CN105732273B - A kind of method of C-2-fraction predepropanization front-end hydrogenation - Google Patents
A kind of method of C-2-fraction predepropanization front-end hydrogenation Download PDFInfo
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Abstract
The present invention relates to a kind of methods of C-2-fraction predepropanization front-end hydrogenation, tower top effluent from predepropanization tower in ethylene unit is entered into fixed bed reactors and carries out selection plus hydrogen, it is characterized in that Pd Au series catalysts are housed in adiabatic reactor reactor, the catalyst is in preparation process, it is combined by alumina series carrier with hydroxyl dipyridyl derivatives, the hydroxyl dipyridyl derivatives being incorporated on carrier form metal complex with active component；Method using the present invention can reduce the influence that temperature runaway carrys out device band, improve the safety of operation, while ensureing while adding hydrogen qualification of acetylene, effectively improve device ethylene increment.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly a kind of C 2 fraction selective hydrogenation is except the method for acetylene.
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 is divided into front-end hydrogenation and back end hydrogenation in ethylene unit, and ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene adds
Hydrogen reactor is for domethanizing column position, and it is before front-end hydrogenation that hydrogenation reactor, which is located at domethanizing column, hydrogenation reactor
It is back end hydrogenation after domethanizing column.It is more and more using two front-end hydrogenation of carbon in current C-2-fraction acetylene hydrogenation
The characteristics of process, the process be hydrogenation reactor before domethanizing column, before being predepropanization important is flow
Add hydrogen, its main feature is that cracking fraction is separated by gas-liquid, carry out carbon fraction below three adds hydrogen, and acetylene is completed to convert, and
Most propine allene is removed,
The key reaction occurred in the reactor is as follows：
Main reaction
C2H2+H2→C2H4 (1)
MAPD+H2→CH3- CH=CH2 (2)
MAPD is propine and allene
Side reaction
C2H4+H2→C2H6 (3)
C2H2+2H2→C2H6 (4)
2C2H2+H2→C4H6 (5)
C3H6+H2→C3H8 (6)
In these are answered, what reaction (1) and (2) was desirable to, acetylene, propine and allene were not only stripped of, but also increased production second
Alkene and propylene；It is undesirable to react (3), (4), (5) and (6).
Due to there is a large amount of hydrogen in reaction mass, the selectivity of catalyst shows particularly important, otherwise can lead to pair
Excessive generation is reacted, causes catalytic reactor temperature runaway.Since the selectivity reacted during low-speed is low, it be easy to cause temperature runaway, mesh
Preceding minimum safe air speed is 4500/h, that is to say, that when device air speed is less than the numerical value, reactor is just easy to occur to fly
Temperature brings threat to the operation of device.After the important difference of two front-end hydrogenation process of carbon and two back end hydrogenation process of carbon is
Hydrogen is artificially incorporated in hydrogenation method, and the degree of reaction progress can be controlled by amounts of hydrogen.And front-end hydrogenation work
In process, hydrogen content is higher, does not need to match hydrogen again, therefore few to the control means of reaction in hydrogenation process, and mutually reply is urged
The performance requirement of agent just greatly improves.
For predepropanization front-end hydrogenation method, with the raising of reaction temperature, catalyst choice declines, and works as catalyst
When selectivity drops to initial reaction temperature 1/3 when, it is believed that reached the maximum operation (service) temperature of catalyst, the temperature and starting
The difference of reaction temperature is known as the action pane of catalyst, and the temperature range is wider, and the processing safety of catalyst is just higher.It passes
Catalyst unite due to selective limitation, generally only 10~15 DEG C of the action pane.
Two front-end hydrogenation of carbon for the front-end hydrogenation technique of predepropanization, is mainly adopted mainly using fixed bed reactors at present
With three sections of adiabatic reactor reactors, preceding two reactor is mainly the acetylene for removing the overwhelming majority, and third section reactor is used to remove
More than 50% propine (MA) and allene (PD).So third section outlet acetylene is less than 1 μ L/L, MAPD and is less than 0.3%
(v)。
Patent US4484015 discloses a kind of predepropanization front-end hydrogenation method, used by this method catalyst using Pd as
Main active component, using Alpha-alumina as carrier, addition co-catalyst silver, the C2 hydrogenation that function admirable is prepared for infusion process is urged
Agent.The catalyst can effectively reduce the excessive hydrogenation of ethylene, reduce the risk of bed temperature runaway.Catalysis disclosed in the patent
The preparation method of agent is using infusion process.Because the surface polar groups of alpha-alumina supports are few, in the dipping of catalyst and dry
Influenced to be especially apparent by maceration extract surface tension and solvation effect in dry processing procedure, metal active constituent presoma with
Aggregate form is deposited on carrier surface.In addition, strong interaction cannot be formed between metal salt species and carrier after dipping, it is high
Temperature roasting is easy to cause metallic migration aggregation and forms big crystal grain.
