CN102206131B - Selective hydrogenation method for C2 fraction - Google Patents
Selective hydrogenation method for C2 fraction Download PDFInfo
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- CN102206131B CN102206131B CN2011100861581A CN201110086158A CN102206131B CN 102206131 B CN102206131 B CN 102206131B CN 2011100861581 A CN2011100861581 A CN 2011100861581A CN 201110086158 A CN201110086158 A CN 201110086158A CN 102206131 B CN102206131 B CN 102206131B
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Abstract
The invention relates to a selective hydrogenation method for a C2 fraction, is used for post-hydrogenation, and introduces C2<+> materials from a front dethanizer in an ethylene device to a fixed bed reactor for selective hydrogenation after pressure hydrogen distribution. The selective hydrogenation method is characterized in that: the fixed bed reactor is provided with a Pd-Ag catalyst, Al2O3 or a mixture of Al2O3 and other oxides is used as a carrier, and the catalyst forms an organic polymer metal complex during preparation process; and the reaction conditions are as follows: the inlet temperature of the fixed bed reactor is 40-100 DEG C, the reaction pressure is 1.5-2.5 MPa and the gas space velocity is 2000-10000 h<-1>. The selective hydrogenation method provided by the invention has higher hydrogenation reaction activity and selectivity than traditional hydrogenation methods, and the generation amount of green oil during hydrogenation process greatly decreases, thus maintaining good activity and selectivity of the catalyst.
Description
Technical field
The present invention relates to a kind of a kind of selection method of hydrotreating, the particularly C 2 fraction selective hydrogenation method except acetylene.
Background technology
Polymer grade ethylene production is the tap of petrochemical industry, and polymer grade ethylene and propylene are the basic raw materials of downstream poly-unit.Wherein the selection hydrogenation of acetylene has extremely important impact to the ethene processing industry, 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, to improving the yield of ethene of whole technological process, improve the device economic benefit significant.
The cracking C-2-fraction contains the acetylene that molar fraction is 0.5%～2.5%, when producing polyethylene, a small amount of acetylene in ethene can reduce the activity of polymerizing catalyst, and make the deterioration in physical properties of polymkeric substance, so the acetylene content in ethene must be dropped to certain limit, could be as the monomer of synthetic high polymer.Therefore acetylene separation and conversion are one of processes important in the ethylene unit flow process.
In ethylene unit, catalysis selective hydrogenation comprises front-end hydrogenation and back end hydrogenation, ethylene front-end hydrogenation and back end hydrogenation refer to that acetylene hydrogenation reactor is for the demethanizing tower position, hydrogenator is front-end hydrogenation before being positioned at demethanizing tower, and hydrogenator is back end hydrogenation after being positioned at demethanizing tower.The advantage of back end hydrogenation technique is that the hydrogenation process control device is many, is difficult for temperature runaway, easy to operate, but the shortcoming easy coking that is catalyzer, the reproduction ratio of catalyzer is more frequent.Its reason is in hydrogenation process, because the amount of allocating into of hydrogen is few, the hydrogenation dimerization reaction of acetylene easily occurs, and generates 1,3-butadiene and generates, and further generate the wider oligopolymer of molecular weight, is commonly called as " green oil ".Green oil is adsorbed on catalyst surface, and further forms coking, blocks the catalyzer duct, and catalyst activity and selectivity are descended.
Carbon two back end hydrogenations mainly adopt two sections or three sections reactors in series techniques at present, and the device that air speed is lower or alkynes content is low can adopt the two reactor series connection.Full scale plant, mainly take three sections reactors in series techniques as main at present.
The back end hydrogenation material generally consists of: the acetylene of 1.0～2.2% (v/v), and 65～85% ethene, all the other are ethane, hydrogen is allocated into after measuring.
This reaction is for thermopositive reaction, but temperature rise is relatively low, and according to the air speed size, the single reactor maximum temperature rise does not wait from 30～60, so substantially adopt adiabatic reactor.
To two reactor, the first paragraph reactor requires to transform the acetylene more than 70%, and the second segment reactor is less than 5 * 10 by remaining acetylene conversion to its content
-6(V/V).
The device higher to air speed or acetylene content is higher, generally adopt three sections reactor process, and first paragraph transforms 50% left and right, and all the other two sections transform remaining acetylene, and three sections reactor outlet acetylene contents are less than 5 * 10
-6(V/V).
