CN105732271B - The front-end hydrogenation method of trace acetylene in methanol-to-olefins device - Google Patents
The front-end hydrogenation method of trace acetylene in methanol-to-olefins device Download PDFInfo
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Abstract
The present invention relates to a kind of front-end hydrogenation methods of trace acetylene in methanol-to-olefins device, for adding the adiabatic reactor reactor of hydrogen to be located at before domethanizing column or dethanizer, it is characterised in that：Pd Cu series catalysts are housed, which is combined in preparation process, by carrier with hydroxyl dipyridyl derivatives, and metal complex is formed with carrier-bound hydroxyl dipyridyl derivatives and active component in fixed bed reactors；The selectivity of method of hydrotreating using the present invention, hydrogenation reaction is significantly better than traditional method of hydrotreating, and ethylene loss reduces；Hydrogenation activity is excellent, it exports acetylene content and is significantly lower than other two kinds of method of hydrotreating, Ethylene purity improves, so as to improve the performance of polymer grade ethylene product very well, the reduction of green oil simultaneously, so that the activated centre of catalyst is not covered by by-product, catalyst activity and selectivity are kept well, and catalyst service life extends.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, the front-end hydrogenation of trace acetylene in especially a kind of methanol-to-olefins device
Method.
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 Lurgi MTP 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 separative element of methanol-to-olefins device generally uses the sequence separation process of Lummus companies at present.Ethylene
Refine two kinds of adoptable front-end hydrogenation, back end hydrogenation techniques.Hydrogenation reactor is front-end hydrogenation, hydrogenation reaction before being located at separative element
Device is back end hydrogenation after being located at separative element.Methanol-to-olefins device generally uses back end hydrogenation technique at present, i.e., by pyrolysis product
The ethylene isolated carries out hydrofinishing removing acetylene, and propylene does not set hydrofining reactor, the four mixing group of carbon isolated
Divide and carries out selective hydrogenation and removing butadiene.But there are drawbacks for the technique, are refined respectively to ethylene, propylene again using first detaching,
Plant energy consumption is relatively high.Therefore, it is proposed to before separative element, finishing reactor is set, is detached again after removing acetylene
Front-end hydrogenation process route helps to reduce plant energy consumption, improves device economic benefit.
For front-end hydrogenation technique, in methanol-to-olefins device ethylene feed the selection of trace acetylene add hydrogen mainly use single hop
Reactor process.The volume content of each substance is as follows：Acetylene 1~10ppm of 5~100ppm, CO, hydrogen use in material in itself
The hydrogen contained, H2Content is generally 1.2%~2.5%.1.5~2.5MPa of reaction pressure, 2000~10000h of air speed-1, enter
25 DEG C~50 DEG C of temperature of mouth.Reactor content composition is complex, and concrete composition is by table 1.
1 methanol-to-olefins device front-end hydrogenation technique acetylene hydrogenation reactor entrance material of table forms
| Component | Compositing range (v%) | Composition citing (v%) |
| H2 | 1.2~2.5 | 1.72 |
| N2 | 0.5~1.0 | 0.72 |
| O2 | 0.005~0.015 | 0.01 |
| CO | 0.60~1.0 | 0.85 |
| CO2 | 0.20~0.60 | 0.38 |
| H2S | 0~0.0008 | 0.0001 |
| CH4 | 6~10 | 8.09 |
| C2H2 | 0~0.01 | 0.0005 |
| C2H6 | 1~2 | 1.64 |
| C2H4 | 40~60 | 51.10 |
| C3H8 | 1.5~3 | 2.06 |
| C3H6 | 15~40 | 20.91 |
| C3H4 | 0~0.01 | 0.001 |
| C4 | 3~6 | 4.49 |
| C5+ | 6~10 | 8.03 |
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-Cu (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 and macromolecule of aluminium oxide
Absorption, the amount of carrier adsorption high-molecular compound will be limited by the hydroxyl quantity of aluminium oxide；By the macromolecule of functionalization
Not strong with the complexing of Pd, activity component load quantity does not reach requirement sometimes, and residual fraction active component is gone back in maceration extract, is made
It is improved at catalyst cost；Preparing C2 hydrogenation catalyst using this method, there is also the disadvantages of technological process complexity.
