CN105732274A - Method of purifying ethylene through selective hydrogenation - Google Patents
Method of purifying ethylene through selective hydrogenation Download PDFInfo
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Abstract
The invention relates to a method of purifying ethylene through selective hydrogenation. An adiabatic bed reactor for hydrogenation is arranged after an ethylene rectification column and before an ethylene polymerization reactor. A Pd-Ni-series catalyst is arranged in a fixed bed reactor and is prepared with an alumina-series carrier. During preparation of the catalyst, the alumina-series carrier is combined with a bipyridine derivative having a hydroxyl group, wherein a metal complex is formed from the hydroxyl bipyridine derivative combined on the carrier and an active component. With the catalyst, activity and selectivity of the hydrogenation method are greatly better than that in a conventional hydrogenation method, and purity of ethylene is increased so that performance of a polymerization-grade ethylene product is improved well. Through reduction on green oil, active center of the catalyst is not covered by side product, thereby prolonging the service life of the catalyst. The catalyst has excellent anti-impurity-interference capability and is suitable for an ethylene selective hydrogenation device being high in content of impurities, such as sulfur, arsenic and the like.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly a kind of ethylene selects hydrorefined method.
Background technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the most basic raw materials of downstream polymerisation device.Wherein ethylene processing industry is had extremely important impact by the selection hydrogenation of acetylene, except the outlet acetylene content of guarantee hydrogenation reactor is up to standard, selectivity of catalyst is excellent, the generation ethane that ethylene is the least possible can be made, to the yield of ethene improving whole technical process, improve device economic benefit significant.
Cracking C-2-fraction contains the acetylene that molar fraction is 0.5%-2.5%, when producing polyethylene, a small amount of acetylene in ethylene can reduce the activity of polymerization catalyst, and make the deterioration in physical properties of polymer, so the acetylene content in ethylene must be dropped to certain limit, could as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are one of processes important in ethylene unit flow process.
In ethylene unit, catalysis selective hydrogenation includes front-end hydrogenation and back end hydrogenation, ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene hydrogenation reactor is for domethanizing column position, hydrogenation reactor is front-end hydrogenation before being positioned at domethanizing column, and hydrogenation reactor is back end hydrogenation after being positioned at domethanizing column.In current C-2-fraction acetylene hydrogenation, more and more many processes adopting carbon two front-end hydrogenation, the feature of this process is that hydrogenation reactor is before domethanizing column.Front-end hydrogenation is divided into again predepropanization and two kinds of techniques of front-end deethanization.Front-end deethanization hydrogenation technique is after hydrogenation reactor is positioned at dethanizer, before domethanizing column.Predepropanization hydrogenation technique is after hydrogenation reactor is positioned at depropanizing tower, before domethanizing column.The difference of flow process, brings the difference of two kinds of hydrogenation material compositions.Containing methane, hydrogen, carbon monoxide, C-2-fraction (acetylene, ethylene, ethane) in front-end deethanization hydrogenation material；Containing methane, hydrogen, carbon monoxide, C-2-fraction (acetylene, ethylene, ethane), C3 fraction (propine, allene, propylene, propane) in predepropanization hydrogenation material.
Material in ethylene unit is after Acetylene converter, then then through ethylene distillation, material still contains the acetylene of 1～10ppm, the CO of trace, owing to polymer grade ethylene product is more and more higher to the requirement of raw material, the existence adding these impurity influences whether the performance of ethylene rolymerization catalyst, therefore, require over the mode selecting hydrogenation, by the selection hydrogenation and removing acetylene of trace acetylene in essence ethylene feed before vinyl polymerization so that it is content is reduced to below 1ppm.
In current ethylene unit, in essence ethylene feed, the selection hydrogenation of trace acetylene is main adopts single hop reactor process.Reactor inlet material forms: ethylene >=99.99% (Φ), acetylene 1～10ppm, CO1～10ppm, and hydrogen adopts the mode of distribution, H2/C2H2=2～20.Reaction pressure 1.5～2.5MPa, air speed 2000～10000h-1, inlet temperature 25 DEG C～60 DEG C.