Patent CN201110086174.0 discloses a kind of method of C 2 fraction selective hydrogenation, the catalysis that this method uses
Agent, using Pd as main active component, using Alpha-alumina as carrier, addition co-catalyst silver.It is specific high by being adsorbed on carrier
Molecular compound forms macromolecule wrapped layer in carrier surface certain thickness, anti-with the compound with functional base and macromolecule
Should, with the function base that can be complexed with active component, it is complexed on carrier surface function base by active component
Reaction, ensure active component orderly and high degree of dispersion.Using the patented method, the specific high-molecular compound of carrier adsorption passes through
The hydroxyl of aluminium oxide carries out chemisorbed with macromolecule, and the amount of carrier adsorption high-molecular compound will be by the hydroxyl value of aluminium oxide
The limitation of amount；The complexing of macromolecule and Pd by functionalization is not strong, and activity component load quantity does not reach requirement sometimes, leaching
Residual fraction active component is gone back in stain liquid, catalyst cost is caused to improve；C2 hydrogenation catalyst is prepared using this method also to deposit
Technological process is complicated the shortcomings that.
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, so as to reach raising device
The purpose of economic benefit.
Invention content
The purpose of the present invention is to provide a kind of method of C-2-fraction predepropanization front-end hydrogenation, by selecting alloy structure
Pd, Au catalyst, improve hydrogenation selectivity, improve yield of ethene, this for the production of ethylene, have it is important
Economic value.
Present disclosure is：A kind of method of C-2-fraction predepropanization front-end hydrogenation will take off in ethylene unit from preceding
The tower top effluent of propane tower enters fixed bed reactors and carries out selection plus hydrogen, special to remove alkynes and alkadienes therein
Sign is in adiabatic reactor reactor that, equipped with Pd-Au series catalysts, Pd-Au series catalysts refer to using Al2O3It is carrier, with catalysis
The quality of agent is 100% meter, and wherein Pd contents are 0.01~0.050%；Au contents are 0.020~0.30%, the ratio of catalyst
Surface area is 1~20m2/ g, pore volume are 0.15~0.50ml/g；The catalyst is carried in preparation process by alumina series
Body is combined with hydroxyl dipyridyl derivatives, and hydroxyl dipyridyl derivatives form metal complex with active component；Instead
The condition is answered to be：40~100 DEG C, 3.5~4.5MPa of reaction pressure of adiabatic reactor reactor inlet temperature, gas space velocity 3000~
30000h-1。
The characteristics of Pd-Au series catalysts used in the present invention is：The catalyst be PdAu- 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 to alumina series to carry
On body, then by the cation of the extra hydroxyl of hydroxyl dipyridyl derivatives and/or nitrogen base and Pd, Au formed complexing from
Son.
The hydroxyl dipyridyl derivatives of the present invention, preferably hydroxyl 2,2, it is-dipyridyl derivatives, hydroxyl
3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, because it is combined rear extra hydroxyl with aluminium oxide
With Pd, Au preferable complex reaction can occur for base and two nitrogen bases at ortho position.
The catalyst type used is defined in the present invention, such catalyst choice has larger area with traditional catalyst
Not.
The principle of the present invention is：In selective hydrogenation reaction, closed as used catalyst activity component Pd, Au is formed
Gold, the quantity for the hydrogen that caltalyst phase is adsorbed are 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 the organic solution of hydroxyl dipyridyl derivatives, dipping
Al2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor prepares the mixed solution mixed solution leaching of Pd, Au
Stain hydroxyl-bipyridyl/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyls-bipyridyl/Al2O3Preceding body
Body.In 300~600 DEG C of 2~12h of roasting temperature, required catalyst is obtained.