In the higher trace acetylene selection hydrogenation process of air speed, especially in the higher front-end hydrogenation technical process of CO contents
In, add hydrogen operating mode more demanding to catalyst activity, and be the bimetal supported catalyst of auxiliary agent by active component, Ag of Pd
For the type device, there are reaction temperature height, activity cannot preferably meet device requirement, be susceptible to the shortcomings that leaking alkynes, need
More suitable auxiliary agent is selected to prepare catalyst, to meet the hydrogenation requirements of device.
Invention content
The purpose of the present invention is to provide a kind of front-end hydrogenation methods of trace acetylene in methanol-to-olefins device.Pass through selection
Active component high degree of dispersion, the Pd-Cu catalyst with height alloy structure, improve hydrogenation selectivity, improve ethylene increasing
Amount, improves device operation stability and economic benefit.
The inventors discovered that when the Pd in catalyst prepared by preparation method using the present invention, catalyst is separated by Cu,
So that the spacing in activated centre widens, catalyst choice improves, and therefore the surface coking rate of catalyst is greatly reduced, urge
The agent cycle of operation extends, and economic benefits are apparent.
The present invention provides a kind of front-end hydrogenation methods of trace acetylene in methanol-to-olefins device.Adiabatic reactor for adding hydrogen
Reactor is located at before domethanizing column or dethanizer, carbon one, two and of carbon in methanol-to-olefins device from drying tower bottom of tower
Carbon 3 material carries out selection plus hydrogen into adiabatic reactor reactor, it is characterised in that：It is urged equipped with Pd-Cu systems in adiabatic reactor reactor
Agent, with Al2O3Or Al2O3It is carrier with other hopcalites, is in terms of 100% by the quality of catalyst, wherein Pd contains
It is 0.02~0.3% to measure 0.015~0.050%, Cu contents, and the specific surface area of catalyst is 20~60m2/ g, pore volume are
0.15~0.70mL/g；The catalyst is combined in preparation process, by carrier with hydroxyl-bipyridyl, the hydroxyl connection on carrier
Pyridine forms metal complex with active component；Reaction condition is：30 DEG C~50 DEG C of adiabatic reactor reactor inlet temperature, reaction pressure
1.5~2.5MPa of power, 5000~15000h of air speed-1。
The characteristics of Pd-Cu series catalysts used in the present invention is：The catalyst is to use PdCu- 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 on carrier, then are led to
It crosses the extra hydroxyl of hydroxyl dipyridyl derivatives and/or nitrogen base and the cation of Pd, Cu forms complex ion.
The hydroxyl dipyridyl derivatives of the present invention, preferably hydroxyl 2,2, it is-dipyridyl derivatives, hydroxyl
3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, because it is combined rear extra hydroxyl with aluminium oxide
With Pd, Cu preferable complex reaction can occur for base and two nitrogen bases at ortho position.
The present invention is 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, propylene, reactor inlet material composition are shown in Table 1.30 DEG C~50 DEG C, 1.5~2.5MPa of reaction pressure of reactor inlet temperature,
5000~10000h 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, Cu is formed
The quantity of gold, the hydrogen that caltalyst phase is adsorbed is greatly reduced, and the trend that deep hydrogenation occurs for acetylene substantially reduces, catalyst
Selectivity significantly improves.
The acquisition of the catalyst preferably includes following steps：With the organic solution of hydroxyl dipyridyl derivatives, dipping
Carrier obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution for preparing Pd, Cu impregnate hydroxyl-connection
Pyridine/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdCu- hydroxyls-bipyridyl/Al2O3Precursor.300~
600 DEG C of 2~12h of roasting temperature, obtain required catalyst.
Carrier of the present invention is preferably aluminium oxide, or mainly contains Al2O3, wherein also doped with other hopcalites,
Other oxides are silica, titanium oxide, magnesia and/or calcium oxide.The aluminium oxide be γ, δ, θ, alpha-crystal form or in which
Several mixing crystal forms, preferably θ, α or its mixing crystal form.
Carrier can be spherical in the present invention, cylindrical, circular ring shape, bar shaped, cloverleaf pattern, bunge bedstraw herb shape etc..
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
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, solution is made to be absorbed, at 20 DEG C~60 DEG C
At a temperature of reaction 2~for 24 hours, take out solid particle, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
Hydroxyl dipyridyl derivatives organic solution volume is preferably equal to or greater than the 80% of carrier total volume.