The amount of allocating into of hydrogen is relevant with acetylene content and adopting process.To three sections reactor process, general first paragraph reactor hydrogen/acetylene is 0.8～1.2, and second segment reactor hydrogen/acetylene is that the 1～1.5, three section reactor hydrogen/acetylene is 1.5～3.
To two reactor technique, general first paragraph reactor hydrogen/acetylene is 1～1.5, and second segment reactor hydrogen/acetylene is 2～4.
This reaction mechanism is as follows:
Main reaction C
2H
2+ H
2→ C
2H
4Δ H=-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)
2C
2H
2+H
2→C
4H
6 (4)
C
2H
2+nC
2H
2+H
2→C
2n+2H
2n+4 (5)
In these reactions, reaction (1) is acetylene hydrogenation, and reaction (2) and (3) is ethylene hydrogenation.Reaction (4) is the hydrogenation dimerization of acetylene, to generating green oil, important contribution is arranged, and reaction (5) is the general reaction formula that generates green oil.
In these reactions, only respond (1) wishes the reaction occurred, and all the other are all not wish the reaction occurred.
US5856262 has reported that take the silicon oxide of potassium hydroxide (or oxyhydroxide of barium, strontium, rubidium etc.) modification is carrier, and the method for the low acid palladium catalyst of preparation, at air speed 3000h
-1, 35 ℃ of temperature ins, entrance acetylene molar fraction 0.71%, under the condition of hydrogen alkynes mol ratio 1.43, outlet acetylene molar fraction is less than 1 * 10
-7, ethylene selectivity reaches 56%.Patent US 4404124 be take aluminum oxide as carrier, adds promotor silver and palladium effect, has prepared carbon two hydrogenation catalysts of excellent property.This catalyzer has the ethane of minimizing growing amount, and the acetylene of restrain adsorption on catalyst surface carries out the partial hydrogenation dimerization reaction, suppresses 1, the 3-divinyl generates, and reduces green oil and generates, and improves ethylene selectivity, reduce the characteristics of oxygenatedchemicals growing amount, be applied widely in ethylene industry.Yet above-mentioned catalyzer all adopts pickling process to prepare, and is subject to preparation method's restriction, metal dispersity is only 30% left and right, and also there are many deficiencies in catalyst performance, and further improved necessity is still arranged.
Traditional Pd-Ag bimetal selective hydrogenation catalyst is all to adopt the preparation of aqueous solution pickling process.Adopt while dividing leaching method, a kind of component is understood the more carrier surface that is enriched in, and another kind of component is enriched in outside surface, only has the part metals atom to interpenetrate, and has formed alloy structure.While adopting the total immersion method, because the presoma of two metal ion species is different from the interaction of carrier, and surface tension and solvation, the very difficult uniform loading that forms two kinds of components, also can only partly form alloy structure.When this catalyzer is applied to C 2 fraction selective hydrogenation, often better in the initial reaction stage selectivity, with the prolongation of working time, selectivity constantly descends, and generally moving 3～6 months just needs regeneration, and financial loss is larger.
Summary of the invention
The object of the present invention is to provide a kind of method of C-2-fraction back end hydrogenation, have the Pd-Ag catalyzer of height alloy structure by selection, the selectivity that improved hydrogenation, improved the increment of ethene, improved the economic benefit of device operation.
Inventor's discovery, after the Pd in catalyzer, Ag form alloy, Pd is separated by Ag, makes the spacing in active centre widen, and hydrodimerized probability occurs during two acetylene molecule hydrogenation and greatly descend.The growing amount of 1,3-butadiene significantly descends, and therefore the surperficial coking rate of catalyzer also reduces greatly, and the catalyzer cycle of operation extends, and economic benefits are obvious.
The invention provides a kind of C-2-fraction process for selective hydrogenation, after being positioned at demethanizing tower for the adiabatic reactor reactor of hydrogenation, by in ethylene unit from carbon two hydrogenation materials of front-end deethanization tower, after adding and being press-fitted hydrogen, enter the adiabatic reactor reactor and selected hydrogenation, it is characterized in that: the Pd-Ag series catalysts is housed, with Al in the adiabatic reactor reactor
2O
3Or Al
2O
3With other hopcalite be carrier, the quality of catalyzer of take is 100%, wherein Pd content is that 0.03～0.06%, Ag content is 0.06～0.2%, the specific surface area of catalyzer is 15～50m
2/ g; Pore volume is 0.25～0.8ml/g; This catalyzer has formed the organic polymer metal complex in preparation process; Reaction conditions is: 40～100 ℃ of adiabatic reactor reactor inlet temperatures, reaction pressure 1.5～2.5MPa, gas space velocity 2000～10000h
-1.
