CN102206130B - Selective hydrogenation method of C2 fraction - Google Patents
Selective hydrogenation method of C2 fraction Download PDFInfo
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- CN102206130B CN102206130B CN2011100860485A CN201110086048A CN102206130B CN 102206130 B CN102206130 B CN 102206130B CN 2011100860485 A CN2011100860485 A CN 2011100860485A CN 201110086048 A CN201110086048 A CN 201110086048A CN 102206130 B CN102206130 B CN 102206130B
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Abstract
The invention provides a selective hydrogenation method of C2 fraction. The selective hydrogenation method adopts a front-end deethanization front-end hydrogenation technology and is characterized in that a Pd-Ag type catalyst is placed in a fixed bed reactor; the Pd-Ag type catalyst comprises Al2O3 as major carriers, and Pd and Ag as active components of the Pd-Ag type catalyst; the active components contain 0.01 to 0.04% of Pd and 0.02 to 0.2% of Ag; a specific surface area of the Pd-Ag type catalyst is 2 to 20 m<2>/g; a pore volume of the Pd-Ag type catalyst is 0.2 to 0.35 ml/g; and organic polymer metal complexes are formed in the preparing process of the Pd-Ag type catalyst. Through the selective hydrogenation method provided by the invention, reactions can be carried out in an isothermal or an adiabatic bed reactor thus energy consumption during processing is reduced greatly. The selective hydrogenation method has the advantages of convenient operation, reduction of temperature runaway phenomenon, improvement of reaction system safety and apparatus economic benefit.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly a kind of C 2 fraction selective hydrogenation except the method for acetylene.
Background technology
The production of ethene is the tap of petrochemical industry, the selection hydrogenation of acetylene in the steam cracking product, the ethene processing industry there is extremely important effect, except the outlet acetylene content that guarantees hydrogenator is up to standard, selectivity of catalyst is good, can make the least possible generation ethane of ethene, significant to the yield of ethene, the raising device economic benefit that improve whole technological process.
In the present C-2-fraction acetylene hydrogenation, much more more and more employing carbon two front-end hydrogenation techniques, the characteristics of this technique are that hydrogenator is before demethanizing tower, therefore a large amount of hydrogen arranged in reaction mass, it is particularly important that selectivity of catalyst shows, otherwise can be owing to more ethylene hydrogenation causes the catalyticreactor temperature runaway.
The front-end hydrogenation method of front-end deethanization, because the content of hydrogen is higher, and does not have C3 fraction in reaction mass, the thermal capacitance of reaction mass is lower, the bed temperature rise is higher than the front-end hydrogenation method of predepropanization.In this case, the catalyzed reaction selectivity is low, and reactor just is easy to occur temperature runaway, and the operation of installing is brought threat.Because the performance limitations of present catalyzer, this technique has to adopt the isothermal bed bioreactor.
This mechanism is as follows:
Main reaction
C
2H
2+H
2→C
2H
4 ΔH＝-175.7kJ/mol (1)
Side reaction
C
2H
4+H
2→C
2H
6 ΔH＝-138.1kJ/mol (2)
C
2H
2+2H
2→C
2H
6 (3)
Even when adopting the isothermal bed bioreactor, the selectivity of reaction also can only reach 50～60%, that is to say, react 2 odds and be reaction 1 50% in addition higher, have quite a few conversion of ethylene to become ethane.
Reaction conditions is: 50～110 ℃ of reactor inlet temperatures, reaction pressure 3.0～4.5MPa, gas volume air speed 5000～30000h
-1
Form in the material and be generally C-2-fraction 40～55 (v/v%), acetylene 0.4～1.0% (v/v%), methane 20～30% (v/v%), hydrogen 19～30% (v/v%), CO 0.02～0.2 (v/v%).
When adopting the isothermal bed process, use shell and tube reactor, heat-eliminating medium is arranged, the heat that produces to take away reaction between tubulation.For this processing method, generally adopt methyl alcohol as heat-eliminating medium, its flow must more accurately be controlled, so that the temperature-stable in the reactor is in suitable scope, temperature is crossed the low alkynes that easily occurs to leak, the temperature height is easy temperature runaway again.At the device driving initial stage, catalyst activity is high, and is to temperature sensitive, especially true.
Patent US 4484015 discloses a kind of catalyzer, adopts take Pd as main active ingredient, take Alpha-alumina as carrier, adds promotor silver, has prepared carbon two hydrogenation catalysts of excellent property with pickling process.This catalyzer has the excessive hydrogenation that can effectively reduce ethene, reduces the risk of bed temperature runaway.