Alkynes and diolefin hydrogenate catalyst are (US4762956) by noble metal such as palladium load being obtained in the Inorganic material carrier of porous.In order to increase selectivity of catalyst, reduce the catalysqt deactivation that the green oil produced by oligomerization when being hydrogenated with causes, prior art have employed that to add such as group ib element in the catalyst be the method for co-catalysis component: Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Ni (US3912789), or adding alkali metal or alkaline-earth metal (US5488024) etc., carrier used has aluminium oxide, silicon dioxide (US5856262), the loyal cordierite of honeycomb (CN1176291) etc..
US5856262 reports with the modified silicon oxide of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) for carrier, and the method for preparation low in acidity palladium catalyst, at air speed 3000h-1, inlet temperature 35 DEG C, entrance acetylene molar fraction 0.71%, when hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity reaches 56%.Patent US4404124, with aluminium oxide for carrier, adds promoter silver and palladium effect, is prepared for the C2 hydrogenation catalyst of function admirable.This catalyst has minimizing ethane growing amount, it is suppressed that is adsorbed on the acetylene on catalyst surface and carries out partial hydrogenation dimerization reaction, it is suppressed that 1,3-butadiene generates, and reduces green oil and generates, improves ethylene selectivity, reduce the feature of oxygenatedchemicals growing amount, be applied widely in ethylene industry.But, above-mentioned catalyst all adopts infusion process to prepare, and by the restriction of preparation method, metal dispersity is only about 30%, and catalyst performance there is also many deficiencies, still has necessity of improvement further.
CN101745389A discloses a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene, belong to the synthesis of oil (natural gas) chemical products and new catalytic material technical field, relate to a kind of egg-shell catalyst that preparation of ethylene through selective hydrogenation of acetylene is had superior catalytic performance.It is characterized in that with aluminium oxide (Al2O3) bead is carrier, adopt infusion process to prepare the loaded catalyst that active component palladium be eggshell type and is distributed, and adopt Ag to eggshell type Pd/Al2O3Catalyst is modified.Pd load capacity is 0.01～0.1wt%, Ag and Pd atomic ratio is 1～5.The invention have the advantages that, a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene provided, can when high conversion of alkyne, especially close to 100% conversion of alkyne time, it is achieved high ethylene selectivity.
Traditional Pd-Ag bimetallic selective hydrogenation catalyst is all adopt aqueous impregnation method to prepare.When adopting sub-dip method, what a kind of component can be more is enriched in carrier surface, and another kind of component is enriched in outer surface, and only part metals atom interpenetrates, and defines alloy structure.When adopting total immersion method, owing to the presoma of two metal ion species and the interaction of carrier are different, surface tension and solvation, it is hardly formed the uniform load of two kinds of components, also can only partly form alloy structure.When this catalyst is applied to C 2 fraction selective hydrogenation, often better at initial reaction stage selectivity, with the prolongation of the time of operation, selectivity constantly declines, and generally runs 3～6 months and is accomplished by regeneration, and economic loss is bigger.
CN201110086174.0 by adsorbing specific macromolecular compound on carrier, macromolecule wrapped layer is formed at carrier surface certain thickness, with with the compound of function base and high molecular weight reactive, can with the function base of active component complexation so as to have, on carrier surface function base, complex reaction is there is, it is ensured that active component is in order and high degree of dispersion by active component.Adopting this patented method, the specific macromolecular compound of carrier adsorption carries out chemisorbed by the hydroxyl of aluminium oxide and macromolecule, and the amount of carrier adsorption macromolecular compound is subjected to the hydroxyl value quantitative limitation of aluminium oxide；Not strong with the complexing of Pd through the macromolecule of functionalization, activity component load quantity does not reach requirement sometimes, goes back residual fraction active component in impregnation liquid, causes catalyst cost to improve；Adopt the method to prepare C2 hydrogenation catalyst and there is also the shortcoming that technological process is complicated.
Ethylene selects in hydro-refining unit, in its trace acetylene hydrogenation plant, containing impurity such as certain As, S, and with Pd be active component, Ag be auxiliary agent bimetal supported catalyst for the type device, the impurity effect catalyst activities such as As, S, catalysqt deactivation can be caused, thus bringing device leakage alkynes risk time serious.