The characteristics of the Pd-Ag series catalysts used in the present invention are: this catalyzer is prepared by the method by employing metal of the present invention-organic polymer complex compound presoma.
The preparation method that catalyzer is recommended is: by complexing agent, make palladium and silver form 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.
Complexing agent of the present invention 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, and the functional group of complexing agent can be amido or two amidos.
Contain the group that can react with complexing agent on organic macromolecule side chain of the present invention, this group can be one or more in halogen, cyano group.
The present invention is the back end hydrogenation processing method, forms in the entrance raw material and is mainly C-2-fraction, acetylene 1.0～2.5 (v/v) % wherein, ethane 11.2-30.3 (v/v) %, ethene 68.8-88.9 (v/v) %.The present invention is not specially limited the hydrogen alkynes ratio of each reactor, uses common hydrogen alkynes to get final product than (V/V), is generally 0.8～4.To three sections reactor process, general first paragraph reactor hydrogen/acetylene is 0.8～1.2, and second segment reactor hydrogen/acetylene is that the 1～1.5, three section reactor hydrogen/acetylene is 1.5～3.To two reactor technique, general first paragraph reactor hydrogen/acetylene is 1～1.5, and second segment reactor hydrogen/acetylene is 2～4.
Define the catalyst type of use in the present invention, such catalyst selectivity and traditional catalyst have larger difference.
Principle of the present invention is: in selective hydrogenation reaction, along with used catalyst activity component Pd, Ag form alloy, the quantity of the hydrogen that the catalyst body phase is adsorbed significantly reduces, and the trend of acetylene generation deep hydrogenation reduces greatly, and the catalyzed reaction selectivity is significantly improved.
The acquisition of this catalyzer preferably includes following steps: by complexing agent, organic polymer is loaded on support of the catalyst, grafted functional group on the macromolecular chain of institute's load, the solution of preparation palladium-Yin, having functionalized high molecular precursor to be impregnated in the solution of the palladium-Yin prepared load is reacted, palladium, silver are complexed on the macromolecular chain of load, 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.In the process of roasting, palladium-silver atoms can carry out oxidizing reaction in position, and in the final crystalline phase formed, the distribution of palladium-Yin is that catalyzer prepared by this method is the alloy-type bimetallic catalyst, possesses excellent selectivity uniformly.
Described Al
2O
3Carrier refers to Al
2O
3Or Al
2O
3With other hopcalite be carrier, Al
2O
3Be preferably γ, δ, θ, α or several mixing crystal formation wherein.Carrier can be spherical, bar shaped, cloverleaf pattern, Herba Galii Bungei shape or tooth ball-type etc.
Catalyzer preparation of the present invention can adopt following process to implement, and this process can be divided into 3 steps and carry out.
1. at first prepare functionalized-polymer (polymer)/Al
2O
3Presoma.
2. prepare again (Pd-Ag)-polymer/Al
2O
3Presoma.
3. carry out roasting 2～6h at 450～550 ℃ of presomas to step 2 preparation.
The method of hydrotreating of present method only limits to the catalyzer that adopts the present invention to limit.
The preparation method of this catalyzer comprises the steps:
A, functionalized-polymer/Al
2O
3The preparation of presoma
Organic polymer (as PVC) is dissolved in to organic solvent fully as in THF (tetrahydrofuran (THF)), forms macromolecular solution, by carrier impregnation, in above-mentioned solution, the standing organic polymer (polymer) that makes is deposited on Al
2O
3Surface, drying; Add the complexing agent that contains functional group, the 30～300min that refluxes, be cooled to room temperature again, with deionized water wash, to neutral, obtains functionalized-polymer/Al
2O
3Presoma.
More specifically method as: under 20～35 ℃, by the macromolecule dissolution that has reactive group on side chain, in organic solvent, by carrier impregnation, in above-mentioned solution, standing 2～6h, make described polymer be deposited on Al
2O
3Surface after drying, adds complexing agent under 20～35 ℃, described complexing agent both can carry out functionalization with high molecular side-chain radical, and ion that again can complexing Pd, Ag after reaction, by the above-mentioned solution 1～4h that refluxes, be cooled to 20～35 ℃, use deionized water wash, drying.
