CN105732280B - C-2-fraction front-end deethanization front-end hydrogenation method - Google Patents
C-2-fraction front-end deethanization front-end hydrogenation method Download PDFInfo
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Abstract
The present invention relates to a kind of C 2 fraction selective hydrogenation method, using the front-end hydrogenation process of front-end deethanization, tower top effluent from front-end deethanization tower in ethylene unit is subjected to selection hydrogenation into fixed bed reactors, it is characterized in that Pd Ni series catalysts are housed in adiabatic reactor reactor, the catalyst is in preparation process, combined by alumina series carrier with hydroxyl dipyridyl derivatives, the hydroxyl dipyridyl derivatives being incorporated on carrier form metal complex with active component；It can increase substantially the activity of hydrogenation reaction, selectivity using the method for the present invention, green oil generating amount reduces, and catalyst service life extends, while can guarantee that the hydrogenation of acetylene is qualified, reaches the stability for improving device operation.Catalyst used in the present invention has excellent anti-impurity interference performance and excellent anti-CO fluctuation abilities, the carbon two front-end hydrogenation device higher particularly suitable for S, As impurity content, can reduce the influence that temperature runaway comes to device band.
Description
Technical field
The present invention relates to one kind to select method of hydrotreating, the method that particularly a kind of C 2 fraction selective hydrogenation removes 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 hydrogenation of wherein acetylene has extremely important influence to ethene processing industry, except 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 ethene is as few as possible, to improving whole work
The yield of ethene of skill process, it is significant to improve device economic benefit.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%-2.5%, when producing polyethylene, lacking in ethene
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 ethene
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 front-end hydrogenation that hydrogenation reactor, which is located at before domethanizing column, hydrogenation reactor
It is back end hydrogenation after domethanizing column.It is more and more using the front-end hydrogenation of carbon two in current C-2-fraction acetylene hydrogenation
Process is hydrogenation reactor the characteristics of the process before domethanizing column.Front-end hydrogenation is divided into predepropanization with before again
Two kinds of techniques of deethanization.Front-end deethanization hydrogenation technique is that hydrogenation reactor is located at after dethanizer, before domethanizing column.It is preceding de-
Propane hydrogenation technique is that hydrogenation reactor is located at after depropanizing tower, before domethanizing column.The difference of flow, bring two kinds of hydrogenation
The difference of material composition.Contain methane, hydrogen, carbon monoxide, C-2-fraction (acetylene, ethene, second in front-end deethanization hydrogenation material
Alkane)；Evaporated in predepropanization hydrogenation material containing methane, hydrogen, carbon monoxide, C-2-fraction (acetylene, ethene, ethane), carbon three
Divide (propine, allene, propylene, propane).
Front-end deethanization technique is compared with predepropanization work, and hydrogen content is higher in hydrogenation material.In order to avoid more Gao Qing
The loss of ethene under Gas content, front-end deethanization require that catalyst has preferably selectivity.
Be not present C3 fraction in front-end deethanization, and predepropanization technique because catalyst in the same of selectively removing acetylene
When, by removing part propine, allene, in hydrogenation process, C3 fraction serves the adjustment effect to catalyst activity indirectly,
The possibility of device temperature runaway is reduced to a certain extent.And in front-end deethanization hydrogenation process, except being avoided by the adjustment of temperature
Beyond the temperature runaway and leakage alkynes of device, the normal operation of device is ensured without any adjustable technological parameter.Therefore, preceding de- second
Alkane is higher to the operating flexibility and stability requirement of hydrogenation catalyst compared with predepropanization.
In the commercial plant using front-end deethanization, domestic device removes alkynes mode using single hop isothermal reactor, and adopts
With the commercial plant of predepropanization, typically alkynes technique is removed using three sections of reactors.Therefore, in front-end deethanization technique, catalyst
Except alkynes load is higher, device is higher to the Active pharmaceutical of catalyst.
The key reaction occurred in the reactor is as follows：
Main reaction
C2H2+H2→C2H4 (1)
Side reaction
C2H4+H2→C2H6 (2)
C2H2+2H2→C2H6 (3)
In these are answered, what reaction (1) was desirable to, acetylene is both stripped of, has increased production ethene again；React (2), (3) are not
Wish what is occurred.
