CN102206131A - Selective hydrogenation method for C2 fraction - Google Patents
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- CN102206131A CN102206131A CN2011100861581A CN201110086158A CN102206131A CN 102206131 A CN102206131 A CN 102206131A CN 2011100861581 A CN2011100861581 A CN 2011100861581A CN 201110086158 A CN201110086158 A CN 201110086158A CN 102206131 A CN102206131 A CN 102206131A
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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 selection method of hydrotreating, particularly a kind of C 2 fraction selective hydrogenation removes the method for 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 influence 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, it is significant to improve the device economic benefit.
It is 0.5%～2.5% acetylene that the cracking C-2-fraction contains molar fraction, when producing polyethylene, a little acetylene in the ethene can reduce the activity of polymerizing catalyst, and make the deterioration in physical properties of polymkeric substance, so the acetylene content in the 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.
Catalysis selective hydrogenation comprises front-end hydrogenation and back end hydrogenation in the ethylene unit, acetylene front-end hydrogenation and back end hydrogenation are meant that acetylene hydrogenation reactor is for the demethanizing tower position, hydrogenator is front-end hydrogenation before being positioned at demethanizing tower, and hydrogenator is a back end hydrogenation after being positioned at demethanizing tower.The advantage of back end hydrogenation technology is that the hydrogenation process control device is many, is difficult for temperature runaway, and is 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 takes place easily, generates 1,3-butadiene and generates, and further generate the oligopolymer of molecular weight broad, 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 current two back end hydrogenations mainly adopt two sections or three sections reactors in series technologies, and the device that air speed is lower or alkynes content is low can adopt the two reactor series connection.Present full scale plant is mainly based on three sections reactors in series technologies.
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 adopt adiabatic reactor substantially.
To two reactor, first section reactor requires to transform the acetylene more than 70%, second section reactor with remaining acetylene conversion to its content less than 5 * 10
-6(V/V).
The device higher to air speed or acetylene content is higher generally adopts three sections reactor process, and first section transforms about 50%, 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 section reactor hydrogen/acetylene is that 0.8～1.2, second section reactor hydrogen/acetylene is that the 1～1.5, three section reactor hydrogen/acetylene is 1.5～3.
To two reactor technology, general first section reactor hydrogen/acetylene is that 1～1.5, second section 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 an acetylene hydrogenation, and reaction (2) and (3) is an 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, the reaction that only respond (1) wish to take place, all the other all are not wish the reaction that takes place.
US5856262 has reported that the silicon oxide with potassium hydroxide (or oxyhydroxide of barium, strontium, rubidium etc.) modification is a carrier, and the method for the low acid palladium catalyst of preparation is at air speed 3000h
-1, 35 ℃ of temperature ins, inlet 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 is a carrier with the aluminum oxide, 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 that suppresses to be adsorbed on the 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, in ethylene industry, obtained widespread use.Yet above-mentioned catalyzer all is to adopt immersion process for preparing, is subjected to preparation method's restriction, and metal dispersity only is about 30%, and also there are many deficiencies in catalyst performance, and further improved necessity is still arranged.
It all is to adopt aqueous solution immersion process for preparing that traditional Pd-Ag bimetal is selected hydrogenation catalyst.Adopt when 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, has only the part metals atom to interpenetrate, and has formed alloy structure.Adopt when being total to leaching method, because the presoma of two metal ion species is different with carrier interactions, 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 was applied to C 2 fraction selective hydrogenation, often better in the initial reaction stage selectivity, with the prolongation of working time, selectivity constantly descended, and generally moving 3～6 months just needs regeneration, and financial loss is bigger.
Summary of the invention
The object of the present invention is to provide a kind of method of C-2-fraction back end hydrogenation, by selecting to have the Pd-Ag catalyzer of height alloy structure, the selectivity that improved hydrogenation has improved the increment of ethene, has improved the economic benefit of device operation.
The inventor finds that after the Pd in the catalyzer, Ag formed alloy, Pd was separated by Ag, makes the spacing in active centre widen, and during two acetylene molecule hydrogenation hydrodimerized probability takes place and descends greatly.The growing amount of 1,3-butadiene descends significantly, and therefore the surperficial coking rate of catalyzer also reduces greatly, and the catalyzer cycle of operation prolongs, and economic benefits are obvious.
The invention provides a kind of C-2-fraction process for selective hydrogenation, the adiabatic reactor reactor that is used for hydrogenation is positioned at after the demethanizing tower, with in the ethylene unit from carbon two hydrogenation materials of front-end deethanization tower, through add be press-fitted hydrogen after, enter the adiabatic reactor reactor and select hydrogenation, it is characterized in that: the Pd-Ag series catalysts is housed, in the adiabatic reactor reactor with Al
2O
3Or Al
2O
3With other hopcalite be carrier, be 100% in the quality of catalyzer, wherein Pd content is 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 that uses among the present invention are: this catalyzer is by the preparation of the method for employing metal of the present invention-organic polymer complex compound presoma.
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 of the present invention is both can carry out functionalization with high molecular side-chain radical, ionic complexing agent that can complexing Pd, Ag after reaction again, 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.
