CN105753624B - Trace acetylene selects method of hydrotreating in a kind of methanol-to-olefins device - Google Patents
Trace acetylene selects method of hydrotreating in a kind of methanol-to-olefins device Download PDFInfo
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Abstract
Two material of carbon from deethanizer overhead in methanol-to-olefins device is carried out selection plus hydrogen by the selection method of hydrotreating of trace acetylene in a kind of methanol-to-olefins device into adiabatic reactor reactor, it is characterised in that：Pd Pb series catalysts are housed, with Al in adiabatic reactor reactor2O3Or Al2O3It is carrier with other hopcalites, which is combined in preparation process, by carrier with hydroxyl bipyridyl, and the hydroxyl bipyridyl being incorporated on carrier forms metal complex with active component；Reaction condition is：25 DEG C~60 DEG C of adiabatic reactor reactor inlet temperature, 1.5~2.5MPa of reaction pressure, 2000~10000h of air speed‑1.When carrying out selective hydrogenation reaction using this method, activity, the selectivity of catalyst reaction are significantly improved, catalyst stability enhancing；When containing a certain amount of C-4-fraction in hydrogenating materials, catalyst also has excellent Hydrogenation.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, in especially a kind of methanol-to-olefins device the selection of trace acetylene add
Hydrogen methods.
Background technology
The low-carbon alkenes such as ethylene, propylene are important basic chemical raw materials, with the development of Chinese national economy, especially
Demand of the development of modern chemical industry to low-carbon alkene increasingly rises, and imbalance between supply and demand will also become increasingly conspicuous.So far, it produces
The important channel of the low-carbon alkenes such as ethylene, propylene, be still by naphtha, light diesel fuel (being all from oil) catalytic cracking,
Cracking, the raw material resources such as naphtha, light diesel fuel as ethylene production raw material are faced with increasingly severe short office
Face.In addition, crude oil in China import volume has accounted for the half or so of processing total amount in recent years, using ethylene, propylene as the polyolefin of raw material
Product will maintain the quite high percentage of import.Therefore, development non-oil resource carrys out the technologies of preparing low-carbon olefins and increasingly causes
The attention of people.
The MTP techniques of methanol ethylene, the MTO techniques of propylene and preparing propylene from methanol are current important Chemical Engineering Technologies.It should
The methanol that technology is synthesized using coal or natural gas produces low-carbon alkene as raw material, is development non-oil resource production ethylene, propylene etc.
The core technology of product.
MTO technology is the committed step in coal base alkene industrial chain, and technological process is predominantly suitably being grasped
Under the conditions of work, using methanol as raw material, suitable catalyst (ZSM-5 zeolite catalyst, SAPO-34 molecular sieves etc.) is chosen, solid
Pass through preparing low-carbon olefin through methanol dehydration in fixed bed and vulcanization bed reactor.According to the difference of purpose product, MTO technology
Be divided into methanol ethylene, propylene (methanol-to-olefin, MTO), preparing propylene from methanol (methanol-to-propylene,
MTP).The representative technology of MTO techniques has AP Oil company (UOP) and Hydro company (Norsk Hydro) joint development
UOP/Hydro MTO technologies, the DMTO technologies of Dalian Inst of Chemicophysics, Chinese Academy of Sciences's autonomous innovation research and development；MTP techniques
Representative technology have Lucci corporation (Lurgi) develop LurgiMTP technologies and the independent research of Tsinghua University of China FMTP skills
Art.
Entirely reaction can be divided into two stages to methanol-to-olefins：Water smoking, cracking reaction stage
1. the water smoking
2CH3OH→CH3OCH3+H2O+Q
2. the cracking reaction stage
The catalysis that the reaction process is mainly dehydration reaction product dimethyl ether and unconverted material benzenemethanol carries out on a small quantity is split
Solution reaction, including：
Main reaction (generates alkene)：
nCH3OH→CnH2n+nH2O+Q
nCH3OH→2CnH2n+nH2O+Q
N=2 and 3 (main), 4,5 and 6 (secondary)
Any of the above olefin product is gaseous state.