Patent US 5587348 adds promotor silver and palladium effect take aluminum oxide as carrier, adds basic metal, and the fluorine of chemical bonding has prepared carbon two hydrogenation catalysts of excellent property.This catalyzer has the green oil of minimizing and generates, improve ethylene selectivity, reduce the characteristics of oxygenatedchemicals growing amount, US 5510550 adopts the method Kaolinite Preparation of Catalyst of wet reducing, by in steeping fluid, adding reductive agent, make Pd, Ag solution is not reduced when dry, reduce the active ingredient that solvation effect causes and disperseed problem of non-uniform, prepared the catalyzer of the good adaptation carbon two front-end hydrogenation techniques of selectivity.
Above hydrogenation catalyst all is to adopt aqueous solution preparation, is subject to the impact of solvation effect in the dipping of catalyzer and drying treatment process, and the metal active constituent presoma is deposited on carrier surface with aggregate form.Because the heterogeneity of disperseing, high-temperature roasting cause easily metallics migration gathering and form large crystal grain; Affect the repeatability of catalyzer preparation, reduce the utilization ratio of active ingredient, adopt in addition the microemulsion method to carry out the preparation of one-component noble metal catalyst among the US 4714692.When adopting this method to prepare multicomponent catalyst, still keep away the impact that unavoidable solvation effect distributes on the catalyst activity component.
Summary of the invention
The object of the present invention is to provide a kind of method of C-2-fraction front-end hydrogenation, a kind of C-2-fraction front-end deethanization front-end hydrogenation processing method particularly is provided, by selecting to have the catalyzer of complete alloy structure, improved hydrogenation selectivity.
The inventor finds that active ingredient Pd, Ag affect the performance of catalyzer greatly in the distribution of catalyst surface, and when Pd, Ag formed alloy, selectivity of catalyst was more excellent.
The selection method of hydrotreating of C-2-fraction of the present invention, adopt the front-end hydrogenation processing method of front-end deethanization, with in the ethylene unit from the overhead product of front-end deethanization tower, select hydrogenation to remove acetylene wherein, this material is with the cracking cut from steam cracking furnace, through over-quenching, washing, behind the oil wash, pass through front-end deethanization tower separation of carbon three and carbon two following cuts, carbon two following cuts enter hydrogenator and select hydrogenation again, this hydrogenation reaction is (hotbed such as to comprise at fixed bed, adiabatic reactor) reactor carries out, and it is characterized in that being equipped with in the fixed-bed reactor Pd-Ag series catalysts, and Pd-Ag series catalysts refers to Al
2O
3Be main carriers, the active ingredient take Pd, Ag as catalyzer, wherein containing Pd content is 0.01～0.04%; Ag content is 0.02～0.2%, and the specific surface area of catalyzer is 2～20m preferably
2/ g; Pore volume is 0.2～0.35ml/g preferably, and this catalyzer has formed the organic polymer metal complex in preparation process.
The preparation method that catalyzer is recommended is: make palladium and silver form the organic polymer metal complex with organic polymer by complexing agent, obtain Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is 2～6h, obtains required catalyzer.
Complexing agent is both can carry out functionalization with the organic macromolecule side-chain radical, the complexing agent of ion that again can complexing Pd, Ag after reaction, and the functional group of complexing agent can be amido or two amidos.
Contain on the organic macromolecule side chain of the present invention can with the group of complexing agent reaction, this group can be one or more in halogen, the cyano group.
Carrier of the present invention is Al
2O
3Or Al
2O
3In be doped with other hopcalite, other oxide compound can be silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.Al
2O
3Crystal formation be preferably θ, α or its and mix crystal formation.
The acquisition of this catalyzer preferably includes following steps: with organic polymer (polymer) grafted functional group and load on the support of the catalyst, obtain functionalized-polymer/Al by complexing agent
2O
3Presoma; The solution of preparation palladium-Yin has load functionalized-polymer/Al
2O
3Presoma is impregnated in the palladium prepared-Yin solution and reacts, and palladium, silver are complexed on the functionalized macromolecular chain, and palladium and silver have formed the organic polymer metal complex with organic polymer, obtain Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is 2～6h, obtains required catalyzer.Because this catalyzer has higher selectivity, is not easy to cause temperature runaway, therefore reactor of the present invention both applicable to waiting hotbed, also went for adiabatic reactor, and the use of adiabatic reactor reduces energy consumption of reaction greatly.
The present invention is not limited especially to the bed number of the catalyzer of fixed-bed reactor, single or many all can, two sections beds preferably.