Carrier of the present invention is alumina series carrier, is Al2O3Or mainly contain Al2O3, wherein also doped with other oxides
Mixture, other oxides be titanium oxide, magnesia and/or calcium oxide.The Al2O3For θ, α or its mixing crystal form.
Carrier can be spherical in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Procedure below may be used to implement in catalyst preparation of the present invention, which can be divided into the progress of 3 steps.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By the organic solution of hydroxyl dipyridyl derivatives, with Al2O3It is carrier mixing, at a temperature of 20 DEG C~60 DEG C
Reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor.Hydroxyl-
The molal quantity of bipyridyl/(Pd+Au) is preferably 1~100；The volume of organic solution is preferably equal to or greater than carrier total volume
80%.
B.PdAu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
The mixed solution of Pd, Au are prepared, hydroxyl-bipyridyl/Al obtained by step A is added at a temperature of 30 DEG C~100 DEG C2O3
Precursor reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyls-bipyridyl/Al2O3Before
Body.The volume of the mixed solution of Pd, Au is preferably hydroxyl-bipyridyl/Al2O3The 60%~200% of precursor total volume；Au
Molal quantity and Pd the ratio between molal quantity preferably 0.4~5；It is preferably 1.0~4.0 to adjust pH value.
C. the preparation of catalyst
PdAu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature,
Cause PdAu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
Roasting preferably carries out in aerobic atmosphere.
It in use, can be by catalyst made from above method, in the reactor using H in catalyst2Carry out reduction treatment,
Obtain reduction-state catalyst.
To the front-end hydrogenation process of predepropanization, composition is mainly C-2-fraction 35~35% (v) in entrance raw material,
Middle acetylene 0.4~0.8% (v) is secondly methane 18~25% (v), hydrogen 12~25% (v), C3 fraction 8~15% (v),
300~1500ppm of CO.
After the catalyst, the safe air speed of device can be reduced to 3500h-1.And safety is empty in traditional method of hydrotreating
Speed cannot be below 4500h-1, otherwise Wen Shengtai high in reactor, it may occur that temperature runaway can bring great prestige to the safety of device
The side of body.
Inventor has found, after method using the present invention, reduces the influence that temperature runaway carrys out device band, improves operation
Safety, while can guarantee the stability for adding hydrogen qualified, reaching raising device operation of acetylene.The method of the present invention is only limitted to adopt
The catalyst prepared with the method for the present invention.
Meanwhile the method for the present invention prepares palladium-gold catalyst, since its alloy structure is apparent, alloy effect is stronger, is more suitable for
Before higher two front-end hydrogenation device of carbon, the alloy catalyst being required to be applied to carbon two catalyst activity, selectivity
Hydrogenation plant at a lower reaction temperature, has excellent activity and selectivity.
Description of the drawings
Fig. 1 is just with a kind of C2 hydrogenation process flow chart using predepropanization technique of the present invention.
1-oil scrubber；2-water scrubber；3-caustic wash tower；4-drier；5-predepropanization tower；6-carbon, two front-end hydrogenation is anti-
Answer device；7-domethanizing column；8-compressor.
Specific embodiment
Analysis test method：
Specific surface area：GB/T-5816
Kong Rong：GB/T-5816
Heap density：Q/SY142-2006
Catalyst Pd, Au assay：Using plasma emission spectrometer measures catalyst Pd contents and Au contents.
Standard GB/T 1537-94
Selective computational methods：
Ethylene selectivity:S=1- △ ethane/△ acetylene
Propylene Selectivity S=1- △ propane/△ (propine+allene)
Embodiment 1
Weigh Φ 4.5mm, length 4.5mm, specific surface area 17m2Column α-the Al of/g, Kong Rongwei 0.22ml/g2O3It carries
Body 500g.
By 27.6g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned molten
In liquid, after 4,4- dihydroxy -2,2- connection pyrrole is caused to load on alumina support completely after standing 2h, 60 DEG C of dry 10h are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 500mL deionized waters containing appropriate hydrochloric acid, and it is 2.1 to adjust pH value, is configured to
Mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min, stands 2h, pours out
Raffinate obtains PdAu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Au)=100).120 DEG C dry
2h is roasted in air atmosphere at a temperature of 550 DEG C after dry 4h, obtains (Pd-Au)/Al2O3Catalyst.Fixed bed is positioned over before use
It is 99.9% with hydrogen purity in reaction unit, air speed 300h-1Gas, restore 4h at a temperature of 100 DEG C, loaded
Type palladium-silver catalyst S-1.It is 0.20% that measure catalyst Pd contents, which be 0.012%, Au contents,.
