forms metal complex with active component；Reaction
Condition is：30~70 DEG C, 1.5~2.5MPa of reaction pressure, 5000~10000h of gas space velocity of adiabatic reactor reactor inlet temperature-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 are loaded on carrier, then more by hydroxyl dipyridyl derivatives
The cation of remaining hydroxyl and/or nitrogen base and Pd, Cu 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 obtains
It must include the following steps：With hydroxyl dipyridyl derivatives organic solution, impregnated carrier obtains hydroxyl-connection pyrrole after drying
Pyridine/Al2O3Precursor, the mixed-cation solution for preparing Pd, Cu impregnate hydroxyl-bipyridyl/Al2O3Precursor, in 60 DEG C~
It is dry at 150 DEG C, obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor；In 300~600 DEG C of 2~12h of roasting temperature, obtain
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 also doped with other oxides, other oxides are silica, titanium oxide, magnesia
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 aluminium oxide 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. selecting method of hydrotreating according to carbon two in any sequence separation process of claim 1-7, 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.PdCu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Cu 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 PdCu- hydroxyls-bipyridyl/Al2O3Before
Body；Its liquor capacity is hydroxyl-bipyridyl/Al2O3The 60%~200% of precursor total volume；
C. the preparation of catalyst
PdCu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor is in 300~600 DEG C of 2~12h of roasting temperature so that
PdCu- hydroxyls-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 A
The ratio between base-bipyridyl and the molal quantity of (Pd+Cu) are 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, Cu are the mixed solution of palladium nitrate and copper 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 the molal quantity of Cu and the molal quantity of Pd are 1~7：1.
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, Cu is 1.5~4.0.
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 reacts
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-
When to answer the device reaction bed number of plies be two sections, first segment reactor hydrogen and acetylene volume ratio are 1~1.5：1, second segment reactor hydrogen
Gas is 2~4 with acetylene volume ratio：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 is 1~1.5 with acetylene volume ratio：1, third section reactor hydrogen is 1.5~3.0 with acetylene volume ratio：1.
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| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
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| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
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| CN101434508A (en) * | 2008-12-11 | 2009-05-20 | 中国石油天然气股份有限公司 | Acetylene hydrocarbon selective hydrogenation method |
| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
| 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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