Side reaction (generates alkane, aromatic hydrocarbons, oxycarbide and coking)：
(n+1)CH3OH→CnH2n+2+C+(n+1)H2O+Q
(2n+1)CH3OH→2CnH2n+2+CO+2nH2O+Q
(3n+1)CH3OH→3CnH2n+2+CO2+(3n-1)H2O+Q
N=1,2,3,4,5 ... ...
nCH3OCH3→CnH2n-6+3H2+nH2O+Q
N=6,7,8 ... ...
The above product has gaseous state (CO, H2、H2O、CO2、CH4Equal alkane, aromatic hydrocarbons etc.) and solid-state (macromolecule hydrocarbon and coke)
Point.
Methanol is after dehydration, cracking, separation, the still second containing 5~100ppm in the ethylene feed of deethanizer overhead
Alkynes, it influences the polymerization process of ethylene, and product quality is caused to decline, and needs by selecting method of hydrotreating to be removed.Ethylene
The selection of trace acetylene plus hydrogen have extremely important influence to the polymerization process of ethylene in material, in addition to ensureing to add hydrogen with enough
Activity, under conditions of low acetylene content have it is good remove alkynes performance, ensure that the acetylene content of reactor outlet is up to standard, instead
It answers the hydrogen content that device exports up to standard outer, also requires the selectivity of catalyst excellent, the generation second that ethylene is as few as possible can be made
Alkane, it is ensured that hydrogenation process does not bring the loss of device ethylene.
The selection of trace acetylene adds hydrogen mainly to use single hop reactor process in methanol-to-olefins device ethylene feed at present.
Reactor inlet material forms：Ethylene >=99.99% (Φ), acetylene 5~100ppm, CO 1~10ppm, H2/C2H2=2~6.
1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-1, 25 DEG C~60 DEG C of inlet temperature.
Alkynes and diolefin hydrogenate catalyst are by the way that noble metal such as palladium is supported on porous Inorganic material carrier
On obtained (US4762956).In order to increase the selectivity of catalyst, the green oil that oligomerization generates when reducing by adding hydrogen is led
The catalyst inactivation of cause, the prior art use the method for adding that such as group ib element is co-catalysis component in the catalyst：
Pd-Au (US4490481), Pd-Ag (US4404124), Pd-Pb (US3912789), or alkali or alkaline earth metal is added
(US5488024) etc., carrier used has aluminium oxide, silica (US5856262), loyal green stone of honeycomb (CN1176291) etc.
Deng.
US5856262 is reported using the modified silica of potassium hydroxide (or hydroxide of barium, strontium, rubidium etc.) as carrier,
The method for preparing low in acidity palladium catalyst, in air speed 3000h-1, 35 DEG C of inlet temperature, entrance acetylene molar fraction 0.71%, hydrogen
Under conditions of alkynes molar ratio 1.43, outlet acetylene molar fraction is less than 0.1 μ L/L, and ethylene selectivity is up to 56%.Patent
Using aluminium oxide as carrier, addition co-catalyst silver acts on US4404124 with palladium, is prepared for the C2 hydrogenation catalysis of function admirable
Agent.The catalyst, which has, reduces ethane production quantity, inhibits the acetylene being adsorbed on catalyst surface to carry out partial hydrogenation dimerization anti-
It answers, 1,3-butadiene is inhibited to generate, reduce the characteristics of green oil generates, improves ethylene selectivity, reduce oxygenatedchemicals production quantity,
It is applied widely in ethylene industry.However, above-mentioned catalyst is prepared using infusion process, limited by preparation method
System, metal dispersity is only 30% or so, and there is also many deficiencies for catalyst performance, still there is further improved necessity.
CN101745389A discloses a kind of egg-shell catalyst for preparation of ethylene through selective hydrogenation of acetylene, belongs to oil
(natural gas) chemical products synthesize and new catalytic material technical field, be related to it is a kind of to preparation of ethylene through selective hydrogenation of acetylene have it is excellent
The egg-shell catalyst of good catalytic performance.It is characterized in that with aluminium oxide (Al2O3) bead be carrier, using infusion process prepare activity
Component palladium is in the loaded catalyst of eggshell type distribution, and using Ag to eggshell type Pd/Al2O3Catalyst is modified.Pd is loaded
It is 1~5 that amount, which is 0.01~0.1wt%, Ag and Pd atomic ratio,.The invention has the advantages that the one kind provided is used for second
Alkynes selects the egg-shell catalyst of Hydrogenation ethylene, can be under the conditions of high conversion of alkyne, especially in the acetylene close to 100%
When conversion ratio, high ethylene selectivity is realized.