The polymer that there is reactive group on described side chain, refer to that polymer side chain contains halogen, the polymer of the groups such as cyano group, as polyvinyl chloride (PVC), polystyrene vinyl cyanide (SAN) etc., described complexing agent, for the micromolecular compound of amido or two amido functional groups can be provided, can be Dyhard RU 100, thanomin, quadrol or oxammonium hydrochloride can be wherein one or more; In mole number, in complexing agent mole number/polymer, the reactive group mole number preferably 100～1.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Preparation Pd (NO
3)
2, Ag NO
3Mixing solutions, and be 1～4 with inorganic acid for adjusting pH value, take prepared functionalized-polymer/Al
2O
3Presoma, by Pd (NO
3)
2, Ag NO
3Mixing solutions join on precursor, stir 5～60min, incline and raffinate, with deionized water by above-mentioned product wash, drying, obtain (Pd-Ag)-polymer/Al
2O
3Presoma; The mole number of functional group's mole number on functionalized rear macromolecular chain/(Pd+Ag) preferably 100～1.
The preparation of C, catalyzer
By the presoma of above-mentioned preparation, in air atmosphere, 450～550 ℃ of roasting 4～8h, obtain Pd-Ag/Al
2O
3Catalyzer.
Also can by more than the catalyzer that makes, use H in reactor
2Reduce processing, obtain (Pd-Ag)/Al
2O
3.Above-mentioned roasting can be carried out in oxygen atmosphere is arranged, and effect is better.
When catalyzer is used, the catalyzer that above method can be made is used H in reactor
2Reduce processing, obtain the reduction-state catalyzer.
Polymer of the present invention is the polymer that contains reactive group on 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.Can be specifically Dyhard RU 100, thanomin, quadrol, oxammonium hydrochloride etc.
The mole number of functional group's mole number on functionalized rear macromolecular chain/(Pd+Ag) preferably 100～1, concrete example is as the mole number of reactive group-CN in SAN (cyanogen root) mole number/(Pd+Ag) preferably 100～1.The mole number of complexing agent mole number/(Pd+Ag) preferably 10000～1.
Adding solvent in steps A is for polymer is dissolved fully, and 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 is how many, is mainly to control institute's solubilizing agent can make polymer fully dissolve and get final product.
In the present invention, reactor refers to the adiabatic reactor reactor.Can be single or many, preferably 2～3.
The inventor also finds, when adopting the method to carry out selective hydrogenation reaction, the selectivity of catalyzed reaction also is improved.The ethene increment improves.
The accompanying drawing explanation
Fig. 1 is carbon two back end hydrogenation process flow sheets.
In figure: the 1-oil scrubber; The 2-water wash column; The 3-soda-wash tower; The 4-moisture eliminator; The 5-demethanizing tower; 6-front-end deethanization tower; 7-carbon two hydrogenators; The 8-interchanger.
Embodiment
Embodiment 1
The catalyzer preparation:
A, functionalized poly vinylchlorid (PVC)/Al
2O
3Preparation
Take Φ 4.5mm, length is 4.5mm, and specific surface area is 15.m
2/ g, pore volume is 0.25ml/g, bulk density is 1.1g/cm
3Column Al
2O
3Carrier 250g.
PVC4.450g is dissolved in 400mlTHF (tetrahydrofuran (THF)) fully, in above-mentioned solution, after standing 2h, makes PVC be adsorbed in Al above-mentioned carrier impregnation
2O
3Surface, drying.Obtain 205gPVC/Al
2O
3Product.
Add 59.64g Dyhard RU 100 and 2.0gNa
2CO
3,, add 205g PVC/Al
2O
3Backflow 1h, be cooled to room temperature, extremely neutral with deionized water wash, drying for standby.Obtain functionalized PVC/Al
2O
3.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take 0.165gPd (NO
3)
2, 0.8gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take prepared functionalized-PVC/Al
2O
3Presoma 255g, join Pd (NO by it
3)
2, AgNO
3Mixing solutions in, stir 30min, incline and raffinate, by above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-PVC/Al
2O
3Presoma.