The present invention is the back end hydrogenation processing method, forms to be 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) % in the inlet raw material.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 section reactor hydrogen/acetylene is that 0.8～1.2, second section reactor hydrogen/acetylene is that the 1～1.5, three section reactor hydrogen/acetylene is 1.5～3.To two reactor technology, general first section reactor hydrogen/acetylene is that 1～1.5, second section reactor hydrogen/acetylene is 2～4.
Define the catalyst type of use among the present invention, such catalyst selectivity and traditional catalyst have bigger difference.
Principle of the present invention is: in selective hydrogenation reaction, along with employed catalyst activity component Pd, Ag form alloy, the quantity of the hydrogen that catalyst body is mutually adsorbed reduces significantly, 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 the 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 that has prepared load reacts, 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 the distribution of palladium-Yin is that catalyzer prepared by this method is the alloy-type bimetallic catalyst, possesses excellent selectivity uniformly in the final crystalline phase that forms.
Described Al
2O
3Carrier is meant Al
2O
3Or Al
2O
3With other hopcalite be carrier, Al
2O
3Be preferably γ, δ, θ, α or wherein several mixing crystal formations.Carrier can be sphere, bar shaped, cloverleaf pattern, Herba Galii Bungei shape or tooth ball-type etc.
Preparation of Catalyst of the present invention can adopt following process to implement, this process can be divided into 3 the step carry out.
1. at first prepare functionalized-polymer (polymer)/Al
2O
3Presoma.
2. refabrication (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.
This Preparation of catalysts method comprises the steps:
A, functionalized-polymer/Al
2O
3The preparation of presoma
Organic polymer (as PVC) is dissolved among organic solvent such as the THF (tetrahydrofuran (THF)) fully, forms macromolecular solution, carrier impregnation in above-mentioned solution, is left standstill and makes organic polymer (polymer) be deposited on Al
2O
3The surface, drying; Add the complexing agent that contains functional group again, the 30～300min that refluxes is cooled to room temperature, to neutral, obtains functionalized-polymer/Al with deionized water wash
2O
3Presoma.
More specifically method as: under 20～35 ℃, the macromolecule dissolution that has reactive group on the side chain in organic solvent, in above-mentioned solution, is left standstill 2～6h with carrier impregnation, makes described polymer be deposited on Al
2O
3The surface after the drying, adds complexing agent down at 20～35 ℃, described complexing agent both can carry out functionalization with high molecular side-chain radical, and ion that can complexing Pd, Ag after reaction again is with the above-mentioned solution 1～4h that refluxes, be cooled to 20～35 ℃, use deionized water wash, drying.
The polymer that has reactive group on the described side chain, be meant that polymer side chain contains halogen, the polymer of groups such as cyano group, as polyvinyl chloride (PVC), polystyrene vinyl cyanide (SAN) etc., described complexing agent can be a Dyhard RU 100 for the micromolecular compound of amido or two amido functional groups can be provided, 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)-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 by weighing the functionalized-polymer/Al that has prepared
2O
3Presoma is with Pd (NO
3)
2, Ag NO
3Mixing solutions join on the precursor, stir 5～60min, inclining raffinate, with deionized water with above-mentioned product wash, drying, obtain (Pd-Ag)-polymer/Al
2O
3Presoma; The mole number of functional group's mole number on the macromolecular chain of functionalized back/(Pd+Ag) preferably 100～1.
C, Preparation of catalysts
With the presoma of above-mentioned preparation, 450～550 ℃ of roasting 4～8h obtain Pd-Ag/Al in air atmosphere
2O
3Catalyzer.
Also can with more than the catalyzer that makes, in reactor, use H
2Reduce processing, obtain (Pd-Ag)/Al
2O
3Above-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 going back the ortho states 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 macromolecular chain of functionalized back/(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 help 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.
Reactor is meant the adiabatic reactor reactor among the present invention.Can be single or many, preferably 2～3.
The inventor finds that also when this method of employing was carried out selective hydrogenation reaction, the selectivity of catalyzed reaction also was improved.The ethene increment improves.
Description of drawings
Fig. 1 is carbon two back end hydrogenation process flow sheets.
Among the 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
Preparation of Catalyst:
A, functionalized poly vinylchlorid (PVC)/Al
2O
3Preparation
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 15.m
2/ g, pore volume are 0.25ml/g, and bulk density is 1.1g/cm
3Column Al
2O
3Carrier 250g.
PVC4.450g is dissolved among the 400mlTHF (tetrahydrofuran (THF)) fully, in above-mentioned solution, makes PVC be adsorbed in Al after leaving standstill 2h above-mentioned carrier impregnation
2O
3The surface, drying.Obtain 205gPVC/Al
2O
3Product.
Add 59.64g Dyhard RU 100 and 2.0gNa
2CO
3,, add 205g PVC/Al
2O
3Backflow 1h is cooled to room temperature, and is 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 by weighing 0.165gPd (NO
3)
2, 0.8gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing the functionalized-PVC/Al that has prepared
2O
3Presoma 255g joins Pd (NO with it
3)
2, AgNO
3Mixing solutions in, stir 30min, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-PVC/Al
2O
3Presoma.