Comparative example 1
The preparation of catalyst
Weigh Φ 4.5mm, length 4.5mm, specific surface area 17m2Column α-the Al of/g, Kong Rongwei 0.22ml/g2O3It carries
Body 500g.
A, it is functionalized PVC/Al2O3Preparation
PVC8.9g is dissolved completely in 800ml tetrahydrofurans (THF), by the carrier impregnation weighed up to above-mentioned solution
Middle 1h makes PVC be deposited on Al2O3Surface pours out raffinate, is dried to obtain PVC/Al2O3Product.
Add in 119.28g dicyandiamides and 2.0gNa2CO3, add in above-mentioned PVC/Al2O3Reflux 4 hours, is cooled to room temperature,
It is washed with deionized to neutrality, drying for standby.Obtain functionalization PVC/Al2O3.Complexing agent dicyandiamide molal quantity/macromolecular chain
Upper reactive group Cl molal quantity=10.
B, (Pd-Au)-high-molecular complex/Al2O3The preparation of presoma
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 500mL deionized waters containing appropriate hydrochloric acid, and it is 2.1 to adjust pH value, is configured to
Mixed solution weighs the functionalization-macromolecule/Al prepared2O3Presoma, by functionalization-macromolecule/Al2O3It is added to chlorine palladium
In sour, gold chloride mixed solution, 1h is adsorbed, raffinate is poured out, above-mentioned product is washed with deionized to neutrality, 120 DEG C dry
Dry 4h obtains (Pd-Au)-polymer/Al2O3Presoma, reactive group Cl molal quantitys/(Pd+Au) molal quantity on macromolecular chain
=100).
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 positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 300h-1Gas, at 100 DEG C
At a temperature of restore 4h, obtain load type palladium-silver catalyst D-1.Measure catalyst Pd contents is for 0.012%, Au contents
0.20%.
Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 1.
1 hydrogenating materials of table composition is as shown in the table
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (Φ %) | 20.0 | 0.7 | 35.1 | 4.2 | 25.0 | 12 | 2.0 | 0.50 | 0.2 | 0.3 |
Reaction condition：Material air speed：8000h-1；Operating pressure：3.0MPa,；Loaded catalyst：500ml.
Adiabatic reactor reactor, two sections of tandem process carry out hydrogenation reaction.Second stage reactor is tied after the examination of 1000 hours
Fruit is as shown in table 2.
2 two sections of the table result of appraisal of adiabatic reactor reactor 1000 hours
Embodiment 2
Weigh 4.0 × 4.0mm of Φ, specific surface area 7m2The cylindrical vector 500g of/g, Kong Rongwei 0.38ml/g, wherein
- the Al containing α2O3460g, TiO240g。
By 104.89g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 800mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 8h 4,4- dihydroxy -2,2- bipyridyls being loaded on alumina support completely, 90 DEG C of dry 8h,
Obtain hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 500mL deionized waters containing appropriate hydrochloric acid, and it is 2.5 to adjust pH value, is configured to
Mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 8h, pours out
Raffinate obtains PdAu- hydroxyls-bipyridyl/Al after the dry 4h of 110 DEG C of remaining solid2O3Precursor (hydroxyl-bipyridyl molal quantity：
(Pd+Au)=70).
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 300h-1Gas, restore 4h at a temperature of 100 DEG C, obtain load type palladium-silver and urge
Agent S-2.It is 0.03% that measure catalyst Pd contents, which be 0.031%, Au contents,.