Summary of the invention
It is an object of the invention to provide a kind of ethylene and select hydrorefined method, by selecting active component high degree of dispersion, there is the Pd-Ni catalyst of height alloy structure, improve hydrogenation activity and selectivity, improve plant running stability and the performance of polymer grade ethylene product.
The inventors discovered that, when the catalyst adopting preparation method of the present invention to prepare, the Pd in catalyst is separated by Ni so that the spacing in active center widens, and occurs hydrodimerized probability to be greatly reduced during two acetylene molecule hydrogenation.The growing amount of 1,3-butadiene significantly declines, and therefore the surface coking rate of catalyst is greatly reduced, and catalyst on-stream cycle time extends, and economic benefit is obvious.
The invention provides a kind of ethylene and select hydrorefined method, after the adiabatic reactor reactor for being hydrogenated with is positioned at ethylene rectifying column, before ethylene polymerization device.By the smart ethylene feed of ethylene distillation column overhead, after joining hydrogen, enter adiabatic reactor reactor to carry out selecting hydrogenation, it is characterized in that: equipped with Pd-Ni series catalysts in adiabatic reactor reactor, carrier is alumina series carrier, with the quality of catalyst for 100%, and wherein Pd content 0.03～0.06%, Ni content is 0.05～0.45%, and the specific surface area of catalyst is 20～60m2/ g, pore volume is 0.15～0.70mL/g；This catalyst, in preparation process, is combined with hydroxyl-bipyridyl by carrier, and hydroxyl dipyridyl derivatives forms metal complex with active component；Reaction condition is: adiabatic reactor reactor inlet temperature 25～60 DEG C, reaction pressure 1.5～2.5MPa, gas volume air speed 2000～10000h-1。
The feature of the Pd-Ni series catalysts used in the present invention is: this catalyst is the PdNi-hydroxyl-bipyridyl/Al adopting the present invention2O3Prepared by the method for precursor.
The catalyst preparation process recommended, at least includes: load on alumina support by hydroxyl dipyridyl derivatives, and the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Ni forms complex ion.
The hydroxyl dipyridyl derivatives of the present invention, preferably hydroxyl 2,2,-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, can there is good complex reaction with Pd, Ni in two nitrilo at hydroxyl unnecessary after being combined with aluminium oxide and ortho position because of it.
The present invention is that a kind of ethylene selects hydrorefined method, and in entrance raw material, composition is mainly ethylene, and reactor inlet material forms: ethylene >=99.99% (Φ), acetylene 5～100ppm, CO1～10ppm, and hydrogen adopts the mode of distribution, H2/C2H2It is generally 2～20.Reaction pressure 1.5～2.5MPa, gas volume air speed 2000～10000h-1, inlet temperature 25 DEG C～60 DEG C.
Defining the catalyst type of use in the present invention, such catalyst selectivity and traditional catalyst have bigger difference.
Principles of the invention is: in selective hydrogenation reaction, along with the catalyst activity component Pd, the Ni that use form alloy, the quantity of the hydrogen that caltalyst phase is adsorbed is greatly reduced, and the trend of acetylene generation deep hydrogenation is substantially reduced, and catalyst selectivity significantly improves.
The acquisition of this catalyst preferably includes following steps: by the organic solution of hydroxyl dipyridyl derivatives, impregnates Al2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Ni2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor.At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
Al of the present invention2O3It is that carrier is preferably aluminium oxide, or mainly contains Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.Described aluminium oxide is γ, δ, θ, alpha-crystal form or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
In the present invention, carrier can be spherical, cylindrical, annular, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc..
Catalyst preparing of the present invention can adopt procedure below to implement, and this process can be divided into 3 steps to carry out.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, makes solution be absorbed, at 20 DEG C～60 DEG C temperature, react 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；Organic solution volume is preferably equal to or greater than the 80% of carrier cumulative volume.
B.PdNi-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Ni, with step A gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle, dry at 60 DEG C～150 DEG C, obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor.
The ratio of the molal quantity of Ni and the molal quantity of Pd is preferably 0.4～11, it is desirable to regulating pH value is 1.5～4.0；The addition of the mixed-cation solution of Pd, Ni is hydroxyl-bipyridyl/Al preferably2O3The 60%～200% of precursor cumulative volume.