Even if using etc. hotbed reactor, the selectivity of reaction also can only achieve 50~60%, that is to say, that reaction 2 hair
Raw probability is 50% even more high of reaction 1, has quite a few ethene to be converted into ethane.
When using isothermal bed process, using shell and tube reactor, there is cooling medium between tubulation, to take away reaction production
Raw heat.For the process, typically must relatively accurately it be controlled as cooling medium, its flow using methanol
System, so that the temperature stabilization in reactor is in suitable scope, temperature is too low easily to occur leakage alkynes, and temperature is high and easy temperature runaway.
Device is driven initial stage, and catalyst activity is high, temperature sensitive, especially true.
Patent US4484015 discloses a kind of catalyst, uses using Pd as main active component, using Alpha-alumina as carrier, adds
Add co-catalyst silver-colored, the C2 hydrogenation catalyst of function admirable is prepared for infusion process.The catalyst has and can effectively reduced
The excessive hydrogenation of ethene, reduce the risk of bed temperature runaway.
Using aluminum oxide as carrier, addition co-catalyst silver acts on patent US5587348 with palladium, adds alkali metal, chemical bond
The fluorine of conjunction is prepared for the C2 hydrogenation catalyst of function admirable.The catalyst, which has, reduces green oil generation, improves ethylene selectivity,
The characteristics of reducing oxygenatedchemicals growing amount.US5510550 prepares catalyst using the method for wet reducing, by maceration extract
Middle addition reducing agent, make Pd, Ag solution is reduced when unseasoned, reduces the scattered inequality of active component caused by solvation effect
Even problem, it is prepared for the catalyst of the excellent adaptation front-end hydrogenation technique of carbon two of selectivity.
More than hydrogenation catalyst be using the aqueous solution prepare, in the dipping of catalyst and drying process process by
The influence of solvation effect, metal active constituent presoma are deposited on carrier surface with aggregate form.It is non-equal due to what is disperseed
Even property, high-temperature roasting easily cause metallic migration aggregation and form big crystal grain；The repeatability of catalyst preparation is influenceed, is reduced
The utilization rate of active component, the preparation of one-component noble metal catalyst is carried out in another US4714692 using micro-emulsion process.Adopt
When preparing multicomponent catalyst in this way, shadow that still unavoidable solvation effect is distributed to catalyst activity component
Ring.
CN201110086048.5 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 in order and height point
Dissipate.Using the patented method, the specific high-molecular compound of carrier adsorption carries out chemistry by the hydroxyl of aluminum oxide with macromolecule
Absorption, the amount of carrier adsorption high-molecular compound will be limited by aluminum oxide hydroxyl quantity；Macromolecule by functionalization with
Pd complexing is not strong, and activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is caused
Catalyst cost improves；C2 hydrogenation catalyst is prepared using this method and the shortcomings that technological process complexity also be present.
In recent years, part ethylene unit contains the impurity such as certain As, S due to raw material in poor quality, its C2 hydrogenation device,
And the impurity effects such as the type device, As, S are used for as the bimetal supported catalyst of active component, Ag for auxiliary agent using Pd and urged
Agent activity, can cause catalyst inactivation when serious, so as to bring device to leak alkynes risk.Particularly using front-end hydrogenation technique
In C2 hydrogenation device, its CO content is high, and fluctuation is big, also can be active component to Pd, the bimetallic support type that Ag is auxiliary agent urges
The activity of agent causes large effect.
The content of the invention
It is an object of the invention to provide a kind of method of C-2-fraction front-end hydrogenation, before being especially to provide a kind of C-2-fraction
Deethanization front-end hydrogenation process, by selecting the catalyst with complete alloy structure, improve hydrogenation selectivity.
Inventor has found that active component Pd, Ni are in the distribution of catalyst surface, the performance of strong influence catalyst, and
Work as Pd, when Ni forms alloy, the selectivity of catalyst is more excellent.