Comparative example 2
Catalyst preparation：
Weigh 4.0 × 4.0mm of Φ, specific surface area 7m2The cylindrical vector 500g of/g, Kong Rongwei 0.38ml/g, wherein
- the Al containing α2O3460g, TiO240g。
A, it is functionalized SAN/Al2O3Preparation
Polystyrene SAN resin 30g are weighed, are dissolved in 600ml DMF solvents, stirring at room temperature makes SAN resins complete
Dissolving adds in 40g hydroxylamine hydrochlorides, adds 10gK2CO3, it is heated to it and is completely dissolved.After stirring half an hour, by Al2O3Carrier 500g
Addition more than solution is added dropwise 400ml ethyl alcohol, and is stirred continuously, and product is taken out after 1 hour, washs to neutrality, after dry, obtains
It is functionalized SAN/Al2O3.In terms of molal quantity, reactive group CN molal quantitys in complexing agent hydroxylamine hydrochloride molal quantity/macromolecule=
1.2。
B, (Pd-Au)-polymer/Al2O3The preparation of presoma
Weigh appropriate palladium bichloride, gold chloride is dissolved in the 500mL deionized waters containing appropriate hydrochloric acid, take the functionalization that has prepared-
SAN/Al2O3Presoma is added in the mixed solution of chlorine palladium acid, gold chloride, pours out raffinate after adsorbing 1h, above-mentioned product is spent
Ion water washing is to neutrality, and dry 6h, obtains (Pd-Au)-polymer/Al at 110 DEG C2O3Presoma.Reactive base in macromolecule
Group's CN molal quantitys/(Pd+Au) molal quantity=42.10.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h, obtain (Pd-Au)/Al in air atmosphere2O3Catalyst S-2.
It is 0.03% that measure catalyst Pd contents, which be 0.031%, Au contents,.
Using the front-end hydrogenation technique of predepropanization, as shown in Figure 1.Reaction raw materials come from predepropanization column overhead, and composition is such as
Shown in table 3.
3 hydrogenating materials of table form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | CO | C3H6 | C3H8 | PDMA |
| Content (Φ %) | 17.95 | 0.45 | 43 | 11.2 | 12 | 0.04 | 12 | 2.9 | 0.46 |
Reaction process condition：The front-end hydrogenation process of predepropanization, two sections of adiabatic reactor reactors.
Material air speed：20000h-1, operating pressure：3.2MPa, loaded catalyst：500ml.
Reaction result：
The results are shown in table below after the examination of 1000 hours for two reactor：
4 three sections of the table result of appraisal of adiabatic reactor reactor 1000 hours
Embodiment 3
Weigh Φ 3.7mm, specific surface area 27m2/ g, Kong Rongwei 0.38ml/g, ball-aluminium oxide of the heap than 0.85g/ml
Carrier 500g, Al2O3Mixing crystal form for θ, α.
By 4.4g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 600mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 120 DEG C of dryings
4h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 400mL deionized waters containing appropriate hydrochloric acid, and it is 3.0 to adjust pH, is configured to mix
Solution is closed, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 12h, pours out
Raffinate, dry 8h obtains PdAu- hydroxyls-bipyridyl/Al at 100 DEG C of remaining solid2O3Precursor (hydroxyl-bipyridyl molal quantity：
(Pd+Au)=2.85).
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 300h-1Gas, restore 4h at a temperature of 100 DEG C, obtain load type palladium-silver and urge
Agent S-3.It is 0.20% that measure catalyst Pd contents, which be 0.035%, Au contents,.
Comparative example 3
Weigh Φ 3.7mm, specific surface area 27m2/ g, Kong Rongwei 0.38ml/g, ball-aluminium oxide of the heap than 0.85g/ml
Carrier 500g, Al2O3Mixing crystal form for θ, α.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 400mL deionized waters containing appropriate hydrochloric acid, and it is 3.0 to adjust pH, by the solution
It is shaken 0.5 hour after being sprayed to above-mentioned carrier, after dry, 500 DEG C of roasting 8h obtain (Pd-Au)/Al in air atmosphere2O3It urges
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 300h-1Gas, 100
4h is restored at a temperature of DEG C, obtains load type palladium-silver catalyst D-3.Measure catalyst Pd contents is for 0.035%, Au contents
0.20%.Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 5.
5 hydrogenating materials of table form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (v/v%) | 17.0 | 0.9 | 40.0 | 10.0 | 29.0 | 2.0 | 0.7 | 0.1 | 0.3 |
Reaction process condition：Predepropanization front-end hydrogenation technique, three sections of adiabatic reactors；Material air speed：3500h-1；Operation pressure
Power：3.2MPa, loaded catalyst：500ml.
6 three sections of the table result of appraisal of adiabatic reactor reactor 1000 hours
Embodiment 4
Weigh Φ 4.0mm, high 4.0mm, specific surface area 27m2The spherical alumina support of/g, Kong Rongwei 0.40ml/g
500g, Al2O3Mixing crystal form for θ, α.