C. the preparation of catalyst
PdNi-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdNi-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
In step, described hydroxyl dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, it is preferred to hydroxyl 2,2 ,-dipyridyl derivatives.May insure that Al2O3While it is produced extensive chemical absorption, two nitrilo that unnecessary hydroxyl is adjacent with bipyridyl combine with active component Pd, Ni.With molar basis, the molal quantity of hydroxyl-bipyridyl/(Pd+Ni) is 1～100.
Adding solvent in step to make hydroxyl dipyridyl derivatives be completely dissolved, to be conducive to macromolecule absorption on carrier, solvent can be ethanol and ether.The addition of solvent is how many, mainly to control institute's solubilizer and macromolecule can be made to be completely dissolved.
In stepb, the solution of palladium-nickel can be the soluble salt solutions of palladium, nickel, as being Pd (NO3)2、Ni(NO3)2Mixed solution.In described mixed solution, palladium, nickel salt consumption are can make Pd, Ni content of final catalyst.
In step C, roasting preferably carries out in having oxygen atmosphere, sintering temperature of the present invention preferably 350 DEG C～500 DEG C.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
The present inventors have additionally discovered that, when adopting the method to carry out selective hydrogenation reaction, the activity of catalyst reaction, selectivity are all significantly improved, and catalyst stability strengthens.
Meanwhile, the inventive method prepares palladium-nickel catalyst, and its alloy structure is more suitably applied to the higher ethylene of the impurity contents such as As, S and selects hydro-refining unit.Under the working condition that the impurity contents such as As, S are higher, still there is hydrogenation activity and the stability of excellence.
Accompanying drawing explanation
Fig. 1 is a kind of device ethylene rectification flow figure adopting back end hydrogenation technological process of the application present invention.
Fig. 2 is a kind of device ethylene rectification flow figure adopting front-end deethanization technological process of the application present invention.
Fig. 3 is a kind of device ethylene rectification flow figure adopting predepropanization technological process of the application present invention.
In figure:
1 oil scrubber；2 water scrubbers；3 caustic wash towers；4 exsiccators；5 domethanizing columns；6 dethanizers；7 Acetylene converter；8, ethylene rectifying column；9, ethylene refining reaction device；10 compressors；11 front-end deethanization towers；12, predepropanization tower.
Detailed description of the invention
Embodiment 1
Weighing Φ 4.4mm, specific surface area is 18.0m2Spherical α-the Al of/g, pore volume 0.36mL/g, bulk density 0.88g/ml2O3Carrier 500g.
By 149.52g4,4-dihydroxy-2,2-bipyridyl is dissolved in 700mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 2h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 60 DEG C of dry 10h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.68gPd (NO3)2、6.94gNi(NO3)2·6H2O is dissolved in the 600mL deionized water containing appropriate nitric acid, and adjusting pH value is 2.0, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=30).After 120 DEG C of dry 4h at 550 DEG C of temperature roasting 2h in air atmosphere, obtain (Pd-Ni)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature reduce, obtain loaded catalyst S-1.Recording this catalyst Pd content is 0.056%, and Ni content is 0.28%.
Comparative example 1
Weighing Φ 4.4mm, specific surface area is 18.0m2Spherical α-the Al of/g, pore volume 0.36mL/g, bulk density 0.88g/ml2O3Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC8.9g is dissolved completely in 800mlTHF (oxolane), in above-mentioned carrier impregnation to above-mentioned solution, after standing 2h, PVC will be made to be adsorbed in Al2O3Surface, drying for standby.Obtain PVC/Al2O3。
Add 119.28g dicyandiamide and 4.0gNa2CO3, add above-mentioned PVC/Al2O3Backflow 1h, is cooled to room temperature, with deionized water wash to neutral, and drying for standby, obtain functionalized PVC/Al2O3。
B、Pd-Ni-polymer/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)、Ni(NO3)2·6H2O is dissolved in the 2400mL deionized water containing appropriate nitric acid, and adjusting pH value is 2.0, is made into mixed solution, takes the functionalized-PVC/Al prepared2O3Presoma, adds it to Pd (NO3)2、Ni(NO3)2Mixed solution in, stir 30min, pour out residual liquid, by above-mentioned product deionized water wash to neutral, at 120 DEG C, after dry 4h, obtain (Pd-Ni)-PVC/Al2O3Presoma.