The present invention is the front-end hydrogenation process using front-end deethanization, i.e., by the tower from front-end deethanization tower in ethylene unit
Distillate is pushed up, carries out selection hydrogenation to remove acetylene therein, the material is by the cracking cut from steam cracking furnace, is passed through
Chilling, wash, after oil wash, then by front-end deethanization tower separation of carbon three and carbon cut below two, carbon cut below two, which enters, to be hydrogenated with
Reactor carries out selection hydrogenation, and the hydrogenation reaction is fixed bed reactors (including etc. hotbed, adiabatic reactor).
A kind of C-2-fraction front-end deethanization front-end hydrogenation method, the tower top from front-end deethanization tower in ethylene unit is flowed out
Thing carries out selection hydrogenation into fixed bed reactors, to remove alkynes and alkadienes therein, it is characterised in that fixed bed reaction
Pd-Ni series catalysts are housed, Pd-Ni series catalysts refer to Al in device2O3It is carrier, is counted using the quality of catalyst as 100%,
Wherein Pd contents are 0.02~0.080%；Ni contents are 0.040~0.30%, and the specific surface area of catalyst is 1~40m2/ g,
Pore volume is 0.15~0.50ml/g；In catalyst in preparation process, pass through alumina series carrier and hydroxyl bipyridyl
Derivative combines, and hydroxyl dipyridyl derivatives form metal complex with active component.
The characteristics of Pd-Ni series catalysts used in the present invention is：The catalyst be using the present invention PdNi- hydroxyls-
Bipyridyl/Al2O3Prepared by the method for precursor.
The catalyst preparation process of recommendation, is comprised at least：Hydroxyl-bipyridyl is loaded on alumina series carrier, then led to
The cation for crossing the unnecessary hydroxyl of hydroxyl dipyridyl derivatives and/or nitrogen base and Pd, Ni 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 unnecessary hydroxyl with aluminum oxide
With Pd, Ni 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 present invention principle be：In selective hydrogenation reaction, closed as used catalyst activity component Pd, Ni is formed
Gold, the quantity that catalyst body phase adsorbs hydrogen are greatly reduced, and the trend that deep hydrogenation occurs for acetylene substantially reduces, catalyst choosing
Selecting property 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, prepare Pd, Ni mixed-cation solution dipping
Hydroxyl-bipyridyl/Al2O3Precursor, dried at 60 DEG C~150 DEG C, obtain PdNi- hydroxyls-bipyridyl/Al2O3Precursor.
In 300~600 DEG C of 2~12h of roasting temperature, required catalyst is obtained.
Carrier of the present invention is alumina series carrier, preferably Al2O3Or mainly contain Al2O3, wherein also doped with other oxygen
The mixture of compound, other oxides are titanium oxide, magnesia and/or calcium oxide.Described Al2O3For θ, α or its mix-crystal
Type.
Carrier can be spherical in the present invention, cylinder, annular, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Catalyst preparation of the present invention can be implemented using procedure below, and the process can be divided into the progress of 3 steps.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By the organic solution and Al of hydroxyl dipyridyl derivatives2O3It is carrier mixing, is absorbed solution, at 20 DEG C
2~24h is reacted at a temperature of~60 DEG C, takes out solid particle, is dried at 60 DEG C~150 DEG C, obtains hydroxyl-bipyridyl/Al2O3
Precursor.Hydroxyl-bipyridyl/(Pd+Ni) molal quantity is preferably 1~100；It is total that the best volume of organic solution is more than or equal to carrier
The 80% of volume.
B.PdNi- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Pd, Ni mixed-cation solution are prepared, hydroxyl-connection pyrrole obtained by step A is added at a temperature of 30 DEG C~100 DEG C
Pyridine/Al2O3Precursor reacts 2~24h, takes out solid particle, is dried at 60 DEG C~150 DEG C, obtains PdNi- hydroxyls-connection pyrrole
Pyridine/Al2O3Precursor.
Wherein, the addition of Pd, Ni mixed-cation solution is preferably hydroxyl-bipyridyl/Al2O3Precursor cumulative volume
60%~200%；The ratio between Ni molal quantity and Pd molal quantity are preferably 0.4~8, and it is 1.5~4.0 preferably to adjust pH value.