Reaction conditions was when fixed-bed reactor were the isothermal bed bioreactor: 50～110 ℃ of reactor inlet temperatures, reaction pressure 3.0～4.5MPa, gas volume air speed 4000～30000h
-1(referring to single bed bioreactor, as follows).
Reaction conditions was when fixed-bed reactor were the adiabatic reactor reactor: 45～100 ℃ of reactor inlet temperatures, and reaction pressure is preferably 3.0～4.5MPa, and single bed bioreactor gas volume air speed is preferably 5000～25000h
-1
The method of hydrotreating that the present invention proposes, the preparation method of the catalyzer that adopts can be: will have the macromolecular material uniform loading of reactive group on the side chain on support of the catalyst, by complexing agent grafted functional group on the macromolecular chain of institute's load, described functional group can form complexing ion with the ion of Pd, Ag, can also be first by complexing agent with the organic polymer grafted functional after, be carried on again on the support of the catalyst; The solution of preparation palladium-Yin has functionalized high molecular precursor to be impregnated in the solution of the palladium-Yin that has prepared load, reacts under certain conditions, makes palladium, silver-colored network and to the macromolecular chain of load.Can also be added to after with the organic polymer grafted functional in the palladium of preparation-Yin solution by complexing agent, again load carriers.Because complex reaction is the chemical reaction of complex-metal ion, metal ion is by chemical reaction but not physical adsorption is attached on the macromolecular chain, therefore the atom of palladium, silver is uniform sequential distribution at macromolecular chain, in the process of roasting, palladium-silver atoms can carry out oxidizing reaction in position, in the process of oxidizing reaction, form the oxide eutectic of palladium, silver.
Catalyzer prepared by this method has overcome steeping fluid surface tension and solvation effect to the impact of the dispersion of palladium-Yin, possesses excellent selectivity.
Catalyzer of the present invention preparation can adopt following process to implement, and this process can be divided into for 3 steps and carry out:
(1). at first prepare functionalized-polymer/Al
2O
3Presoma;
(2). preparation Pd-Ag-polymer/Al
2O
3Presoma;
(3). carry out roasting 2～6h at 380～550 ℃ of presomas to step 2 preparation.
The preparation method of this catalyzer of recommending comprises the steps:
A. functionalized-polymer/Al
2O
3The preparation of presoma
Organic polymer is dissolved in the organic solvent, forms macromolecular solution, again with carrier impregnation in mentioned solution, leave standstill and make organic polymer (polymer) be deposited on Al
2O
3The surface, drying; Add again the complexing agent backflow 0.5～300min that contains functional group, prepare functionalized-polymer/Al
2O
3Presoma;
More specifically method as: under 20～35 ℃, the organic polymer that has reactive group on the side chain is dissolved in the organic solvent, carrier impregnation in mentioned solution, is left standstill 2～6h, make described polymer be deposited on Al
2O
3The surface is after the drying, at 20～35 ℃ of lower complexing agents that add.Described complexing agent both can carry out functionalization with the organic macromolecule side-chain radical, and ion that again can complexing Pd, Ag after reaction with the above-mentioned solution 1～4h that refluxes, is cooled to 20～35 ℃, uses deionized water wash, drying.
Have reactive group on the described side chain of organic polymer and refer to that polymer side chain contains halogen, the polymer of the groups such as cyano group, such as polyvinyl chloride (PVC), polystyrene vinyl cyanide (SAN) etc., described complexing agent is for providing the micromolecular compound of amido or two amido functional groups, can be Dyhard RU 100, thanomin, quadrol or oxammonium hydrochloride can be wherein one or more; In mole number, the reactive group mole number preferably 100～1 in complexing agent mole number/polymer;
B. (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Preparation palladium-Yin solution, and with inorganic acid for adjusting pH value 1～4 takes by weighing prepared functionalized-polymer/Al
2O
3Presoma joins the solution of preparing palladium-Yin on the precursor, 20～35 ℃ of lower dipping 5～30min, and washing, drying obtain Pd-Ag-polymer/Al
2O
3Presoma; The mole number of functional group's mole number on the functionalized rear macromolecular chain/(Pd+Ag) preferably 100～1.
C. the preparation of catalyzer
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h obtain (Pd-Ag)/Al
2O
3Catalyzer.
Above-mentioned roasting can be carried out in oxygen atmosphere is arranged, and effect is better.
When catalyzer used, the catalyzer that above method can be made used H in reactor
2Reduce processing, obtain the reduction-state catalyzer.
Polymer of the present invention is the polymer that contains reactive group on the side chain, and described reactive group is preferably cyano group or chlorine atom.