C, catalyst preparation
By above-mentioned presoma roasting 2h in air atmosphere at 550 DEG C of temperature, obtain (Pd-Ni)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature reduce, obtain loaded catalyst D-1.Recording this catalyst Pd content is 0.056%, and Ni content is 0.28%.
Adopting ethylene to select hydrorefined method, as shown in Figure 1, raw material composition and working condition are in Table 1 for its process chart.
Table 1 micro anti-evaluation parameter
Table 2 catalyst 200h performance meansigma methods
| Catalyst | Inlet temperature DEG C | Temperature rise DEG C | C2H2Residual volume (μ L/L) | Hydrogenation selectivity, % | Green oil amount (g) |
| S-1 | 60 | 19 | 0 | 55 | 0.1 |
| D-1 | 60 | 15 | 0.8 | 32 | 0.6 |
Embodiment 2
Weighing Φ 3.6mm, high 3.6mm, specific surface area is 60.0m2/ g, pore volume is 0.67ml/g, and bulk density is the cylindrical δ-Al of 0.67g/ml2O3Carrier 500g.
By 17.16g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 90 DEG C of dry 8h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.98gPd (NO3)2、3.47gNi(NO3)2·6H2O is dissolved in 600mL deionized water, and adjusting pH value is 2.5, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=5).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst S-2.Recording this catalyst Pd content is 0.08%, and Ni content is 0.14%.
Comparative example 2
Catalyst preparing
Weighing Φ 3.6mm, high 3.6mm, specific surface area is 60.0m2/ g, pore volume is 0.67ml/g, and bulk density is the cylindrical δ-Al of 0.67g/ml2O3Carrier 500g.
Weigh appropriate Pd (NO3)2Being dissolved in 300ml deionized water, the pH value regulating solution is 2.5, by described carrier impregnation in the solution prepared, stirs 5min, pours out residual liquid, weigh appropriate Ni (NO3)2·6H2O, adds the 600ml deionized water containing a certain amount of nitric acid, obtains PdNi/Al after drying2O3Precursor.
Above-mentioned presoma is joined in the solution prepared, stir 5min, pour out residual night, after drying at 500 DEG C of roasting temperature 4h, obtain (Pd-Ni)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature reduce, obtain loaded catalyst D-2.Recording this catalyst Pd content is 0.08%, and Ni content is 0.14%.
Adopting ethylene to select hydrorefined method, as shown in Figure 2, raw material composition and working condition are in Table 1 for its process chart.
Table 3 micro anti-evaluation parameter
Table 4 catalyst 200h performance meansigma methods
| Catalyst | Inlet temperature DEG C | Temperature rise DEG C | C2H2Residual volume (μ L/L) | Hydrogenation selectivity, % | Green oil amount (g) |
| S-2 | 70 | 22 | 0 | 55 | 0.3 |
| D-2 | 70 | 20 | 0.5 | 25 | 1.2 |
Embodiment 3
Weighing Φ 4.5mm, specific surface area is 45.0m2/ g, pore volume is 0.20mL/g, and heap is than the tooth ball type carrier 500g, wherein θ-Al for 0.79g/ml2O3460g, titanium oxide 40g.
By 40.430g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 700mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 12h, make 6,6'-dihydroxy-3,3'-bipyridyl loads to after on alumina support completely, 120 DEG C of dry 4h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.683gPd (NO3)2, 1.74gNi (NO3)2·6H2O is dissolved in the 600mL deionized water containing appropriate nitric acid, and adjusting pH value is 3.0, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid is dry 8h at 100 DEG C, obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=25).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst S-3.Recording this catalyst Pd content is 0.056%, and Ni content is 0.07%.
Comparative example 3
Weighing Φ 4.5mm, specific surface area is 45.0m2/ g, pore volume is 0.20mL/g, and heap is than the tooth ball type carrier 500g, wherein θ-Al for 0.79g/ml2O3460g, titanium oxide 40g.