The preparation of C, catalyzer
By the presoma of above-mentioned preparation, 550 ℃ of roasting 2h in air atmosphere, obtain oxidation state (Pd-Ag)/Al
2O
3Catalyzer.Before use, being positioned in fixed-bed reactor, is N by mol ratio
2: H
2=0.1: 1 mixed gas, at 120 ℃ of temperature, air speed 100h
-1The time, 12h is processed in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is that 0.03%, Ag content is 0.2%.
Adopt back end hydrogenation technique, raw material forms as shown in table 1.
Table 1 hydrogenating materials forms
| Hydrogenating materials | C 2H 4 | C 2H 2 | C 2H 6 |
| Content (mol%) | 75.5 | 1.5 | 23 |
The technological reaction condition is: use two sections adiabatic reactor reactors.
Material air speed: 2000h
-1, working pressure: 1.5MPa, loaded catalyst: 300ml.45 ℃ of reactor inlet temperatures, first stage reactor entrance H
2/ C
2H
2=1: 1 (V/V); Second stage reactor entrance H
2/ C
2H
2=2: 1 (V/V), result is as shown in table 2.
Comparative Examples 1
The catalyzer preparation
Take Φ 4.5mm, length is 4.5mm, and specific surface area is 15m
2/ g, pore volume is 0.25ml/g, bulk density is 1.1g/cm
3Column Al
2O
3Carrier 250g.
Take 0.165gPd (NO
3)
2, 0.8gAg NO
3, measure 0.5ml nitric acid, be mixed with 180ml solution.Above-mentioned carrier is joined in the solution of having prepared, stir 30min, incline and raffinate, after drying, at 550 ℃ of roasting temperature 8h, obtain (Pd-Ag)/Al
2O
3Catalyzer.Before use, being positioned in fixed-bed reactor, is N by 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 0.03%, Ag content is 0.2%.
Carbon two hydrogenation flow processs and processing condition are identical with embodiment 1.After the examination of 500 hours, result is as shown in table 2.
Reaction result after table 2 examination of 500 hours
Embodiment 2
The catalyzer preparation
A, functionalized polystyrene vinyl cyanide (SAN)/Al
2O
3Preparation
Take Φ 2.5mm, specific surface area is 50m
2/ g, pore volume is 0.8ml/g, bulk density is 0.65g/cm
3Spherical Al
2O
3Carrier 250g
Take SAN resin 1.1g, be dissolved in 300ml DMF (dimethyl formamide) solvent, under room temperature, stir the SAN resin is dissolved fully, add the above-mentioned carrier of weighing in this solution, fully stir latter standing 6 hours, dry after the separation solvent, obtain SAN/Al
2O
3.
By SAN/Al obtained above
2O
3, join in the 500ml deionized water, add the 28.8g quadrol, backflow 4h, cooling rear taking-up product, washing is to neutral, drying obtains functionalized-SAN/Al
2O
3.
B, (Pd-Ag)-SAN/Al
2O
3The preparation of presoma
Take 0.47gPd (NO
3)
2, 0.4gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take prepared functionalized-SAN/Al
2O
3Presoma 251.1g, by functionalized-SAN/Al
2O
3Join Pd (NO
3)
2, AgNO
3Mixing solutions in, stir 5min, incline and raffinate, by above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-SAN/Al
2O
3Presoma.
The preparation of C, catalyzer
By the presoma of above-mentioned preparation, at 450 ℃ of roasting 4h of air atmosphere, obtain (Pd-Ag)/Al
2O
3Catalyzer.Recording this catalyst P d content is that 0.06%, Ag content is 0.1%.
Comparative Examples 2
The catalyzer preparation
Take Φ 2.5mm, specific surface area is 50m
2/ g, pore volume is 0.8ml/g, bulk density is 0.65g/cm
3Spherical θ-Al
2O
3Carrier 250g.
Take 0.47gPd (NO
3)
2Being dissolved in the 300ml deionized water, is 2.8 with the pH value of dilute hydrochloric acid regulator solution, and described carrier impregnation, in the solution prepared, is stirred to 5min, inclines and raffinate, 120 ℃ of dryings 10 hours, obtains catalyst A.
Take 0.4gAgNO
3, measure 0.5ml nitric acid and be mixed with 300ml solution.Above-mentioned carrier is joined in the solution of having prepared, stir 5min, incline and raffinate, after drying, at 450 ℃ of roasting temperature 2h, obtain (Pd-Ag)/Al
2O
3Catalyzer. recording this catalyst P d content is that 0.06%, Ag content is 0.1%.