Described complexing agent is to carry out graft reaction with above-mentioned reactive group, and the molecule that can carry out complex reaction with palladium, silver ions.Specifically can be Dyhard RU 100, thanomin, quadrol, oxammonium hydrochloride etc.
The mole number of functional group's mole number on the functionalized rear macromolecular chain/(Pd+Ag) preferably 100～1, the mole number of reactive group-CN among concrete example such as the SAN (cyanogen root) mole number/(Pd+Ag) preferably 100～1.The mole number of complexing agent mole number/(Pd+Ag) preferably 10000～1.
Add solvent be in steps A for polymer is dissolved fully, to be conducive to the absorption of polymer on carrier, solvent can be tetrahydrofuran (THF) (THF), toluene, dimethyl formamide (DMF) equal solvent.The add-on of solvent what, mainly be that control institute solubilizing agent can make polymer dissolve fully to get final product.
In step B, palladium, silver salt consumption in the solution of described preparation palladium-Yin, with Pd, the Ag content that can make final catalyzer, wherein to be preferably in be 0.01～0.4%, Ag content preferably 0.02～0.2% to Pd.
Using plasma emission spectrometer or atomic absorption spectrum can record this catalyst P d content and Ag content (standard GB/T 15337-94).
The inventor also finds, when adopting method of hydrotreating of the present invention, under isothermal bed process condition, catalyzer can move moving than traditional catalyst under the much lower condition of desired minimum safe air speed, greatly improve the security of technological operation, improved the level of safety of device operation.After adopting this catalyzer, the safe air speed of device can be reduced to 4000h
-1
The inventor finds, adopt method of hydrotreating of the present invention after, can change traditional isothermal bed bioreactor into the adiabatic reactor reactor, reduce the consumption of energy, greatly simplified the operation of reactor, improve reliability, significant to the steady running that improves device.
Description of drawings
Fig. 1 is the carbon two front-end hydrogenation technical process of front-end deethanization technique.
Among the figure: 1---oil scrubber; 2---water wash column; 3---alkali is inhaled tower; 4---drying tower; 5---the front-end deethanization tower; 6---carbon two hydrogenators; 7---demethanizing tower.
Embodiment
Analytical procedure and standard:
Specific surface area: GB/T-5816
Pore volume: GB/T-5816
Catalyst P d, Ag assay: use plasma emission spectrometer to record.
The selective calculation method:
Ethylene selectivity: S=1-| Δ ethane/Δ acetylene |
The preparation of catalyzer
A, functionalized PVC/Al
2O
3Preparation
Take by weighing Φ 4mm, length is 4mm, and specific surface area is 15m
2/ g, pore volume are the column Al of 0.25ml/g
2O
3Carrier 250g.
PVC4.45g is dissolved in the 400ml tetrahydrofuran (THF) (THF) fully, makes PVC be deposited on Al the carrier impregnation that weighed up 0.5h in the mentioned solution
2O
3The surface, inclining raffinate, and drying obtains 208gPVC/Al
2O
3Product.
Add 59.64g Dyhard RU 100 and 2.0gNa
2CO
3, add 208g PVC/Al
2O
3Refluxed 2 hours, and be cooled to room temperature, extremely neutral with deionized water wash, drying for standby.Obtain functionalized PVC/Al
2O
3Reactive group Cl mole number=10 on complexing agent Dyhard RU 100 mole number/macromolecular chain.
B, (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Take by weighing 0.077gPd (NO
3)
2, 0.08gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing prepared functionalized-polymer/Al
2O
3Presoma 254.45g is with functionalized-polymer/Al
2O
3Join Pd (NO
3)
2, Ag NO
3Mixing solutions in, absorption 0.5h, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-polymer/Al
2O
3Presoma, mole number=100 of reactive group Cl mole number on the macromolecular chain/(Pd+Ag)).
The preparation of C, catalyzer
With the presoma of above-mentioned preparation, 550 ℃ of roasting 4h obtain oxidation state Pd-Ag/Al in air atmosphere
2O
3Catalyzer is positioned over before the use in the reaction unit, is N with mol ratio
2: H
2=1: 1 mixed gas, 120 ℃ of temperature, 12h is processed in reduction.Recording this catalyst P d content is that 0.01%, Ag content is 0.02%.
Comparative Examples 1
Take by weighing Φ 4mm, length is 4mm, and specific surface area is 15m
2/ g, pore volume are the column Al of 0.25ml/g
2O
3Carrier 250g.