A, functionalized chlorinated polyethylene (CPE) preparation
CPE16.0g is dissolved completely in 800mlTHF, adds 480g dicyandiamide and 4.0gNa2CO3, add CPE and reflux 2 hours, be cooled to room temperature, with deionized water wash to neutral, obtain functionalized CPE standby.
B, (Pd-Ni)-high-molecular complex/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2、Ni(NO3)2·6H2O, measures appropriate nitric acid, joins in above-mentioned functionalized CPE solution, stirs 60min, obtains (Pd-Ni)-CPE.
Being added by 500g carrier in mixed solution, stand 4h after being sufficiently stirred for, by above-mentioned product deionized water wash to neutral, remaining solid is dry 8h at 100 DEG C, obtains (Pd-Ni)-high-molecular complex/Al2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere, obtain oxidation state (Pd-Ni)/Al2O3Catalyst.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst D-3.Recording this catalyst Pd content is 0.056%, and Ni content is 0.07%.
Adopting ethylene to select hydrorefined method, as shown in Figure 1, raw material composition and working condition are in Table 1 for its process chart.
Table 5 micro anti-evaluation parameter
Table 6 catalyst 200h performance meansigma methods
| Catalyst | Inlet temperature DEG C | Temperature rise DEG C | C2H2Residual volume (μ L/L) | Hydrogenation selectivity, % | Green oil amount (g) |
| S-3 | 65 | 19 | 0 | 54 | 0.3 |
| D-3 | 65 | 22 | 1.3 | 30 | 0.7 |
Embodiment 4
Weighing Φ 3.5mm, high 3.5mm, specific surface area is 51.0m2/ g, pore volume is 0.58ml/g, and bulk density is the cylindrical δ-Al of 0.75g/ml2O3Carrier 500g.
By 110.28g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 10h, dihydroxy-2,2-bipyridyl are loaded to after on alumina support completely, 100 DEG C of dry 6h, obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.854gPd (NO3)2、10.41gNi(NO3)2·6H2O is dissolved in the 600mL deionized water containing appropriate nitric acid, and adjusting pH value is 3.5, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and at 90 DEG C, dry 10h obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=15).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst S-4.Recording this catalyst Pd content is 0.07%, and Ni content is 0.42%.
Comparative example 4
Weighing Φ 3.5mm, high 3.5mm, specific surface area is 51.0m2/ g, pore volume is 0.58ml/g, and bulk density is the cylindrical δ-Al of 0.75g/ml2O3Carrier 500g.
Weighing appropriate 4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 10h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 100 DEG C of dry 6h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2、AgNO3Being dissolved in the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 3.5, is made into mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and at 90 DEG C, dry 10h obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ag=15).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Being positioned over before using in fixed-bed reactor, be 99.9% by hydrogen purity, air speed is 200h-1Gas, at 120 DEG C of temperature, obtain loaded catalyst D-4.Recording this catalyst Pd content is 0.07%, and Ni content is 0.42%.
Adopting ethylene to select hydrorefined method, as shown in Figure 3, raw material composition and working condition are in Table 1 for its process chart.
Table 7 micro anti-evaluation parameter
Table 8 catalyst 200h performance meansigma methods
| Catalyst | Inlet temperature DEG C | Temperature rise DEG C | C2H2Residual volume (μ L/L) | Hydrogenation selectivity, % | Green oil amount (g) |
| S-4 | 67 | 23 | 0 | 54 | 0.7 |
| D-4 | 67 | 21 | 1.5 | 31 | 1.9 |
Can be seen that, compared with adopting tradition preparation catalyst, with adopt organic polymer grafted functional group load on a catalyst support, the solution of this carrier impregnation activity Pd, Ni obtains the method for organic polymer metal complex again prepare catalyst and compare, catalyst used by the present invention, the activity of hydrogenation reaction and selectivity are significantly better than traditional method of hydrotreating, embodiment device middle outlet acetylene content substantially reduces, Ethylene purity improves, such that it is able to improve the performance of polymer grade ethylene product very well.The reduction of green oil simultaneously so that the active center of catalyst is not covered by by-product, catalyst activity and selectivity are able to good maintenance, and catalyst extends service life.