The reduction of catalyzer:
Reducing gas: hydrogen, reduction air speed: 100h
-1, 80 ℃ of temperature, keep 8h.
Adopt back end hydrogenation technique, its process flow sheet raw material as shown in Figure 1 consists of:
C
2H
2：1.5％(V％) C
2H
4 80％(V％)，C
2H
618.5％(V％)。
Reaction conditions: two sections adiabatic reactor reactors in series reactions, the first stage reactor outlet material enters second stage reactor.Every section reactor all has independently gas distributing system.
Material gas space velocity: 5000h
-1, working pressure: 1.9MPa, each reactor catalyst loadings: 300ml.40 ℃ of first stage reactor temperature ins, H
2/ C
2H
2=3: 1 (V/V); 50 ℃ of second stage reactor temperature ins, H
2/ C
2H
2=2: 1 (V/V), after the examination of 500 hours, result is as shown in table 3.
Reaction result after table 3 examination of 500 hours
Embodiment 3
The catalyzer preparation
Take Φ 4.5mm, length is 4.5mm, and specific surface area is 25.m
2/ g, pore volume is 0.35ml/g, bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
The preparation of A, functionalized chlorinatedpolyethylene (CPE)
CPE 8.0g is dissolved in 400mlTHF fully, adds 240g Dyhard RU 100 and 2.0gNa
2CO
3,, add CPE to reflux 2 hours, be cooled to room temperature, to neutral, obtain functionalized CPE standby with deionized water wash.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take 0.22gPd (NO
3)
2, 0.28gAg NO
3, measure 0.5ml nitric acid, join in above-mentioned functionalized CPE solution, stir 60min, obtain (Pd-Ag)-CPE.
The 250g carrier is added in mixing solutions, standing 4h after fully stirring, above-mentioned product is extremely neutral with deionized water wash, obtain (Pd-Ag)-CPE/Al
2O
3Presoma.
The preparation of C, catalyzer
By the presoma of above-mentioned preparation, 500 ℃ of roasting 4h in air atmosphere, obtain oxidation state (Pd-Ag)/Al
2O
3Catalyzer.Before use, being positioned in fixed-bed reactor, is N by 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 0.04%, Ag content is 0.06%.
Comparative Examples 3
The catalyzer preparation
Take Φ 4.5mm, length is 4.5mm, and specific surface area is 25m
2/ g, pore volume is 0.35ml/g, bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
Take 0.22gPd (NO
3)
2, 0.28gAgNO
3, add 0.5ml nitric acid, prepare to obtain 87.5ml solution, this solution spraying to be shaken 0.5 hour to above-mentioned carrier, after drying, in air atmosphere, 500 ℃ of roasting 4h obtain (Pd-Ag)/Al
2O
3Catalyzer.Recording this catalyst P d content is that 0.04%, Ag content is 0.06%.
The reduction of catalyzer: reducing gas: hydrogen, reduction air speed: 200h
-1, 180 ℃ of temperature, keep 8h.
Adopt back end hydrogenation technique, reaction raw materials is:
C
2H
2：2.5(V％) C
2H
4 80(V％)，C
2H
617.5(V％)。
Reaction conditions: three sections adiabatic reactor reactors in series techniques, the first stage reactor outlet material enters second stage reactor, and the second stage reactor outlet material enters three sections reactors, and every section reactor all has independently gas distributing system.
Material air speed: 10000h
-1, working pressure: 2.5MPa, loaded catalyst: 300ml.50 ℃ of first stage reactor temperature ins, H
2/ C
2H
2=1: 1 (V/V); 80 ℃ of second stage reactor temperature ins, H
2/ C
2H
2=2: 1 (V/V); 100 ℃ of three sections reactor inlet temperatures, H
2/ C
2H
2=3: 1 (V/V) result after the examination of 500 hours is as shown in table 4.
Reaction result after table 4 examination of 500 hours
Can find out, adopted method of hydrotreating of the present invention, the activity of hydrogenation reaction and selectivity are better than traditional method of hydrotreating greatly, also decrease of the growing amount of green oil in hydrogenation process.Because the reduction of green oil, make the active centre of catalyzer do not covered by by product, catalyst activity and selectivity are able to good maintenance.