Traditional Pd-Ag bimetallics selective hydrogenation catalyst is prepared using aqueous solution infusion process.Using sub-dip method
When, a kind of group of branch it is more be enriched in carrier surface, and another component is enriched in outer surface, only part metals atom phase
Mutually infiltration, forms alloy structure.When using total immersion method, due to the interaction of the presoma and carrier of two metal ion species
Difference and surface tension and solvation are hardly formed the uniform load of two kinds of components, also can only partly form alloy knot
Structure.It is often selectively preferable in initial reaction stage when this catalyst is applied to C 2 fraction selective hydrogenation, with prolonging for run time
Long, selectivity constantly declines, and generally runs 3~6 months and just needs to regenerate, economic loss is larger.
CN201110086174.0 on carrier by adsorbing specific high-molecular compound, in carrier surface certain thickness
Macromolecule wrapped layer is formed, with compound and high molecular weight reactive with functional base, with can be complexed with active component
Function base, complex reaction is occurred on carrier surface function base by active component, ensures active component orderly and height point
It dissipates.Using the patented method, the specific high-molecular compound of carrier adsorption carries out chemistry by the hydroxyl of aluminium oxide with macromolecule
Absorption, the amount of carrier adsorption high-molecular compound will be limited by aluminium oxide hydroxyl quantity；Macromolecule by functionalization with
The complexing of Pd 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；Preparing C2 hydrogenation catalyst using this method, there is also the disadvantages of technological process complexity.
Invention content
The purpose of the present invention is to provide a kind of selection method of hydrotreating of trace acetylene in methanol-to-olefins device.Pass through choosing
Active component high degree of dispersion, the Pd-Pb catalyst with height alloy structure are selected, hydrogenation selectivity is improved, improves ethylene
Increment improves device operation stability and economic benefit.
Inventor has found, when catalyst prepared by preparation method using the present invention, the Pd in catalyst is separated by Pb, makes
The spacing for obtaining activated centre widens, and catalyst choice improves, and therefore the surface coking rate of catalyst is greatly reduced, be catalyzed
The agent cycle of operation extends, and economic benefits are apparent.
The present invention provides a kind of selection method of hydrotreating of trace acetylene in methanol-to-olefins device.Thermal insulation for adding hydrogen
Bed reactor is located at after dethanizer, i.e., by two material of carbon from deethanizer overhead in methanol-to-olefins device, enters
Adiabatic reactor reactor carries out selection plus hydrogen, it is characterised in that：Pd-Pb series catalysts are housed, with Al in adiabatic reactor reactor2O3Or
Al2O3With other hopcalites be carrier, by the quality of catalyst be 100% in terms of, wherein Pd contents 0.025~
The specific surface area of 0.06%, preferably 0.05~0.7%, catalyst is 15~60m2/ g, pore volume are 0.15~0.70mL/g；
The catalyst is combined in preparation process, by carrier with hydroxyl-bipyridyl, and active component forms metal with hydroxyl-bipyridyl
Complex compound；Reaction condition is：25 DEG C~60 DEG C, 1.5~2.5MPa of reaction pressure of adiabatic reactor reactor inlet temperature, volume space velocity
2000~10000h-1。
The characteristics of Pd-Pb series catalysts used in the present invention is：The catalyst is to use PdPb- hydroxyls by the present invention
Base-bipyridyl/Al2O3Prepared by the method for precursor.
The catalyst preparation process of recommendation, includes at least：Hydroxyl dipyridyl derivatives are loaded into alumina support
On, then by the cation of the extra hydroxyl of hydroxyl dipyridyl derivatives and/or adjacent nitrogen base and Pd, Pb 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, Pb preferable complex reaction can occur for base and two nitrogen bases at ortho position.
The present invention is the selection method of hydrotreating of trace acetylene in methanol-to-olefins device, and it is mainly second to be formed in entrance raw material
Alkene, reactor inlet material composition：Ethylene >=99.99% (Φ), acetylene 5~100ppm, CO 1~10ppm, H2/C2H2=2~
20.25 DEG C~60 DEG C of reactor inlet temperature, 1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-1。
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, Pb is formed
The quantity of gold, the hydrogen that caltalyst phase is adsorbed is greatly reduced, and the trend that deep hydrogenation occurs for acetylene substantially reduces, catalyst
Selectivity significantly improves.