Take by weighing 0.077gPd (NO
3)
2, 0.08gAg NO
3, measure 0.5ml nitric acid, be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, ultrasonic vibration 0.5h, dry rear at 550 ℃ of roasting temperature 4h, obtain Pd-Ag/Al
2O
3Catalyzer.Being positioned over before the use in the reaction unit, is N with mol ratio
2: H
2=1: 1 mixed gas, 120 ℃ of temperature, 12h is processed in reduction.Recording this catalyst P d content is that 0.01%, Ag content is 0.02%.
Reaction raw materials: from the front-end deethanization column overhead, material forms such as table 1.
Table 1 reaction raw materials forms
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C + 3 |
| Content (V%) | 19 | 1.0 | 46 | 8. | 25.5 | 0.2 | 0.3 |
Reaction conditions 1: adopt two sections isothermal bed bioreactors; Single hop reactor content volume space velocity 8000h
-1, working pressure 3.0MPa, each section reactor catalyst loadings 800ml.
Two sections isothermal bed bioreactors of table 2 are average result after reaction in 800 hours
Reaction conditions 2: adopt two sections adiabatic reactor reactors; Single hop reactor content volume space velocity 7000h
-1, working pressure 3.0MPa, each section reactor catalyst loadings 700ml.
Reaction result is as follows:
Two sections adiabatic reactor reactors of table 3 are average result after reaction in 800 hours
Find out that from embodiment 1 under same reaction conditions, adopt processing method of the present invention, the activity of its reaction and selectivity all are better than traditional method.
Catalyzer adopts method preparation of the present invention.
A, functionalized SAN/Al
2O
3Preparation
Take by weighing Φ 4.5 * 4.5mm, specific surface area is 20m
2/ g, pore volume are the cylindrical vector 250g of 0.35ml/g, wherein contain Al
2O
3200g, TiO
250g.
Take by weighing SAN resin 1.1g, be dissolved in 300ml dimethyl formamide (DMF) solvent, stirring is dissolved the SAN resin fully under the room temperature, in this solution, add above-mentioned weighing carrier, left standstill 1 hour after fully stirring, dry behind the separation solvent, obtain SAN/ (Al
2O
3+ TiO
2).
With SAN/ (Al obtained above
2O
3+ TiO
2), join in the 500ml deionized water, add the 28.8g quadrol, back flow reaction 1h takes out product after the cooling, and washing is to neutral, and drying obtains functionalized SAN/ (Al
2O
3+ TiO
2) presoma.Reactive group Cl mole number=19 on the mole number/macromolecular chain of complexing agent quadrol.
B (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Take by weighing 0.22gPd (NO
3)
2, 0.4gAg NO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing prepared functionalized-SAN/Al
2O
3+ TiO
2Presoma 251.1g is with functionalized polymer/Al
2O
3+ TiO
2Join Pd (NO
3)
2, Ag NO
3Mixing solutions in, absorption 6h, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag) polymer/Al
2O
3+ TiO
2Presoma, mole number=54.71 of reactive group CN mole number on the macromolecular chain/(Pd+Ag).
The preparation of C catalyzer
With the presoma of above-mentioned preparation, 380 ℃ of roasting 6h obtain (Pd-Ag)/Al in air atmosphere
2O
3+ TiO
2Catalyzer, recording this catalyst P d content is that 0.04%, Ag content is 0.1%.
Comparative Examples 2:
Method according to patent US 4484015 embodiment 1.
Take by weighing Φ 4.5 * 4.5mm, specific surface area is 20m
2/ g, pore volume are 0.35ml/g
3Cylindrical vector 250g, wherein contain Al
2O
3200g, TiO
250g.
Take by weighing 0.22gPd (NO
3)
2Being dissolved in the 100ml deionized water, is 2.8 with the pH value of dilute hydrochloric acid regulator solution, and described carrier impregnation in the solution that has prepared, 120 ℃ of dryings 10 hours, is obtained catalyst A.
Take by weighing 0.4gAg NO
3, measure 0.5ml nitric acid and be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, absorption 1h, dry rear at 380 ℃ of roasting temperature 8h, obtain (Pd-Ag)/(Al
2O
3+ TiO
2) catalyzer.Recording this catalyst P d content is that 0.04%, Ag content is 0.1%.Reaction mass: from the front-end deethanization column overhead, raw material forms such as table 4.
Table 4 hydrogenating materials forms
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C + 3 |
| Content (V%) | 23.64 | 0.73 | 44 | 7.5 | 24. | 0.1 | 0.3 |
Reaction conditions 1: adopt two sections isothermal bed bioreactors; Single hop volume of material air speed: 4000h
-1, working pressure: 2.5MPa, each section reactor catalyst loadings: 500ml.