Claims (15)
1. ethylene selects a hydrofinishing process, after the adiabatic reactor reactor for being hydrogenated with is positioned at ethylene rectifying column, before ethylene polymerization device；By the smart ethylene feed of ethylene distillation column overhead, after joining hydrogen, enter adiabatic reactor reactor to carry out selecting hydrogenation, it is characterized in that: equipped with Pd-Ni series catalysts in adiabatic reactor reactor, carrier is alumina series carrier, with the quality of catalyst for 100%, and wherein Pd content 0.03～0.06%, Ni content is 0.05～0.45%, and the specific surface area of catalyst is 20～60m2/ g, pore volume is 0.15～0.70mL/g；This catalyst, in preparation process, is combined with hydroxyl dipyridyl derivatives by carrier, and hydroxyl dipyridyl derivatives forms metal complex with active component；Reaction condition is: adiabatic reactor reactor inlet temperature 25～60 DEG C, reaction pressure 1.5～2.5MPa, gas volume air speed 2000～10000h-1。
2. ethylene according to claim 1 selects hydrofinishing process, it is characterized in that catalyst preparation process, at least including: loaded to by hydroxyl dipyridyl derivatives on alumina series carrier, the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Ni forms complex ion.
3. ethylene according to claim 2 selects hydrofinishing process, it is characterised in that hydroxyl dipyridyl derivatives, it is preferred to hydroxyl 2,2,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.
4. ethylene according to claim 1 selects hydrofinishing process, it is characterised in that the acquisition of catalyst comprises the steps: the organic solution with hydroxyl dipyridyl derivatives, impregnates carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Ni2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor；At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
5. ethylene according to claim 1 selects hydrofinishing process, it is characterised in that carrier is aluminium oxide or mainly contains Al2O3, wherein also doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide；Described aluminium oxide is γ, δ, θ, alpha-crystal form or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
6. ethylene according to claim 1 selection hydrofinishing process, it is characterised in that carrier is spherical, cylindrical, annular, bar shaped, cloverleaf pattern or Herba Galii Bungei shape.
7. the arbitrary ethylene according to claim 1-6 selects hydrofinishing process, it is characterised in that the preparation method of catalyst comprises the steps:
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, at 20 DEG C～60 DEG C temperature, reacts 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdNi-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Ni, at 30 DEG C～100 DEG C temperature and step A gained hydroxyl-bipyridyl/Al2O3Precursor reaction 2～24h, takes out solid particle, dry at 60 DEG C～150 DEG C, obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor；
C. the preparation of catalyst
PdNi-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdNi-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
8. ethylene according to claim 7 selects hydrofinishing process, it is characterised in that in step A, the molal quantity of hydroxyl-bipyridyl/(Pd+Ni) is 1～100:1.
9. ethylene according to claim 7 selects hydrofinishing process, it is characterised in that in stepb, the mixed solution that mixed-cation solution is Palladous nitrate. and nickel nitrate of Pd, Ni.
10. ethylene according to claim 7 selects hydrofinishing process, it is characterised in that in stepb, and the ratio of the molal quantity of Ni and the molal quantity of Pd is 0.4～11:1.
11. a kind of ethylene according to claim 7 selects hydrofinishing process, it is characterised in that in stepb, the mixed-cation solution ph regulating Pd, Ni is 1.5～4.0.
12. ethylene according to claim 1 selects hydrofinishing process, it is characterised in that hydrogen and acetylene volume ratio are 2～20:1.
13. ethylene according to claim 1 selects hydrofinishing process, it is characterised in that adiabatic reactor reactor reaction bed number is single.
14. ethylene according to claim 1 selects hydrofinishing process, it is characterised in that unstripped gas can contain the sulfur-containing impurities not higher than 30ppm.
15. ethylene according to claim 1 select hydrofinishing process, it is characterised in that in unstripped gas can contain not higher than 30ppb containing arsenic impurities.
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| CN108250018A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of process for purification of ethylene feed acetylene hydrogenation |
| CN108250030A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of ethylene feed selects hydrofinishing process |
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| RU2759086C1 (en) * | 2020-07-15 | 2021-11-09 | Общество с ограниченной ответственностью "Юнайтед Кэталист Текнолоджис" | Method for purifying polymer-purity ethylene |
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| CN108250018A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of process for purification of ethylene feed acetylene hydrogenation |
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