The acquisition of the catalyst preferably includes following steps：With hydroxyl bipyridyl organic solution, impregnated carrier, through dry
Hydroxyl-bipyridyl/Al is obtained after dry2O3Precursor, the mixed-cation solution for preparing Pd, Pb impregnate hydroxyl-bipyridyl/Al2O3
Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyls-bipyridyl/Al2O3Precursor.At a temperature of 300~600 DEG C
2~12h is roasted, required catalyst is obtained.
Carrier of the present invention is alumina series carrier, preferably Al2O3Or preferably mainly contain Al2O3, wherein doped with it
Its hopcalite, other oxides are silica, titanium oxide, magnesia and/or calcium oxide.The Al2O3For γ,
δ, θ, α or in which several mixing crystal form Al2O3, preferably θ, α or its mix crystal form Al2O3。
Carrier can be spherical in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
Following procedure may be used to implement in catalyst preparation of the present invention, which can be divided into the progress of 3 steps.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
Hydroxyl dipyridyl derivatives organic solution is mixed with carrier, solution is made to be absorbed, in 20 DEG C~60 DEG C temperature
The lower reaction of degree 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl bipyridyl/Al2O3Preceding body
Body；The volume of organic solution is preferably greater than 80% equal to carrier total volume.
B.PdPb- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Connection hydroxyl obtained by step A is added in the mixed-cation solution for preparing Pd, Pb at a temperature of 30 DEG C~100 DEG C
Pyridine/Al2O3Precursor reaction 2~for 24 hours, solid particle is taken out after cooling, it is dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyls
Base-bipyridyl/Al2O3Precursor；The mixed-cation liquor capacity of Pd, Pb are preferably hydroxyl-bipyridyl/Al2O3Precursor
The 80%~120% of total volume, the ratio between the molal quantity of best Pb and the molal quantity of Pd are 0.4~5, and it is 1.5 preferably to adjust pH value
~4.0.
C. the preparation of catalyst
PdPb- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature,
Make PdPb- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
In catalyst in use, can H be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
In step, hydroxyl dipyridyl derivatives are hydroxyl 2,2 ,-dipyridyl derivatives, hydroxyl 3,
3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.It may insure Al2O3Extensive chemical suction is generated to it
While attached, the extra hydroxyl two nitrogen bases adjacent with bipyridyl are combined with active component Pd, Pb.In terms of molal quantity,
The molal quantity of best hydroxyl-bipyridyl/(Pd+Pb) is 20~80.
Solvent is added in step in order to make hydroxyl-bipyridyl be completely dissolved, to be conducive to suction of the macromolecule on carrier
Attached, solvent can be ethyl alcohol and ether.How much is the addition of solvent, and mainly to control institute's solubilizer can make macromolecule completely molten
Solution.
In stepb, the solution of palladium-lead can be the soluble salt solutions of palladium, lead, such as can be Pd (NO3)2、Pb
(NO3)2Mixed solution.Palladium, lead salt dosage are can make Pd, Pb content of final catalyst in the mixed solution.
In step C, roasting carries out in having oxygen atmosphere, and calcination temperature of the present invention is preferably 300 DEG C~600 DEG C.
In catalyst in use, can H be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
Inventor also found, when carrying out selective hydrogenation reaction using this method, the active of catalyst reaction, selectivity are
It is significantly improved, catalyst stability enhancing.
Description of the drawings
Attached drawing 1 is the C2 hydrogenation technological process using a kind of methanol-to-olefins using sequence separation process of the present invention
Figure.
1-reactor, 2-regenerators, 3-separators, 4-caustic wash towers, 5-drying towers, 6-domethanizing columns, 7-de- second
Alkane tower, 8-ethylene separation towers, 9-propylene separation towers, 10-depropanizing towers, 11-ethylene finishing reactors.
Specific implementation mode
Embodiment 1
Weigh Φ 4.2, specific surface area 16.0m2/ g, hole hold 0.38mL/g, the spherical α-Al of heap density 0.86g/ml2O3
Carrier 500g.