Two sections isothermal bed bioreactors of table 5 were through 200 hours reaction results
2: two sections adiabatic reactor reactors of reaction conditions; Single hop reactor content volume space velocity: 5000h
-1, working pressure: 2.5MPa, each section reactor catalyst loadings: 700ml.
Two sections adiabatic reactor reactors of table 6 were through 200 hours reaction average results
Can find out from the above embodiments and Comparative Examples, when adopting catalyzer of the present invention, the isothermal bed bioreactor can be changed into the adiabatic reactor reactor.Equity hotbed reactor can drop to 4000h with air speed
-1
Embodiment 3
The preparation of catalyzer adopts method of the present invention to be prepared.
A, functionalized SAN/Al
2O
3Preparation
Take by weighing 4.0 * 4.0mm, specific surface area is 2m
2/ g, pore volume are the cylindric Al of 0.2ml/g
2O
3Carrier 250g.
Take by weighing SAN resin 25g, be dissolved in the 300ml DMF solvent, stirring is dissolved the SAN resin fully under the room temperature, adds the 20g oxammonium hydrochloride, adds 5gK
2CO
3, be heated to it and dissolve fully.After stirring half an hour, carrier 250g is added above solution, drip 200ml ethanol, and constantly stir, take out product after 1 hour, washing obtains functionalized SAN/Al to neutral after the drying
2O
3Reactive group CN mole number=1.21 on complexing agent oxammonium hydrochloride mole number/macromolecular chain.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take by weighing 0.11gPd (NO
3)
2, 0.8gAg NO
3, 3.17gK
2CO
3, be mixed with the mixing solutions of 1200ml, take by weighing prepared functionalized-SAN/Al
2O
3Presoma 258g joins Pd (NO
3)
2, Ag NO
3Mixing solutions in, behind the absorption 1h, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-polymer/Al
2O
3Presoma.Mole number=90.53 of reactive group CN mole number on the macromolecular chain/(Pd+Ag).
The preparation of C, catalyzer
With the presoma of above-mentioned preparation, 550 ℃ of roasting 2h obtain Pd-Ag/Al in air atmosphere
2O
3Catalyzer.Recording this catalyst P d content is that 0.02%, Ag content is 0.2%.
Comparative Examples 3
Take by weighing 4.0 * 4.0mm, specific surface area is 2m
2/ g, pore volume are the cylindric Al of 0.2ml/g
2O
3Carrier vector 250g.
Take by weighing 0.11g Pd (NO
3)
22H
2O is dissolved in the 235ml deionized water.
In the mentioned solution behind the 1h, inclining raffinate, at 120 ℃ of dry 3h, obtains catalyst A with carrier impregnation.
Take by weighing 0.8gAgNO
3, be dissolved in the 225ml deionized water, be 2.5 with rare nitre acid for adjusting pH value.Above-mentioned catalyst A be impregnated in the solution that has prepared, place the vibration still, behind the vibration 30min, take out at 120 ℃ of dry 2h, at 550 ℃ of roasting temperature 8h.
Recording this catalyst P d content is that 0.02%, Ag content is that 0.2%, Pd and the total metal dispersity of Ag are 5.2%.
Embodiment 4
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 20.m
2/ g, pore volume are 0.35ml/g, and bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
The preparation of A, functionalized chlorinatedpolyethylene (CPE)
CPE 8.0g is dissolved among the 400mlTHF fully, adds 240g Dyhard RU 100 and 2.0gNa
2CO
3, refluxed 2 hours, be cooled to room temperature, obtain functionalized CPE solution for standby.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take by weighing 0.11gPd (NO
3)
2, 0.47gAgNO
3, measure 0.5ml nitric acid, join in the above-mentioned functionalized CPE solution, stir 0.5h, obtain (Pd-Ag)-polymer.
The 250g carrier is added in the mixing solutions, leave standstill 1h after fully stirring, above-mentioned product is extremely neutral with deionized water wash.Obtain (Pd-Ag)-polymer/Al
2O
3Presoma.
The preparation of C, catalyzer
With the presoma of above-mentioned preparation, 500 ℃ of roasting 4h in air atmosphere obtain oxidation state (Pd-Ag)/Al
2O
3Catalyzer.Being positioned over before the use in the fixed-bed reactor, is N with mol ratio
2: H
2=0.1: 1 mixed gas, 120 ℃ of temperature, 12h is processed in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is that 0.02%, Ag content is 0.1%.