B.PdCu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Cu mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl-bipyridyl 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 PdCu- hydroxyls-connection
Pyridine/Al2O3Precursor.The volume of the mixed-cation solution of Pd, Cu is preferably hydroxyl-bipyridyl/Al2O3Precursor is overall
Long-pending 60%~200%；The ratio between the molal quantity of best Cu and molal quantity of Pd are 0.4~5, preferably adjust pH value be 1.0~
4.0。
C. the preparation of catalyst
PdCu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor in 300~600 DEG C of 2~12h of roasting temperature,
Make PdCu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
In catalyst in use, can H be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
In step, hydroxyl dipyridyl derivatives, preferably hydroxyl 2,2, it is-dipyridyl derivatives, hydroxyl
3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.It may insure Al2O3Reinforcing is generated to it
While learning absorption, the extra hydroxyl two nitrogen bases adjacent with bipyridyl are combined with active component Pd, Cu.With molal quantity
The molal quantity of meter, hydroxyl-bipyridyl/(Pd+Cu) is 3~100.
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-copper can be the soluble salt solutions of palladium, copper, such as can be Pd (NO3)2、CuNO3
Mixed solution.Palladium, mantoquita dosage are can make Pd, Cu content of final catalyst in the mixed solution.
In step C, what roasting preferably carried out in having oxygen atmosphere, calcination temperature of the present invention is preferably 350 DEG C~500
℃。
In catalyst in use, can H be used catalyst made from above method in the reactor2Reduction treatment is carried out,
Obtain reduction-state catalyst.
The present inventors have additionally discovered that when carrying out selective hydrogenation reaction using this method, activity, the selectivity of catalyst reaction
It is significantly improved, catalyst stability enhancing.
Meanwhile the method for the present invention prepares palladium-copper catalyst, alloy structure is more suitably applied to catalyst activity requirement
Higher working condition.Air speed is higher, in raw material in the higher trace acetylene selection hydrogenation process of CO contents, has reaction temperature
Spend low, the good advantage of hydrogenation activity.
Description of the drawings：
Attached drawing 1 is the C2 hydrogenation technological process using a kind of methanol-to-olefins using predepropanization technique of the present invention
Figure.
In figure：1-DME reactors；2-MTP reactors；3-pre- chilling separation；4-chillings detach；5-level Four are compressed；
6-level Four detach；7-drying towers；8- acetylene hydrogenation reactors；9-domethanizing columns；10-dethanizers.
Specific implementation mode
Embodiment 1
Weigh Φ 4.2mm, specific surface area 23.0m2/ g, hole hold 0.36mL/g, the spherical α-of heap density 0.87g/mL
Al2O3Carrier 500g.
By 87.72g 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 are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.44g Pd (NO3)2、2.59g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
1.5, it is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 10min,
2h is stood, raffinate is poured out, obtains PdAg- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity：(Pd+Cu)=
30).2h is roasted in air atmosphere at a temperature of 550 DEG C after 120 DEG C of dry 4h, obtains (Pd-Cu)/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 loaded catalyst S-1.It is that 0.036%, Cu contents are to measure catalyst Pd contents
0.18%.
Comparative example 1
Weigh Φ 4.2mm, specific surface area 23.0m2/ g, hole hold 0.36mL/g, the spherical α-of heap density 0.87g/mL
Al2O3Carrier 500g.
A, functionalized poly vinyl chloride (PVC)/Al2O3Preparation
PVC 8.9g are dissolved completely in 800mLTHF (tetrahydrofuran), by above-mentioned carrier impregnation to above-mentioned solution,
PVC is set to be adsorbed in Al after standing 2h2O3Surface, drying for standby.Obtain PVC/Al2O3。
119.28g dicyandiamides and 4.0gNa is added2CO3, PVC/Al is prepared in addition stating2O3Flow back 1h, is cooled to room temperature, and uses
Deionized water is washed to neutrality, 60 DEG C of dry 10h, obtains functionalization PVC/Al2O3。
B, Pd-Cu- high-molecular complexes/Al2O3The preparation of presoma
Weigh 0.44g Pd (NO3)2、2.59g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
1.5, it is configured to mixed solution, takes the functionalization-PVC/Al prepared2O3Presoma adds it to Pd (NO3)2、Cu(NO3)2
Mixed solution in, stir 30min, pour out raffinate, above-mentioned product be washed with deionized to neutrality, 120 DEG C of dry 4h are obtained
To (Pd-Cu)-PVC/Al2O3Presoma.