By 162g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned molten
In liquid, after after standing 2h 4,4- dihydroxy -2,2- bipyridyls being loaded on alumina support completely, 80 DEG C of dry 10h are obtained
To hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.36g Pd (NO3)2、5.19g Pb(NO3)2500mL deionized waters are dissolved in, 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 2.5h, inclines
Go out raffinate, obtains Pd Pb- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Pb)=50).110℃
2h is roasted in air atmosphere at a temperature of 550 DEG C after dry 4h, obtains (Pd-Pb)/Al2O3Catalyst.
It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas,
It is restored at a temperature of 120 DEG C, obtains load type palladium-lead catalyst S-1.It is that 0.030%, Pb contents are to measure catalyst Pd contents
0.63%.
Comparative example 1
Weigh Φ 4.2, specific surface area 16.0m2/ g, hole hold 0.38mL/g, the spherical α-Al of heap density 0.86g/ml2O3
Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC 8.9g are dissolved completely in 800mlTHF (tetrahydrofuran), by above-mentioned carrier impregnation to above-mentioned solution,
PVC is set to be adsorbed in Al after standing 2h2O3Surface obtains PVC/Al after dry2O3It is spare.
By 119.28g dicyandiamides and 4.0gNa2CO3, above-mentioned PVC/Al is added2O3Flow back 1h, be cooled to room temperature, spend from
Sub- water washing is dried to obtain functionalization PVC/Al to neutrality2O3, spare.
B、Pd-Pb-polymer/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2、Pb(NO3)2It is dissolved in the 2400mL deionized waters containing appropriate nitric acid, is heated to completely molten
Solution, it is 1.5 to adjust pH value.Take the functionalization-PVC/Al prepared in step A2O3Presoma adds it to Pd (NO3)2、Pb
(NO3)2Mixed solution in, stir 30min, pour out raffinate, above-mentioned product be washed with deionized to neutrality, (Pd- is obtained
Pb)-PVC/Al2O3Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h, obtain oxidation state (Pd-Pb)/Al in air atmosphere2O3Catalysis
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas, at 120 DEG C
At a temperature of, obtain load type palladium-lead catalyst D-1.It is 0.63% that measure catalyst Pd contents, which be 0.030%, Pb contents,.
Using the C2 hydrogenation technique of methanol-to-olefins, process flow chart is as shown in Fig. 1, is evaluated and is filled using 500mL
It sets, raw material composition and working condition are shown in Table 1.
1 evaluation parameter of table
| Project | Parameter | Project | Parameter |
| Air speed | 2500/h | Inlet temperature | 32℃ |
| Acetylene content | 4.99μL/L | Loaded catalyst | 300mL |
2 catalyst 200h performance average values of table
Embodiment 2
Weigh Φ 4.2mm, high 4.2mm, specific surface area 55cm2/ g, Kong Rongwei 0.41ml/g, heap density are 0.74g/ml
Cylindrical θ-Al2O3Carrier 500g.
By 40.2g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned molten
In liquid, after after standing 8h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 90 DEG C of dry 8h obtain hydroxyl
Base-bipyridyl/Al2O3Precursor.
Weigh 0.73g Pd (NO3)2、2.60g Pb(NO3)2500mL deionized waters are dissolved in, 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, remaining solid dry 6h at 110 DEG C.Obtain (hydroxyl-bipyridyl molal quantity：(Pd+Pb)=20).
By above-mentioned PdPb- hydroxyls-bipyridyl/Al2O3Precursor, 500 DEG C of roasting 4h in air atmosphere.Use preceding placement
It is 99.9% with hydrogen purity in fixed-bed reactor, air speed 200h-1Gas born at a temperature of 120 DEG C
Load type palladium-lead catalyst S-2.It is 0.32% that measure catalyst Pd contents, which be 0.060%, Pb contents,.
Comparative example 2
Weigh Φ 4.0mm, length 4.0mm, specific surface area 80m2Column δ-the Al of/g, Kong Rongwei 0.60ml/g2O3It carries
Body 500g.