Comparative Examples 4
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 20.m
2/ g, pore volume are 0.35ml/g, and bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
Take by weighing 0.11gPd (NO
3)
2, 0.47gAgNO3 adds 0.5ml nitric acid, prepares to get 87.5ml solution, and this solution spraying was shaken 0.5 hour to above-mentioned carrier, and after the drying, 500 ℃ of roasting 4h obtain (Pd-Ag)/Al in air atmosphere
2O
3Catalyzer.Recording this catalyst P d content is that 0.02%, Ag content is 0.1%.
Reaction mass: from the front-end deethanization column overhead, raw material forms such as table 7.
Table 7 hydrogenating materials forms
| Hydrogenating materials | H 2 | C 2H 2 | C 2H 4 | C 2H 6 | CH 4 | CO | C 4 + |
| Content (v/v%) | 30 | 0.4 | 33.4 | 5.88 | 30 | 0.02 | 0.3 |
Reaction conditions 1: adopt the front-end deethanization front-end hydrogenation technique shown in the accompanying drawing 1, single hop isothermal bed bioreactor, the material air speed is 30000h
-1, working pressure is 4.5MPa, loaded catalyst is 300ml.
Table 8 single hop isothermal bed bioreactor reaction in 600 hours average result
Reaction conditions 2: single hop adiabatic reactor reactor, material air speed are 25000h
-1, working pressure is 4.5MPa, loaded catalyst is 300ml.
Table 9 single hop adiabatic reactor reactor reaction in 600 hours average result
Can find out from above embodiment, adopt method of the present invention after, the selectivity of C-2-fraction hydrogenation reaction increases substantially.
Claims (16)
1. the selection method of hydrotreating of a C-2-fraction, adopt the front-end hydrogenation processing method of front-end deethanization, with in the ethylene unit from the overhead product of front-end deethanization tower, select hydrogenation to remove acetylene wherein, this material is with the cracking cut from steam cracking furnace, through over-quenching, washing, behind the oil wash, pass through front-end deethanization tower separation of carbon three and carbon two following cuts, carbon two following cuts enter hydrogenator and select hydrogenation again, and this hydrogenation reaction is carried out at fixed-bed reactor, it is characterized in that being equipped with in the fixed-bed reactor Pd-Ag series catalysts, the Pd-Ag series catalysts refers to Al
2O
3Be main carriers, the active ingredient take Pd, Ag as catalyzer, take the quality of catalyzer as 100%, wherein containing Pd content is 0.01～0.04%; Ag content is 0.02～0.2%, and the specific surface area of catalyzer is 2～20m
2/ g; Pore volume is 0.2～0.35ml/g, and this catalyzer makes palladium and silver form the organic polymer metal complex with organic polymer by complexing agent in preparation process, obtains Pd-Ag-polymer/Al
2O
3Presoma; Complexing agent is both can carry out functionalization with high molecular side-chain radical, the complexing agent of ion that again can complexing Pd, Ag after reaction.
2. selection method of hydrotreating according to claim 1, it is characterized in that catalyzer be by at 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out that 2～6h roasting obtains.
3. selection method of hydrotreating according to claim 1 is characterized in that the contained functional group of complexing agent is amido or two amidos.
4. selection method of hydrotreating according to claim 1, it is characterized in that containing on the organic macromolecule side chain can with the group of complexing agent reaction.
5. selection method of hydrotreating according to claim 4, it is characterized in that containing on the organic macromolecule side chain can be in halogen, the cyano group one or more with the group of complexing agent reaction.
6. selection method of hydrotreating according to claim 1, the acquisition that it is characterized in that catalyzer comprise the steps: by complexing agent to obtain functionalized-polymer/Al with the organic polymer grafted functional group and load on the support of the catalyst
2O
3Presoma; The solution of preparation palladium-Yin has load functionalized-polymer/Al
2O
3Presoma is impregnated in the palladium prepared-Yin solution and reacts, and palladium, silver are complexed on the functionalized macromolecular chain, and palladium and silver have formed the organic polymer metal complex with organic polymer, obtain Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is 2～6h.
7. selection method of hydrotreating according to claim 1, when it is characterized in that fixed-bed reactor are the isothermal bed bioreactor, reaction conditions is: 50～110 ℃ of reactor inlet temperatures, reaction pressure 3.5～4.5MPa, single bed bioreactor gas volume air speed 4000～30000h
-1
8. selection method of hydrotreating according to claim 1, reaction conditions is when it is characterized in that fixed-bed reactor are the adiabatic reactor reactor: 45～100 ℃ of reactor inlet temperatures, reaction pressure is 3.0～4.5MPa, and single bed bioreactor gas volume air speed is preferably 5000～25000h
-1
9. selection method of hydrotreating according to claim 1 is characterized in that carrier is Al
2O
3Or Al
2O
3In be doped with other hopcalite, other oxide compound is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.