C. the preparation of catalyst
PdNi- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature,
So that PdNi- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
In use, can be by catalyst made from above method, in the reactor using H in catalyst2Carry out reduction treatment,
Obtain reduction-state catalyst.
The present invention is not limited especially to the type of fixed reactor, isothermal reactor or adiabatic reactor.
The present invention is not limited especially to the bed number of the catalyst of fixed bed reactors, single or more.
Fixed bed reactors are that reaction condition is when waiting hotbed reactor：70~150 DEG C of reactor inlet temperature, reaction pressure
3.5~5.0MPa of power, 4000~15000h of single hop gas reactor volume space velocity-1.(referring to single hop reactor, as follows).
Reaction condition is when fixed bed reactors are adiabatic reactor reactor：45~100 DEG C of reactor inlet temperature, reaction pressure
3.0~4.5MPa of power, 5000~25000h of gas reactor volume space velocity-1(referring to single hop reactor, as follows).
Solvent is added in step in order that hydroxyl dipyridyl derivatives are completely dissolved, and is existed with being advantageous to macromolecule
Absorption on carrier, solvent can be ethanol and ether.How much is the addition of solvent, mainly to control institute's solubilizer to make height
Molecule is completely dissolved.
In stepb, the solution of palladium-nickel can be the soluble salt solutions of palladium, nickel, such as can be Pd (NO3)2、Ni
(NO3)2·6H2O mixed solution.Palladium in the mixed solution, nickel salt dosage are can make Pd, Ni content of final catalyst.
In step C, what roasting was preferably carried out in having oxygen atmosphere, sintering temperature of the present invention is preferably 350 DEG C~500
℃。
The present inventors have additionally discovered that when using the method for hydrotreating of the present invention, under the conditions of isothermal bed process, catalyst can be with
Run under conditions of the minimum safe air speed more required than traditional catalyst operation is much lower, greatly improve the peace of technological operation
Quan Xing, improve the safe coefficient of plant running.After the catalyst, the safe air speed of device can be reduced to 4000h-1。
The inventors discovered that after using method of hydrotreating of the invention, hotbed reactor can be waited to be changed to thermal insulation traditional
Bed reactor, reduces the consumption of energy, enormously simplify the operation of reactor, improves reliability, is transported to improving the stable of device
Row is significant.
Meanwhile the inventive method prepares palladium-nickel catalyst, its alloy structure be more suitably applied to the impurity contents such as As, S compared with
High carbon two selects hydrogenation plant.Under the higher working condition of the impurity contents such as As, S, still with excellent hydrogenation activity and
Stability, in the front-end hydrogenation device of carbon two, showing preferably anti-CO fluctuations ability, effectively improve plant running stability.
Brief description of the drawings
Accompanying drawing 1 is a kind of C2 hydrogenation process chart using front-end deethanization technique of the application present invention.
1-oil scrubber；2-water scrubber；3-caustic wash tower；4-drying tower；5-front-end deethanization tower；6-C2 hydrogenation reacts
Device；7-domethanizing column.
Embodiment
Analysis test method：
Specific surface area：GB/T-5816
Pore volume：GB/T-5816
Heap density：Q/SY142-2006
Catalyst Pd, Ni assay：Using plasma emission spectrometer measures catalyst Pd contents and Ni 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 4.3mm, length 4.3mm, specific surface area 19m2/ g, pore volume are 0.22ml/g column α-Al2O3Carry
Body 500g.
By 68.72g 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 dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 60 DEG C of dry 10h, obtain
Hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.256g Pd (NO3)2、1.04g Ni(NO3)2·6H2O is dissolved in the 600mL deionized waters containing appropriate nitric acid,
It is 2.0 to adjust pH, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, stirring
10min, 2h is stood, raffinate is poured out, obtains PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+
Ni)=80).2h is calcined in air atmosphere at a temperature of 550 DEG C after 125 DEG C of dryings, obtains (Pd-Ni)/Al2O3Catalyst.Use
Before be positioned in fixed-bed reactor, with hydrogen purity be 99.9%, air speed 300h-1Gas, at a temperature of 100 DEG C also
Former 4h, obtain loaded catalyst S-1.It is that 0.021%, Ni contents are 0.042% to measure catalyst Pd contents.