Weigh 0.73g Pd (NO3)2、2.60g Pb(NO3)2, 300mL deionized waters are dissolved in, it is 2.5 to adjust pH value, is configured to
Mixed solution.Above-mentioned carrier is added in the solution prepared, stirs 30min, it is dry after in 550 DEG C of roasting temperature 2h,
Obtain Pd-Pb/Al2O3Catalyst.It is positioned in fixed-bed reactor before use, uses H2In air speed 400h-1, 120 DEG C of temperature,
Reduction treatment 8h obtains load type palladium-lead catalyst D-2.It is that 0.060%, Pb contents are to measure catalyst Pd contents
0.32%.
Using the C2 hydrogenation technique of methanol-to-olefins, process flow chart is as shown in Fig. 1, is evaluated and is filled using 500mL
It sets, raw material composition and working condition are shown in Table 1.
3 evaluation parameter of table
| Project | Parameter | Project | Parameter |
| Air speed | 6000/h | Inlet temperature | 32℃ |
| Acetylene content | 10μL/L | Loaded catalyst | 300mL |
4 catalyst 200h performance average values of table
Embodiment 3
Weigh Φ 3.3mm, specific surface area 38.0m2/ g, Kong Rongwei 0.19ml/g, heap are more spherical than the tooth for 0.78g/ml
Carrier 500g, wherein aluminium oxide 460g, titanium oxide 40g, aluminium oxide crystal form are θ-Al2O3。
By 87.52g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation upper
It states in solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 100 DEG C dry
Dry 6h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.49g Pd (NO3)2,1.30g Pb(NO3)2It is dissolved in 500mL deionized waters, it is 3.2 to adjust pH value, is prepared
At mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 12h,
Raffinate is poured out, remaining solid dry 8h at 105 DEG C obtains PdPb- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl
Molal quantity：(Pd+Pb)=80), spare.
By the presoma of above-mentioned preparation, 460 DEG C of roasting 6h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain load type palladium-lead catalyst S- at a temperature of 120 DEG C
3.It is 0.160% that measure catalyst Pd contents, which be 0.040%, Pb contents,.
Comparative example 3
Weigh Φ 3.0mm, specific surface area 40.0m2/ g, Kong Rongwei 0.18ml/g, heap are more spherical than the tooth for 0.78g/ml
Carrier 500g, wherein aluminium oxide 460g, titanium oxide 40g, aluminium oxide crystal form are θ-Al2O3。
A, the preparation of functionalization haloflex (CPE)
CPE 16.0g are dissolved completely in 800mlTHF, 480g dicyandiamides and 4.0gNa is added2CO3, CPE reflux is added
It 2 hours, is cooled to room temperature, is washed with deionized to neutrality, it is spare to obtain functionalization CPE.
B, (Pd-Pb)-high-molecular complex/Al2O3The preparation of presoma
Weigh 0.49g Pd (NO3)2,1.30g Pb(NO3)2, 1ml nitric acid is measured, above-mentioned functionalization CPE solution is added to
In, 60min is stirred, (Pd-Pb)-CPE is obtained.
By 500g carriers be added mixed solution in, stand 4h after being sufficiently stirred, by above-mentioned product be washed with deionized to
Neutrality, remaining solid dry 8h at 100 DEG C, obtains (Pd-Pb)-high-molecular complex/Al2O3Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 450 DEG C of roasting 8h, obtain oxidation state (Pd-Pb)/Al in air atmosphere2O3Catalysis
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas, at 120 DEG C
At a temperature of, obtain load type palladium-lead catalyst D-3.It is 0.160% that measure catalyst Pd contents, which be 0.040%, Pb contents,.
Using the C2 hydrogenation technique of methanol-to-olefins, process flow chart is as shown in Fig. 1, is evaluated and is filled using 500mL
It sets, raw material composition and working condition are shown in Table 1.
5 evaluation parameter of table
6 catalyst 200h performance average values of table
Embodiment 4
Weigh Φ 4.2mm, high 4.2mm, specific surface area 46.0m2/ g, Kong Rongwei 0.38ml/g, heap ratio are 0.76g/ml
Tooth ball type carrier 500g, wherein aluminium oxide 460g, titanium oxide 40g, aluminium oxide crystal form be θ-Al2O3。
By 79.89g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation upper
It states in solution, after after standing 10h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 100 DEG C dry
Dry 5h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.61g Pd (NO3)2, 3.90g Pb (NO3)2It is dissolved in 500mL deionized waters, it is 3.8 to adjust pH value, is prepared
At mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 12h,
Raffinate is poured out, remaining solid dry 6h at 115 DEG C obtains PdPb- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl
Molal quantity：(Pd+Pb)=30), spare.