By 47.2g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 600mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 10h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 100 DEG C of dryings
6h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 300mL deionized waters containing appropriate hydrochloric acid, and it is 3.5 to adjust pH, is configured to mix
Solution is closed, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 10h, pours out
Raffinate, dry 10h obtains PdAu- hydroxyls-bipyridyl/Al at 90 DEG C of remaining solid2O3Precursor (hydroxyl-bipyridyl molal quantity：
(Pd+Au)=30).
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 300h-1Gas, restore 4h at a temperature of 100 DEG C, obtain load type palladium-silver and urge
Agent S-4.It is 0.032% that measure catalyst Pd contents, which be 0.018%, Au contents,.
Comparative example 4
Weigh Φ 4.0mm, high 4.0mm, specific surface area 27m2The spherical alumina support of/g, Kong Rongwei 0.40ml/g
500g, Al2O3Mixing crystal form for θ, α.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 300mL deionized waters containing appropriate hydrochloric acid, and it is 3.5 to adjust pH, by the solution
It is shaken 0.5 hour after being sprayed to above-mentioned carrier, after dry, 600 DEG C of roasting 2h obtain (Pd-Au)/Al in air atmosphere2O3It urges
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 300h-1Gas, 100
4h is restored at a temperature of DEG C, obtains load type palladium-silver catalyst D-3.Measure catalyst Pd contents is for 0.018%, Au contents
0.032%.Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 7.
7 hydrogenating materials of table form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (v/v%) | 16.0 | 0.9 | 39.0 | 9.5 | 29.5 | 2.0 | 0.7 | 0.1 | 0.3 |
Reaction process condition：Predepropanization front-end hydrogenation technique, three sections of adiabatic reactors；Material air speed：10000h-1；Operation
Pressure：3.9MPa, loaded catalyst：500ml.
8 three sections of the table result of appraisal of adiabatic reactor reactor 1000 hours
It can be seen that compared with using traditional preparation catalyst from above embodiment, with using organic high score
Sub- grafted functional group simultaneously loads on a catalyst support, then the solution of carrier impregnation activity Pd, Au is obtained organic polymer
The method of metal complex prepares catalyst and compares, after method using the present invention, the activity of C-2-fraction hydrogenation reaction, selection
Property increases substantially.
Embodiment 5
Weigh Φ 3.7mm, specific surface area 27m2/ g, Kong Rongwei 0.38ml/g, ball-aluminium oxide of the heap than 0.85g/ml
Carrier 500g, Al2O3Mixing crystal form for θ, α.
Appropriate palladium bichloride is weighed, gold chloride is dissolved in the 500mL deionized waters containing appropriate hydrochloric acid, and it is 3.0 to adjust pH, by the solution
It is shaken 0.5 hour after being sprayed to above-mentioned carrier, after dry, 500 DEG C of roasting 8h obtain (Pd-Au)/Al in air atmosphere2O3It urges
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 300h-1Gas, 100
4h is restored at a temperature of DEG C, obtains load type palladium-silver catalyst S-5.Measure catalyst Pd contents is for 0.04%, Au contents
0.27%.
Comparative example 5
Weigh Φ 3.7mm, specific surface area 27m2/ g, Kong Rongwei 0.38ml/g, ball-aluminium oxide of the heap than 0.85g/ml
Carrier 500g, Al2O3Mixing crystal form for θ, α.
By 4.4g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 600mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 120 DEG C of dryings
4h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Appropriate palladium nitrate is weighed, silver nitrate is dissolved in the 500mL deionized waters containing appropriate hydrochloric acid, and it is 3.0 to adjust pH, is configured to mix
Solution is closed, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 12h, pours out
Raffinate, dry 8h obtains PdAg- hydroxyls-bipyridyl/Al at 100 DEG C of remaining solid2O3Precursor (hydroxyl-bipyridyl molal quantity：
(Pd+Ag)=2).
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 300h-1Gas, restore 4h at a temperature of 100 DEG C, obtain load type palladium-silver and urge
Agent D-5.It is 0.15% that measure catalyst Pd contents, which be 0.04%, Ag contents,.
Using the front-end hydrogenation technique of predepropanization, reaction raw materials come from predepropanization column overhead, and composition is as shown in table 5.