Comparative example 1
Weigh Φ 4.3mm, length 4.3mm, specific surface area 19m2/ g, pore volume are 0.22ml/g column α-Al2O3Carry
Body 500g.
Weigh appropriate Pd (NO3)2、Ni(NO3)2·6H2O is dissolved in the 260mL deionized waters containing appropriate nitric acid, and tune pH value is
2.0.Above-mentioned carrier is added in the solution prepared, ultrasonic vibration 0.5h, after 125 DEG C of dryings at a temperature of 550 DEG C air
2h is calcined in atmosphere, obtains (Pd-Ni)/Al2O3Catalyst.It is positioned over before use in fixed-bed reactor, is with hydrogen purity
99.9%, air speed 300h-1Gas, reduce 4h at a temperature of 100 DEG C, obtain loaded catalyst D-1.Measure the catalyst
Pd contents are that 0.021%, Ni contents are 0.042%.
Reaction raw materials：From front-end deethanization column overhead, material composition such as table 1.
The reaction raw materials of table 1 form
| 9 | H2 | C2H2 | C2H4 | C2H6 | CH4 | CO | C+ 3 | S | As |
| Content (V%) | 18.1 | 0.9 | 45.3 | 7.7 | 27.5 | 0.15 | 0.35 | 23ppm | 18ppb |
Reaction condition 1：Hotbed reactor is waited using two sections；Single hop reactor content volume space velocity 7000h-1, operating pressure
3.0MPa, each section of reactor catalyst loadings 500ml.
Table 2 catalyst, 200 hours performance average value
Embodiment 2
Weigh 3.5 × 3.5mm of Φ, specific surface area 35m2/ g, pore volume are 0.38ml/g cylindrical vector 500g, wherein
Containing Al2O3400g, TiO2100g, Al2O3For θ, α mixing crystal formation.
By 231.71g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 750mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 8h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 90 DEG C of dry 8h, obtain
Hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.683g Pd (NO3)2, 5.2g Ni (NO3)2·6H2O is dissolved in the 600mL deionized waters containing appropriate nitric acid, adjusts
PH value is 2.5, is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, stirring
60min, 8h is stood, pour out raffinate, remaining solid dries 6h at 115 DEG C and obtains PdNi- hydroxyls-bipyridyl/Al2O3Precursor
(hydroxyl-bipyridyl molal quantity：(Pd+Ni)=60).
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, reduce 4h at a temperature of 100 DEG C, obtain loaded catalyst
S-2.It is that 0.056%, Ni contents are 0.21% to measure catalyst Pd contents.
Comparative example 2
Weigh 3.5 × 3.5mm of Φ, specific surface area 35m2/ g, pore volume are 0.38ml/g cylindrical vector 500g, wherein
Containing Al2O3400g, TiO2100g, Al2O3For θ, α mixing crystal formation.
A, functionalization SAN/Al2O3Preparation
SAN resin 2.5g are weighed, are dissolved in 600mL dimethylformamides (DMF) solvent, stirring at room temperature makes SAN trees
Fat is completely dissolved, add in this solution it is above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred, separate solvent after dry, obtain
To SAN/ (Al2O3+TiO2)。
By SAN/ (Al obtained above2O3+TiO2), it is added in 1000mL deionized waters, adds 57.6g ethylenediamines, returns
Stream reaction 1h, takes out product after cooling, washs to neutrality, be dried to obtain functionalization SAN/ (Al2O3+TiO2) presoma.Complexing agent
Reactive group Cl molal quantity=19 on molal quantity/macromolecular chain of ethylenediamine.
B, (Pd-Ni)-high-molecular complex/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2、Ni(NO3)2·6H2O is dissolved in the 600mL deionized waters containing appropriate nitric acid, is configured to mix
Solution, it is 2.5 to adjust pH value, takes the functionalization-SAN/Al prepared2O3+TiO2Presoma is added to Pd (NO3)2, Ni (NO3)2's
In mixed solution, 6h is adsorbed, raffinate is poured out, above-mentioned product is washed with deionized to neutrality, obtain (Pd-Ni) polymer/
Al2O3+TiO2Presoma, reactive group CN molal quantitys/(Pd+Ni) molal quantity=54.71 on macromolecular chain.