By the presoma of above-mentioned preparation, in air atmosphere, 510 DEG C of roasting 4h.Fixed bed reaction dress is positioned over before use
It is 99.9% with hydrogen purity in setting, air speed 200h-1Gas obtain load type palladium-lead catalyst at a temperature of 120 DEG C
S-4.It is 0.48% that measure catalyst Pd contents, which be 0.05%, Pb contents,.
Comparative example 4
Weigh Φ 4.2mm, high 4.2mm, specific surface area 46.0m2/ g, Kong Rongwei 0.38ml/g, heap ratio are 0.76g/ml
Tooth ball type carrier 500g, wherein aluminium oxide 460g, titanium oxide 40g, aluminium oxide crystal form be θ-Al2O3。
By 79.89g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 650mL ethanol solutions, by above-mentioned carrier impregnation upper
It states in solution, after after standing 10h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 100 DEG C dry
Dry 5h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate 0.61g Pd (NO3)2, 2.0g AgNO3It is dissolved in the 500mL deionized waters containing appropriate nitric acid, heats
To being completely dissolved, it is 3.8 to adjust pH value.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, stirring
60min stands 12h, pours out raffinate, and remaining solid dry 6h at 115 DEG C obtains Pd-Ag- hydroxyls-bipyridyl/Al2O3Preceding body
Body (hydroxyl-bipyridyl molal quantity：(Pd+Ag)=30), spare.
By the presoma of above-mentioned preparation, in air atmosphere, 510 DEG C of roasting 4h.Fixed bed reaction dress is positioned over before use
It is 99.9% with hydrogen purity in setting, air speed 200h-1Gas obtain load type palladium-silver catalyst at a temperature of 120 DEG C
D-4.It is 0.24% that measure catalyst Pd contents, which be 0.05%, Ag contents,.
Using the C2 hydrogenation technique of methanol-to-olefins, process flow chart is as shown in Fig. 1, is evaluated and is filled using 500mL
It sets, raw material composition and working condition are shown in Table 1.
8 evaluation parameter of table
9 catalyst 200h performance average values of table
It, will be organic and when active component content is identical as can be seen that compared with using traditional preparation catalyst
Macromolecular grafted functional group simultaneously loads on a catalyst support, then the active solution of the carrier impregnation is obtained organic polymer gold
The method of category complex compound prepares catalyst and compares, method of hydrotreating using the present invention, and the activity and selectivity of hydrogenation reaction are significantly
Better than traditional method of hydrotreating, outlet acetylene content is significantly lower than other two kinds of method of hydrotreating, and Ethylene purity improves, so as to
The performance of polymer grade ethylene product is improved very well.The reduction of green oil simultaneously so that the activated centre of catalyst is not by by-product
It is covered, catalyst activity and selectivity are kept well, and catalyst service life extends.
Claims (15)
1. the selection method of hydrotreating of trace acetylene in a kind of methanol-to-olefins device will come from deethanization in methanol-to-olefins device
Two material of carbon of column overhead carries out selection plus hydrogen into adiabatic reactor reactor, it is characterised in that：It is equipped in fixed bed reactors
Pd-Pb series catalysts, with Al2O3Or Al2O3It is carrier with other hopcalites, with the quality of catalyst for 100%
Meter, wherein Pd contents 0.025~0.06%, Pb contents are 0.05~0.7%, and the specific surface area of catalyst is 15~60m2/ g,
Pore volume is 0.15~0.70mL/g；The catalyst passes through carrier and hydroxyl dipyridyl derivatives knot in preparation process
It closes, hydroxyl dipyridyl derivatives form metal complex with active component；Reaction condition is：Adiabatic reactor reactor inlet temperature
25 DEG C~60 DEG C of degree, 1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-1。
2. selection method of hydrotreating according to claim 1, it is characterised in that catalyst preparation process includes at least：Passing through will
Hydroxyl dipyridyl derivatives load on carrier, then pass through the extra hydroxyl of hydroxyl dipyridyl derivatives and/or phase
The cation of adjacent nitrogen base and Pd, Pb forms complex ion.