9 hydrogenating materials of table form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | C3H6 | C3H8 | PDMA | CO | C4 + |
| Content (v/v%) | 17.0 | 0.9 | 40.0 | 10.0 | 29.0 | 2.0 | 0.7 | 0.1 | 0.3 |
Reaction process condition：Predepropanization front-end hydrogenation technique, three sections of adiabatic reactors；Material air speed：10000h-1；Operation
Pressure：3.9MPa, loaded catalyst：500ml.
10 3 sections of the table result of appraisal of adiabatic reactor reactor 1000 hours
Claims (10)
1. a kind of method of C-2-fraction predepropanization front-end hydrogenation, by the tower top effluent from predepropanization tower in ethylene unit
Selection plus hydrogen are carried out into fixed bed reactors, to remove alkynes and alkadienes therein, it is characterised in that adiabatic reactor reactor
In equipped with Pd-Au series catalysts, Pd-Au series catalysts refer to using Al2O3It is carrier, is counted using the quality of catalyst as 100%,
Wherein Pd contents are 0.01~0.050%；Au contents are 0.020~0.30%, and the specific surface area of catalyst is 1~20m2/ g,
Pore volume is 0.15~0.50ml/g；Catalyst is spread out in preparation process by alumina series carrier and hydroxyl bipyridyl
Bioconjugation, hydroxyl dipyridyl derivatives form metal complex with active component；Reaction condition is：Adiabatic reactor reactor
40~100 DEG C, 3.0~4.5MPa of reaction pressure, 3000~30000h of gas space velocity of inlet temperature-1。
2. according to the method described in claim 1, it is characterized in that catalyst preparation process, includes at least：By hydroxyl connection
Pyridine derivate is loaded on alumina series carrier, then passes through the extra hydroxyl of hydroxyl dipyridyl derivatives and/or nitrogen base
Complex ion is formed with the cation of Pd, Au.
3. according to the method described in claim 1, it is characterized in that hydroxyl dipyridyl derivatives be hydroxyl 2,2 ,-connection
Pyridine derivate or hydroxyl 3,3 ,-dipyridyl derivatives.
4. according to the method described in claim 1, it is characterized in that catalyst is included the following steps：With hydroxyl connection
The organic solution of pyridine derivate impregnates Al2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor is prepared
Mixed solution mixed solution dipping hydroxyl-bipyridyl/Al of Pd, Au2O3Precursor, it is dry at 60 DEG C~150 DEG C, it obtains
PdAu- hydroxyls-bipyridyl/Al2O3Precursor；In 300~600 DEG C of 2~12h of roasting temperature, required catalyst is obtained.
5. according to the method described in claim 1, it is characterized in that Al2O3Be carrier be Al2O3Or mainly contain Al2O3, wherein
Also doped with other hopcalites, other oxides are titanium oxide, magnesia and/or calcium oxide；The aluminium oxide
For θ, α or its mixing crystal form.
6. according to any methods of claim 1-5, it is characterised in that the preparation process of catalyst includes：
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By the organic solution and Al of hydroxyl dipyridyl derivatives2O3It is carrier mixing, reacts 2 at a temperature of 20 DEG C~60 DEG C
~for 24 hours, and solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdAu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare the mixed solution mixed solution of Pd, Au, at a temperature of 30 DEG C~100 DEG C with step A obtained by hydroxyl-bipyridyl/
Al2O3Precursor reaction 2~for 24 hours, takes out solid particle, dry at 60 DEG C~150 DEG C, obtain PdAu- hydroxyls-bipyridyl/
Al2O3Precursor；
C. the preparation of catalyst
PdAu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor is in 300~600 DEG C of 2~12h of roasting temperature so that
PdAu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
7. according to the method described in claim 6, it is characterized in that the molal quantity of hydroxyl-bipyridyl/(Pd+Au) is 1 in step A
~100：1.
8. according to the method described in claim 6, it is characterized in that in stepb, the mixed solution mixed solution of Pd, Au are chlorine
Change palladium, the mixed solution of gold chloride.
9. according to the method described in claim 6, it is characterized in that in stepb, the ratio between the molal quantity of Au and the molal quantity of Pd
It is 1~8：1.
10. according to the method described in claim 6, it is characterized in that in stepb, the mixed solution mixing for adjusting Pd, Au is molten
Liquid pH value is 1.5~4.0.
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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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| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
| 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 |
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