C, the preparation of catalyst
After 6h dryings being dried at 115 DEG C of the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Before use
It is positioned in fixed-bed reactor, is 99.9% with hydrogen purity, air speed 300h-1Gas, reduced at a temperature of 100 DEG C
4h, obtain loaded catalyst D-2.It is that 0.056%, Ni contents are 0.21% to measure catalyst Pd contents.
Reaction mass：From front-end deethanization column overhead, raw material composition such as table 3.
The reaction raw materials of table 3 form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | CO | C+ 3 | S | As |
| Content (V%) | 17.1 | 0.7 | 47.5 | 7.7 | 26.5 | 0.10 | 0.40 | 15ppm | 12ppb |
Reaction condition 2：Using the hotbed reactor such as single hop, single hop volume of material air speed：4000h-1, operating pressure：
3.5MPa, each section of reactor catalyst loadings：500ml.
The hotbed reactors such as the single hop of table 4 were through 200 hours reaction results
Embodiment 3
Weigh Φ 3.5mm, specific surface area 5.0m2/ g, pore volume 0.25ml/g, heap is than the spherical load of tooth for 0.95g/ml
Body 500g, wherein α-Al2O3460g, titanium oxide 40g.
By 25.54g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation upper
State in solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 120 DEG C dry
Dry 4h, obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.854gPd (NO3)2, 6.94g Ni (NO3)2·6H2O is dissolved in the 600mL deionized waters containing appropriate nitric acid, adjusts
PH is 3.0, is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, stirring
60min, 12h is stood, pour out raffinate, remaining solid dries 8h at 110 DEG C, obtains PdNi- hydroxyls-bipyridyl/Al2O3Preceding body
Body (hydroxyl-bipyridyl molal quantity：(Pd+Ni)=5).
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, reduced at a temperature of 120 DEG C, obtain loaded catalyst S-
3.It is that 0.070%, Ni contents are 0.28% to measure catalyst Pd contents.
Comparative example 3
Weigh Φ 3.5mm, specific surface area 5.0m2/ g, pore volume 0.25ml/g, heap is than the spherical load of tooth for 0.95g/ml
Body 500g, wherein α-Al2O3460g, titanium oxide 40g.
A, functionalization 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, raffinate is poured out, be dried to obtain PVC/Al2O3Product.
Add 119.28g dicyandiamides and 2.0gNa2CO3, add above-mentioned PVC/Al2O3Backflow 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-Ni)-high-molecular complex/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2、Ni(NO3)2·6H2O is dissolved in the 400mL deionized waters containing appropriate nitric acid, and tune pH value is
3.0, mixed solution is configured to, weighs the functionalization-macromolecule/Al prepared2O3Presoma, by functionalization-macromolecule/Al2O3
It is added to Pd (NO3)2, Ni (NO3)2·6H2In O mixed solution, 1h is adsorbed, raffinate is poured out, by above-mentioned product deionized water
Wash to neutrality, 115 DEG C of dry 4h and obtain (Pd-Ni)-polymer/Al2O3Presoma.
C, the preparation of catalyst
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, reduced at a temperature of 120 DEG C, obtain loaded catalyst D-
3.It is that 0.070%, Ni contents are 0.28% to measure catalyst Pd contents.
Reaction mass comes from front-end deethanization column overhead, and composition is as shown in table 5.
The hydrogenating materials of table 5 form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | CO | C4 + | S | As |
| Content (v/v%) | 29 | 0.4 | 32.4 | 5.88 | 32 | 0.005 | 0.315 | 26ppm | 18ppb |
Reaction condition 3：Using the hotbed reactor such as front-end deethanization front-end hydrogenation technique, single hop shown in accompanying drawing 1, material air speed
For 18000h-1, operating pressure 4.0MPa, loaded catalyst 500ml.