C, the preparation of catalyst
By the presoma of above-mentioned preparation, 550 DEG C of roasting 2h, obtain oxidation state (Pd-Cu)/Al in air atmosphere2O3Catalysis
Agent.It is positioned in fixed-bed reactor before use, is 99.9% with hydrogen purity, air speed 200h-1Gas, at 120 DEG C
At a temperature of, obtain loaded catalyst D-1.It is 0.18% that measure catalyst Pd contents, which be 0.036%, Cu 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, working condition is shown in Table 1, and raw material composition is shown in Table 2.
1 micro anti-evaluation parameter of table
2 raw material of table forms
| Component | Compositing range (%) | Component | Compositing range (%) |
| H2 | 1.2~2.5 | C2H2 | 0~0.01 |
| N2 | 0.5~1.0 | C2H6 | 1~2 |
| O2 | 0.005~0.015 | C2H4 | 40~60 |
| CO | 0.60~1.0 | C3H8 | 1.5~3 |
| CO2 | 0.20~0.60 | C3H6 | 15~40 |
| H2S | 0~0.0008 | C3H4 | 0~0.01 |
| CH4 | 6~10 | C4 | 3~6 |
| C2H2 | 0~0.01 | C5+ | 6~10 |
3 catalyst 1000h performance average values of table
Embodiment 2
Weigh Φ 4.0mm, high 4.0mm, specific surface area 58.0m2/ g, Kong Rongwei 0.44mL/g, heap density are 0.75g/
The cylindrical vector 500g, Al of mL2O3For the mixing crystal form of δ and θ.
By 18.46g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 650mL 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 are obtained
Hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.59gPd (NO3)2、2.59g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
2.0, it is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min,
8h is stood, raffinate is poured out, remaining solid dry 8h at 110 DEG C obtains PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-
Bipyridyl molal quantity：(Pd+Cu)=30).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst S-2 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.048%, Cu contents are 0.096%.
Comparative example 2
Weigh Φ 4.0mm, high 4.0mm, specific surface area 58.0m2/ g, Kong Rongwei 0.44mL/g, heap density are 0.75g/
The cylindrical vector 500g, Al of mL2O3For the mixing crystal form of δ and θ.
A, functionalized polystyrene acrylonitrile (SAN)/Al2O3Preparation
SAN resin 2.2g are weighed, are dissolved in 600mL DMF (dimethylformamide) solvent, stirring at room temperature makes SAN trees
Fat is completely dissolved, be added in this solution it is above-mentioned weighed carrier, stand 1 hour after being sufficiently stirred, detach dry after solvent, obtain
To SAN/Al2O3。
By SAN/Al obtained above2O3, it is added in 1000mL deionized waters, 57.6g ethylenediamines is added, flows back 4h, cold
But product is taken out afterwards, is washed to neutrality, is dried to obtain functionalization-SAN/Al2O3。
B、(Pd-Cu)-SAN/Al2O3The preparation of presoma
Weigh 0.59gPd (NO3)2、2.59g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
2.0, it is configured to mixed solution, takes the functionalization-SAN/Al prepared2O3Presoma, by functionalization-SAN/Al2O3It is added to Pd
(NO3)2、Cu(NO3)2Mixed solution in, stir 5min, pour out raffinate, above-mentioned product be washed with deionized to neutrality,
(Pd-Cu)-SAN/Al is obtained after drying2O3Presoma.
C, the preparation of catalyst
The presoma of above-mentioned preparation is obtained into Pd-Cu/Al in 500 DEG C of roasting 4h of air atmosphere2O3Catalyst.Before use
It is positioned in fixed-bed reactor, is 99.9% with hydrogen purity, air speed 200h-1Gas obtained at a temperature of 120 DEG C
To loaded catalyst D-2.It is 0.096% that measure catalyst Pd contents, which be 0.048%, Cu 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, working condition is shown in Table 4, and raw material composition is shown in Table 2.
4 micro anti-evaluation parameter of table
5 catalyst 1000h performance average values of table
Embodiment 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 θ-Al2O3460g, titanium oxide 40g.
By 80.62g 6,6'- dihydroxy -3,3'- bipyridyls are dissolved in 700mL ethanol solutions, by above-mentioned carrier impregnation upper
It states in solution, after after standing 12h 6,6'- dihydroxy -3,3'- bipyridyls being loaded on alumina support completely, 120 DEG C dry
Dry 4h obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.41gPd (NO3)2,0.74g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
3.2, it is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min,
8h is stood, raffinate is poured out, remaining solid dry 4h at 120 DEG C obtains PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-
Bipyridyl molal quantity：(Pd+Cu)=85).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst S-3 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.034%, Cu contents are 0.05%.