10. selection method of hydrotreating according to claim 9 is characterized in that Al
2O
3Crystal formation be that θ, α or its mix crystal formation.
11. selection method of hydrotreating according to claim 6, when it is characterized in that catalyzer prepares, by complexing agent with the organic polymer grafted functional group and load on the support of the catalyst, refer to: organic polymer is loaded on the support of the catalyst, then by complexing agent grafted functional group on the macromolecular chain of institute's load.
12. selection method of hydrotreating according to claim 6, when it is characterized in that catalyzer prepares, by complexing agent with the organic polymer grafted functional group and load on the support of the catalyst, refer to: by complexing agent first with after the organic polymer grafted functional, be carried on again on the support of the catalyst, prepare functionalized-polymer/Al
2O
3Presoma.
13. selection method of hydrotreating according to claim 6 is characterized in that the acquisition of catalyzer comprises the steps: that the preparation method of catalyzer comprises the steps:
A. functionalized-polymer/Al
2O
3The preparation of presoma
Organic polymer is dissolved in the organic solvent, forms macromolecular solution, again with carrier impregnation in mentioned solution, leave standstill and make organic polymer be deposited on Al
2O
3The surface, drying; Add again the complexing agent backflow 0.5～300min that contains functional group, prepare functionalized-polymer/Al
2O
3Presoma;
B.Pd-Ag-high-molecular complex/Al
2O
3The preparation of presoma
Preparation palladium-Yin solution, and with inorganic acid for adjusting pH value 1～4 takes by weighing prepared functionalized-polymer/Al
2O
3Presoma joins the solution of preparing palladium-Yin on the precursor, 20～35 ℃ of lower dipping 5～30min, and washing, drying obtain Pd-Ag-high-molecular complex/Al
2O
3Presoma;
C. the preparation of catalyzer
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h obtain Pd-Ag/Al
2O
3Catalyzer.
14. selection method of hydrotreating according to claim 13, it is characterized in that on the functionalized rear macromolecular chain functional group's mole number/(Pd+Ag) mole number is 100～1.
15. selection method of hydrotreating according to claim 13 is characterized in that in mole number, the reactive group mole number is 100～1 in complexing agent mole number/polymer.
16. selection method of hydrotreating according to claim 13 is characterized in that the mole number of complexing agent mole number/(Pd+Ag) is 10000～1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2792645B1 (en) * | 1999-04-26 | 2003-06-13 | Inst Francais Du Petrole | PROCESS FOR THE SELECTIVE HYDROGENATION OF UNSATURATED COMPOUNDS IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL AND AN ADDITIONAL IV METAL INTRODUCED IN THE FORM OF A HYDROSOLUBLE ORGANOMETALLIC COMPOUND |
| CN101906014A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | C2 fraction selective hydrogenation method |
| CN101913976A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 distillate |
-
2011
- 2011-04-07 CN CN2011100860485A patent/CN102206130B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2792645B1 (en) * | 1999-04-26 | 2003-06-13 | Inst Francais Du Petrole | PROCESS FOR THE SELECTIVE HYDROGENATION OF UNSATURATED COMPOUNDS IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL AND AN ADDITIONAL IV METAL INTRODUCED IN THE FORM OF A HYDROSOLUBLE ORGANOMETALLIC COMPOUND |
| CN101906014A (en) * | 2009-09-15 | 2010-12-08 | 中国石油天然气股份有限公司 | C2 fraction selective hydrogenation method |
| CN101913976A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 fraction |
| CN101913975A (en) * | 2009-09-15 | 2010-12-15 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C2 distillate |
Non-Patent Citations (4)
| Title |
|---|
| 以Β-环糊精为介质的高分散钯催化剂的制备及其催化性能;王寰等;《催化学报》;20060228;第27卷(第02期);124－128 * |
| 徐筠等.负载型钯催化剂用于不饱和化合物的加氢反应.《应用化学》.1988,第5卷(第05期), |
| 王寰等.以Β-环糊精为介质的高分散钯催化剂的制备及其催化性能.《催化学报》.2006,第27卷(第02期), |
| 负载型钯催化剂用于不饱和化合物的加氢反应;徐筠等;《应用化学》;19881231;第5卷(第05期);71-73页，72页第1段、表1 * |
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