The hotbed reactors such as the single hop of table 6 were through 200 hours reaction results
| Project | Inlet temperature | Temperature rise (DEG C) | C2H2Residual volume | Ethylene selectivity | Green oil amount (%) |
| (℃) | (μL/L) | % | |||
| S-3 | 95 | 28 | 0.01 | 61 | 1.3 |
| D-4 | 95 | 25 | 1 | 57 | 1.5 |
Embodiment 4
Weigh Φ 3.6mm, specific surface area 6.0m2/ g, pore volume 0.45ml/g, heap is than the tooth ball-type load for 0.89g/ml
Body 500g, wherein α-Al2O3480g, magnesia 20g.
By 39.24g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after standing 6h causes dihydroxy -2,2- bipyridyl to load to completely on alumina support, 100 DEG C of dry 6h, hydroxyl is obtained
Base-bipyridyl/Al2O3Precursor.
Weigh 0.512gPd (NO3)2, 3.47g Ni (NO3)2·6H2O adds the 600ml deionized waters containing appropriate nitric acid, adjusts
It is 3.5 to save pH value.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 3h,
Raffinate is poured out, PdNi- hydroxyls-bipyridyl/Al is obtained after 120 DEG C of dry 4h2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+
Ni)=15).
By the presoma of above-mentioned preparation, 400 DEG C of roasting 8h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas, at a temperature of 120 DEG C, obtain loaded catalyst S-4.Survey
It is that 0.042%, Ni contents are 0.14% to obtain catalyst Pd contents.
Comparative example 4
Weigh Φ 3.6mm, specific surface area 6.0m2/ g, pore volume 0.45ml/g, heap is than the tooth ball-type load for 0.89g/ml
Body 500g, wherein α-Al2O3480g, magnesia 20g.
Appropriate 4,4- dihydroxy -2,2- bipyridyl is dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation in above-mentioned solution
In, stand after 6h causes dihydroxy -2,2- bipyridyl to load to completely on alumina support, 100 DEG C of dry 6h, obtain hydroxyl -
Bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2、AgNO3The 600ml deionized waters containing appropriate nitric acid are added, regulation pH value is 3.5.Will be upper
State hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 3h, pours out raffinate, and 120 DEG C dry
PdNi- hydroxyls-bipyridyl/Al is obtained after dry 4h2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Ag)=15).
By the presoma of above-mentioned preparation, 400 DEG C of roasting 8h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas, at a temperature of 120 DEG C, obtain loaded catalyst D-4.Survey
It is that 0.042%, Ni contents are 0.14% to obtain catalyst Pd contents.
Reaction mass comes from front-end deethanization column overhead, and composition is as shown in table 7.
The hydrogenating materials of table 7 form
| Hydrogenating materials | H2 | C2H2 | C2H4 | C2H6 | CH4 | CO | C4 + | S | As |
| Content (v/v%) | 28 | 0.6 | 34.2 | 5.88 | 31 | 0.008 | 0.312 | 18ppm | 21ppb |
Reaction condition 1：Using the hotbed reactor such as front-end deethanization front-end hydrogenation technique, single hop shown in accompanying drawing 1, material air speed
For 13000h-1, operating pressure 3.8MPa, loaded catalyst 300ml.
The hotbed reactors such as the single hop of table 8 were through 200 hours reaction results
| Project | Inlet temperature (DEG C) | Temperature rise (DEG C) | C2H2Residual volume (μ L/L) | Ethylene selectivity % |
| S-4 | 110 | 30 | 75 | 66 |
| D-5 | 110 | 29 | 89 | 65 |
After embodiment more than can be seen that the method using the present invention, the activity of C-2-fraction hydrogenation reaction, selection
Property increase substantially, green oil generating amount reduce, catalyst service life extend.
Claims (14)
1. a kind of C-2-fraction front-end deethanization front-end hydrogenation method, the tower top effluent from front-end deethanization tower in ethylene unit is entered
Enter fixed bed reactors and carry out selection hydrogenation, to remove alkynes and alkadienes therein, it is characterised in that in fixed bed reactors
Equipped with Pd-Ni series catalysts, Pd-Ni series catalysts use Al2O3It is carrier, is counted using the quality of catalyst as 100%, wherein Pd
Content is 0.02~0.080%；Ni contents are 0.040~0.30%, and the specific surface area of catalyst is 1~40m2/ g, pore volume
For 0.15~0.50ml/g；The catalyst passes through alumina series carrier and hydroxyl dipyridyl derivatives in preparation process
With reference to hydroxyl dipyridyl derivatives form metal complex with active component.
2. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that fixed bed reactors are
Reaction condition is during Deng hotbed reactor：70~150 DEG C, 3.5~5.0MPa of reaction pressure of reactor inlet temperature, single hop reaction
4000~15000h of device gas volume air speed-1。
3. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that fixed bed reactors are
Reaction condition is during adiabatic reactor reactor：45~100 DEG C, 3.0~4.5MPa of reaction pressure of reactor inlet temperature, single hop reaction
5000~25000h of device gas volume air speed-1。
4. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that catalyst preparation process,
Comprise at least：Hydroxyl dipyridyl derivatives are loaded on alumina series carrier, then derived by hydroxyl bipyridyl
The cation of the unnecessary hydroxyl of thing and/or nitrogen base and Pd, Ni forms complex ion.
5. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that hydroxyl bipyridyl
Derivative refers to hydroxyl 2,2 ,-dipyridyl derivatives or hydroxyl 3, and 3 ,-dipyridyl derivatives.
6. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that the preparation of this catalyst
Comprise the following steps：With the organic solution of hydroxyl dipyridyl derivatives, Al is impregnated2O3It is carrier, obtains hydroxyl after drying
Base-bipyridyl/Al2O3Precursor, prepare Pd, Ni mixed-cation solution dipping hydroxyl-bipyridyl/Al2O3Precursor, in
Dried at 60 DEG C~150 DEG C, obtain PdNi- hydroxyls-bipyridyl/Al2O3Precursor；300~600 DEG C of roasting temperatures 2~
12h, obtain required catalyst.
7. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that Al2O3It is that carrier is
Al2O3Or mainly contain Al2O3, wherein also doped with other hopcalites, other oxides are titanium oxide, magnesia
And/or calcium oxide；Described aluminum oxide is θ, α or it mixes crystal formation.
8. any C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1-7, it is characterised in that catalyst
Obtaining specific steps 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
~24h, solid particle is taken out, dried at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdNi- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Ni mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with step A obtained by hydroxyl bipyridyl/
Al2O3Precursor react 2~24h, take out solid particle, at 60 DEG C~150 DEG C dry, obtain PdNi- hydroxyls-bipyridyl/
Al2O3Precursor；
C. the preparation of catalyst
PdNi- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor is in 300~600 DEG C of 2~12h of roasting temperature so that
PdNi- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
9. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 8, it is characterised in that hydroxyl-connection in step A
Pyridine/(Pd+Ni) molal quantity is 1~100：1.
10. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 8, it is characterised in that in stepb, Pd,
Ni mixed-cation solution is the mixed solution of palladium nitrate and nickel nitrate.
11. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 8, it is characterised in that in stepb, Ni's
The ratio between molal quantity and Pd molal quantity is 0.4~8：1.
12. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 8, it is characterised in that adjust in stepb
Pd, Ni mixed-cation solution ph are 1.5~4.0.
13. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that can contain in unstripped gas
Sulfur-containing impurities not higher than 30ppm.
14. C-2-fraction front-end deethanization front-end hydrogenation method according to claim 1, it is characterised in that can contain in unstripped gas
Contain arsenic impurities not higher than 30ppb.
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| CN101613621A (en) * | 2008-06-26 | 2009-12-30 | 中国石油化工股份有限公司 | Splitting gas is selected hydrogenation and separation method |
| CN103635480A (en) * | 2011-07-01 | 2014-03-12 | 株式会社大赛璐 | Palladium complex and method for producing same, method for producing vinyl ether compound, and method for collecting palladium complex |
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| CN101613621A (en) * | 2008-06-26 | 2009-12-30 | 中国石油化工股份有限公司 | Splitting gas is selected hydrogenation and separation method |
| CN103635480A (en) * | 2011-07-01 | 2014-03-12 | 株式会社大赛璐 | Palladium complex and method for producing same, method for producing vinyl ether compound, and method for collecting palladium complex |
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