Comparative example 3
Catalyst preparation
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 θ-Al2O3460g, titanium oxide 40g.
Weigh 0.41gPd (NO3)2, 0.74g Cu (NO3)2The 400mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
3.2, it is configured to mixed solution, will be shaken 0.5 hour after the solution spraying to above-mentioned carrier, after dry, in air atmosphere
450 DEG C of roasting 6h obtain (Pd-Cu)/Al2O3Catalyst.It is positioned in fixed-bed reactor before use, is with hydrogen purity
99.9%, air speed 200h-1Gas obtain loaded catalyst D-3 at a temperature of 120 DEG C.Measure catalyst Pd contents
It is 0.05% for 0.034%, Cu 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, working condition is shown in Table 6, and raw material composition is shown in Table 2.
6 micro anti-evaluation parameter of table
7 catalyst 500h performance average values of table
Embodiment 4
Weigh Φ 4.2mm, high 4.2mm, specific surface area 54.0m2/ g, Kong Rongwei 0.48mL/g, heap density are 0.74g/
The cylindrical vector 500g, Al of mL2O3For the mixing crystal form of δ and θ.
By 93.06g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 600mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 10h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 100 DEG C of dry 6h are obtained
To hydroxyl-bipyridyl/Al2O3Precursor.
Weigh 0.54gPd (NO3)2、4.24g Cu(NO3)2The 600mL deionized waters containing appropriate nitric acid are dissolved in, tune pH is
2.8, it is configured to mixed solution, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min,
10h is stood, raffinate is poured out, remaining solid dry 10h at 90 DEG C obtains PdCu- hydroxyls-bipyridyl/Al2O3Precursor (hydroxyl-
Bipyridyl molal quantity：(Pd+Cu)=20).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst S-4 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.044%, Cu contents are 0.29%.
Comparative example 4
Weigh Φ 4.2mm, high 4.2mm, specific surface area 54.0m2/ g, Kong Rongwei 0.48mL/g, heap density are 0.74g/
The cylindrical vector 500g, Al of mL2O3For the mixing crystal form of δ and θ.
By 93.06g 4,4- dihydroxy -2,2- bipyridyls are dissolved in 600mL ethanol solutions, by above-mentioned carrier impregnation above-mentioned
In solution, after after standing 10h dihydroxy -2,2- bipyridyl being loaded on alumina support completely, 100 DEG C of dry 6h are obtained
To hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2、AgNO3The 600mL deionized waters containing appropriate nitric acid are dissolved in, it is 2.8 to adjust pH, is configured to mix
Solution is closed, by above-mentioned hydroxyl-bipyridyl/Al2O3Precursor is added to the solution prepared, and stirs 60min, stands 10h, pours out
Raffinate, remaining solid dry 10h at 90 DEG C obtain PdAg- hydroxyls-bipyridyl/Al2O3Precursor.
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.Fixed-bed reactor is positioned over before use
In, it is 99.9% with hydrogen purity, air speed 200h-1Gas obtain loaded catalyst D-4 at a temperature of 120 DEG C.It surveys
Catalyst Pd contents be 0.044%, Ag contents are 0.29%.
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, working condition is shown in Table 8, and raw material composition is shown in Table 2.
8 micro anti-evaluation parameter of table
9 catalyst 500h performance average values of table
It is and organic and when active component content is identical as can be seen that compared with using traditional preparation catalyst
Macromolecular grafted functional group simultaneously loads on a catalyst support, then the solution of carrier impregnation activity Pd, Cu is obtained organic high
The method of molecular metal complex compound prepares catalyst and compares, and uses the method for hydrotreating of the present invention, the activity of hydrogenation reaction and choosing
Selecting property is significantly better than traditional method of hydrotreating, and outlet acetylene content is significantly lower than other two kinds of method of hydrotreating, and Ethylene purity improves,
So as to improve the performance of polymer grade ethylene product, while the reduction of green oil very well so that the activated centre of catalyst does not have
It is covered by by-product, catalyst activity and selectivity are kept well, and catalyst service life extends.