3. selection method of hydrotreating according to claim 2, it is characterised in that hydroxyl dipyridyl derivatives are hydroxyl
2,2 ,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives.
4. selection method of hydrotreating according to claim 1, it is characterised in that the preparation process of catalyst includes the following steps：
With hydroxyl dipyridyl derivatives organic solution, impregnated carrier obtains hydroxyl-bipyridyl/Al after drying2O3Precursor is matched
The mixed-cation solution of Pd, Pb processed impregnate hydroxyl-bipyridyl/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, it obtains
PdPb- hydroxyls-bipyridyl/Al2O3Precursor；In 300~600 DEG C of 2~12h of roasting temperature, required catalyst is obtained.
5. selection method of hydrotreating according to claim 1, it is characterised in that carrier Al2O3Or mainly contain Al2O3Wherein
Doped with other hopcalites, other oxides are silica, titanium oxide, magnesia and/or calcium oxide；The oxygen
Change aluminium is γ, δ, θ, alpha-crystal form or in which several mixing crystal form Al2O3。
6. selection method of hydrotreating according to claim 5, it is characterised in that aluminium oxide θ, α or its mixing crystal form Al2O3。
7. selection method of hydrotreating according to claim 1, it is characterised in that carrier is spherical shape, cylindrical, circular ring shape, item
Shape, cloverleaf pattern or bunge bedstraw herb shape.
8. according to any selection method of hydrotreating in claim 1-7, it is characterised in that the preparation method of catalyst includes
Following steps：
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By hydroxyl dipyridyl derivatives organic solution, mixed with carrier, at a temperature of 20 DEG C~60 DEG C react 2~for 24 hours, take
Go out solid particle, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl bipyridyl/Al2O3Precursor；
B.PdPb- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Pb mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with bipyridyl hydroxyl obtained by step A/
Al2O3Precursor reaction 2~for 24 hours, solid particle is taken out after cooling, it is dry at 60 DEG C~150 DEG C, obtain PdPb- hydroxyls-connection
Pyridine/Al2O3Precursor；
C. the preparation of catalyst
PdPb- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor is in 300~600 DEG C of 2~12h of roasting temperature so that
PdPb- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
9. selection method of hydrotreating according to claim 8, it is characterised in that hydroxyl-bipyridyl/(Pd+Pb) in step A
Molal quantity is 20~80：1.
10. selection method of hydrotreating according to claim 8, it is characterised in that in stepb, the mixed-cation of Pd, Pb
Solution is the mixed solution of palladium nitrate and plumbi nitras.
11. selection method of hydrotreating according to claim 8, it is characterised in that in stepb, the molal quantity of Pb and rubbing for Pd
The ratio between your number is 4~12：1.
12. selection method of hydrotreating according to claim 8, it is characterised in that in stepb, adjust the mixing sun of Pd, Pb
Solion pH value is 1.5~4.0.
13. selection method of hydrotreating according to claim 1, it is characterised in that adiabatic reactor reactor reaction bed number is single hop
Bed.
14. selection method of hydrotreating according to claim 1, it is characterised in that hydrogen is 2~20 with acetylene volume ratio：1.
15. selection method of hydrotreating according to claim 1, it is characterised in that can contain in hydrogenating materials gas and be not higher than
The C-4-fraction of 100ppm.
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Citations (2)
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| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN102206130A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081366A (en) * | 2007-02-02 | 2007-12-05 | 中国石油天然气股份有限公司长庆石化分公司 | Pd radicel duplex metal selective hydrogenation catalyzer and method for preparing the same and application thereof |
| CN102206130A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C2 fraction |
Non-Patent Citations (3)
| Title |
|---|
| POLYMER-SUPPORTED 2，2’-DIPYRIDYLMETHANE：SYNTHESIS AND FORMATION OF TRANSITION METAL COMPLEXES;BJORN ELMAN等;《Journal of Organometallic Chemistry》;19851231;第294卷;第117-122页 * |
| 络合催化剂的多相化;鲁奇林等;《辽宁师范大学自然科学学报》;19911231;第14卷(第1期);第41-45,79页 * |
| 高分子负载加氢催化剂中钯流失的研究 Ⅰ.高分子载体的影响;何炳林等;《应用化学》;19891231;第6卷(第2期);第52-55页 * |
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