Claims (16)
1. a C-2-fraction process for selective hydrogenation, after being positioned at demethanizing tower for the fixed-bed reactor of hydrogenation, by in ethylene unit from carbon two hydrogenation materials of front-end deethanization tower, after adding and being press-fitted hydrogen, enter the adiabatic reactor reactor and selected hydrogenation, it is characterized in that: the Pd-Ag series catalysts is housed, with Al in fixed-bed reactor
2O
3Or Al
2O
3With other hopcalite be carrier, the quality of catalyzer of take is 100%, wherein Pd content is that 0.03～0.06%, Ag content is 0.06～0.2%, the specific surface area of catalyzer is 15～50m
2/ g; Pore volume is 0.25～0.8ml/g; This catalyzer has formed the organic polymer metal complex in preparation process; Reaction conditions is: 40～100 ℃ of fixed-bed reactor temperature ins, reaction pressure 1.5～2.5MPa, gas volume air speed 2000～10000h
-1The acquisition of catalyzer comprises the steps: by complexing agent the organic polymer grafted functional group and loads on support of the catalyst, obtains functionalized-polymer/Al
2O
3Presoma; The solution of preparation palladium-Yin, have load functionalized-polymer/Al
2O
3Presoma is impregnated in the palladium prepared-Yin solution and is reacted, and palladium, silver are complexed on 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.
2. method of hydrotreating according to claim 1, is characterized in that 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.
3. method of hydrotreating according to claim 2, is characterized in that the contained functional group of complexing agent is amido.
4. method of hydrotreating according to claim 1, is characterized in that on the organic macromolecule side chain containing the group that can react with complexing agent.
5. method of hydrotreating according to claim 4, is characterized in that on the organic macromolecule side chain containing the group that can react with complexing agent and be one or more in halogen, cyano group.
6. method of hydrotreating according to claim 1, is characterized in that Al
2O
3Crystal formation be γ, δ, θ, α or several mixing crystal formation wherein.
7. method of hydrotreating according to claim 1, while it is characterized in that prepared by catalyzer, by complexing agent by the organic polymer grafted functional group and load on support of the catalyst, refer to: organic polymer is loaded on support of the catalyst, then by complexing agent grafted functional group on the macromolecular chain of institute's load.
8. method of hydrotreating according to claim 1, while it is characterized in that prepared by catalyzer, by complexing agent by the organic polymer grafted functional group and load on support of the catalyst, refer to: first by complexing agent by after the organic polymer grafted functional, be carried on again on support of the catalyst, prepare functionalized-polymer/Al
2O
3Presoma.
9. method of hydrotreating according to claim 1, 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 organic solvent, forms macromolecular solution, then by carrier impregnation in above-mentioned solution, the standing organic polymer that makes is deposited on Al
2O
3Surface, 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, take prepared functionalized-polymer/Al
2O
3Presoma, join the solution of preparation palladium-Yin on precursor, floods 5～60min under 20～35 ℃, and washing, drying, obtain Pd-Ag-high-molecular complex/Al
2O
3Presoma;
C. the preparation of catalyzer
By the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h, obtain Pd-Ag/Al
2O
3Catalyzer.
10. method of hydrotreating according to claim 9, it is characterized in that on functionalized rear macromolecular chain functional group's mole number/(Pd+Ag) mole number is 100～1.
11. method of hydrotreating according to claim 9, is characterized in that in mole number, in complexing agent mole number/polymer, the reactive group mole number is 100～1.
12. method of hydrotreating according to claim 9, is characterized in that the mole number of complexing agent mole number/(Pd+Ag) is 10000～1.
13. method of hydrotreating according to claim 1, is characterized in that hydrogen/acetylene volume ratio is 0.8～4.
14. method of hydrotreating according to claim 1, is characterized in that adiabatic reactor reactor reaction bed number is two sections or three sections beds.
15. method of hydrotreating according to claim 14, while it is characterized in that adiabatic reactor reactor reaction bed number is two sections, first paragraph reactor hydrogen/acetylene volume ratio is 1～1.5, and second segment reactor hydrogen/acetylene volume ratio is 2～4.
16. method of hydrotreating according to claim 14, while it is characterized in that adiabatic reactor reactor reaction bed number is three sections, first paragraph reactor hydrogen/acetylene volume ratio is 0.8～1.2, second segment reactor hydrogen/acetylene volume ratio is that the 1～1.5, three section reactor hydrogen/acetylene volume ratio is 1.5～3.
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