Claims (14)
1. a kind of front-end hydrogenation method of trace acetylene in methanol-to-olefins device, for adding the adiabatic reactor reactor of hydrogen to be located at piptonychia
Before alkane tower or dethanizer, the carbon one, carbon two in methanol-to-olefins device from drying tower bottom of tower and carbon 3 material, into exhausted
Hott bed reactor carries out selection plus hydrogen, it is characterised in that：Pd-Cu 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 0.015~
0.050%, Cu content are 0.02~0.3%, and the specific surface area of catalyst is 20~60m2/ g, pore volume be 0.15~
0.70mL/g；The catalyst is combined in preparation process, by carrier with hydroxyl dipyridyl derivatives, hydroxyl connection pyrrole
Piperidine derivatives form metal complex with active component；Reaction condition is：30 DEG C~50 DEG C of adiabatic reactor reactor inlet temperature, instead
Answer 1.5~2.5MPa of pressure, 5000~15000h of air speed-1。
2. front-end hydrogenation method according to claim 1, it is characterised in that catalyst preparation process includes at least：It will be with hydroxyl
The dipyridyl derivatives of base load on carrier, then by the extra hydroxyl of hydroxyl dipyridyl derivatives and/or nitrogen base with
The cation of Pd, Cu form complex ion.
3. the front-end hydrogenation method of trace acetylene in a kind of methanol-to-olefins device 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. front-end hydrogenation method according to claim 1, it is characterised in that catalyst is included the following steps：With band hydroxyl
The organic solution of the dipyridyl derivatives of base, impregnated carrier obtain hydroxyl-bipyridyl/Al after drying2O3Precursor is prepared
The mixed-cation solution of Pd, Cu impregnate hydroxyl-bipyridyl/Al2O3Precursor, it is dry at 60 DEG C~150 DEG C, obtain PdCu-
Hydroxyl-bipyridyl/Al2O3Precursor obtains required catalyst in 300~600 DEG C of 2~12h of roasting temperature.
5. front-end hydrogenation method according to claim 1, it is characterised in that carrier mainly contains Al2O3, wherein also 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 forms.
6. according to the front-end hydrogenation method described in claim 5, it is characterised in that Al2O3For θ, α or its mixing crystal form Al2O3。
7. front-end hydrogenation method according to claim 1, it is characterised in that carrier is spherical shape, cylindrical, circular ring shape, bar shaped,
Cloverleaf pattern or bunge bedstraw herb shape.
8. according to any front-end hydrogenation methods of claim 1-7, it is characterised in that the preparation method of catalyst includes as follows
Step：
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
The organic solution of hydroxyl dipyridyl derivatives is mixed with carrier, at a temperature of 20 DEG C~60 DEG C react 2~for 24 hours, take
Go out solid particle, it is dry at 60 DEG C~150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdCu- hydroxyls-bipyridyl/Al2O3The preparation of precursor
Prepare Pd, Cu mixed-cation solution, at a temperature of 30 DEG C~100 DEG C with hydroxyl-bipyridyl/Al obtained by step A2O3
Precursor reaction 2~for 24 hours, solid particle is taken out, it is dry at 60 DEG C~150 DEG C, obtain PdCu- hydroxyls-bipyridyl/Al2O3Before
Body；
C. the preparation of catalyst
PdCu- hydroxyls-bipyridyl/Al prepared by step B2O3Precursor is in 300~600 DEG C of 2~12h of roasting temperature so that
PdCu- hydroxyls-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
9. front-end hydrogenation method according to claim 8, it is characterised in that hydroxyl-bipyridyl/(Pd+Cu's) rubs in step A
Your number is 1~100：1.
10. front-end hydrogenation method according to claim 8, it is characterised in that in stepb, the mixed-cation of Pd, Cu are molten
Liquid is the mixed solution of palladium nitrate and copper nitrate.
11. front-end hydrogenation method according to claim 8, it is characterised in that in stepb, the molal quantity of Cu and mole of Pd
The ratio between number is 0.4~11：1.
12. front-end hydrogenation method according to claim 8, it is characterised in that in stepb, adjust Pd, Cu mixing sun from
Sub- solution ph is 1.5~4.0.
13. front-end hydrogenation method according to claim 1, it is characterised in that adiabatic reactor reactor reaction bed number is single hop
Bed.
14. front-end hydrogenation method according to claim 1, it is characterised in that hydrogen is 2~6 with acetylene volume ratio：1.
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