C, Preparation of catalysts
With the presoma of above-mentioned preparation, 550 ℃ of roasting 2h 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 is at 120 ℃ of temperature, air speed 100h
-1The time, 12h is handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is 0.03%, and Ag content is 0.2%.
Adopt back end hydrogenation technology, raw material is formed as shown in table 1.
Table 1 hydrogenating materials is formed
| 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 inlet H
2/ C
2H
2=1: 1 (V/V); Second stage reactor inlet H
2/ C
2H
2=2: 1 (V/V), the result is as shown in table 2.
Comparative Examples 1
Preparation of Catalyst
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 15m
2/ g, pore volume are 0.25ml/g, and bulk density is 1.1g/cm
3Column Al
2O
3Carrier 250g.
Take by weighing 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, inclining raffinate, and dry back obtains (Pd-Ag)/Al at 550 ℃ of roasting temperature 8h
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 handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is 0.03%, and Ag content is 0.2%.
Carbon two hydrogenation flow processs and processing condition are identical with embodiment 1.The result is as shown in table 2 after 500 hours examination.
500 hours examination afterreaction result of table 2
Preparation of Catalyst
A, functionalized polystyrene vinyl cyanide (SAN)/Al
2O
3Preparation
Take by weighing Φ 2.5mm, specific surface area is 50m
2/ g, pore volume are 0.8ml/g, and bulk density is 0.65g/cm
3Spherical Al
2O
3Carrier 250g
Take by weighing SAN resin 1.1g, be dissolved in 300ml DMF (dimethyl formamide) solvent, stirring is dissolved the SAN resin fully under the room temperature, adds the above-mentioned carrier of weighing in this solution, leaves standstill 6 hours after fully stirring, and separates the solvent after drying, obtains SAN/Al
2O
3
With the above-mentioned SAN/Al that obtains
2O
3, join in the 500ml deionized water, add the 28.8g quadrol, backflow 4h, product is taken out in the cooling back, and washing is to neutral, drying obtains functionalized-SAN/Al
2O
3
B, (Pd-Ag)-SAN/Al
2O
3The preparation of presoma
Take by weighing 0.47gPd (NO
3)
2, 0.4gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing the functionalized-SAN/Al that has prepared
2O
3Presoma 251.1g is with functionalized-SAN/Al
2O
3Join Pd (NO
3)
2, AgNO
3Mixing solutions in, stir 5min, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-SAN/Al
2O
3Presoma.
C, Preparation of catalysts
With the presoma of above-mentioned preparation,, obtain (Pd-Ag)/Al at 450 ℃ of roasting 4h of air atmosphere
2O
3Catalyzer.Recording this catalyst P d content is 0.06%, and Ag content is 0.1%.
Comparative Examples 2
Preparation of Catalyst
Take by weighing Φ 2.5mm, specific surface area is 50m
2/ g, pore volume are 0.8ml/g, and bulk density is 0.65g/cm
3Spherical θ-Al
2O
3Carrier 250g.
Take by weighing 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 that has prepared, is stirred 5min, and inclining raffinate, 120 ℃ of dryings 10 hours, obtains catalyst A.
Take by weighing 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, inclining raffinate, and dry back obtains (Pd-Ag)/Al at 450 ℃ of roasting temperature 2h
2O
3Catalyzer. recording this catalyst P d content is 0.06%, and 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 technology, 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, promptly 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), the result is as shown in table 3 after 500 hours examination.
500 hours examination afterreaction result of table 3
Preparation of Catalyst
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 25.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,, add CPE and refluxed 2 hours, be cooled to room temperature, to neutral, it is standby to obtain functionalized CPE with deionized water wash.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take by weighing 0.22gPd (NO
3)
2, 0.28gAg NO
3, measure 0.5ml nitric acid, join in the above-mentioned functionalized CPE solution, stir 60min, obtain (Pd-Ag)-CPE.
The 250g carrier is added in the mixing solutions, leave standstill 4h after fully stirring, above-mentioned product is extremely neutral with deionized water wash, obtain (Pd-Ag)-CPE/Al
2O
3Presoma.
C, Preparation of catalysts
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 handled in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is 0.04%, and Ag content is 0.06%.
Comparative Examples 3
Preparation of Catalyst
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 25m
2/ g, pore volume are 0.35ml/g, and bulk density is 0.75g/cm
3Column Al
2O
3Carrier 250g.
Take by weighing 0.22gPd (NO
3)
2, 0.28gAgNO
3, add 0.5ml nitric acid, prepare 87.5ml solution, with the concussion 0.5 hour to the above-mentioned carrier of this solution spraying, after the drying, 500 ℃ of roasting 4h obtain (Pd-Ag)/Al in air atmosphere
2O
3Catalyzer.Recording this catalyst P d content is 0.04%, and 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 technology, 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 technologies, promptly 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 500 hours examination is as shown in table 4.
500 hours examination afterreaction result of table 4
As can be seen, adopted method of hydrotreating of the present invention, the activity of hydrogenation reaction and selectivity are better than traditional method of hydrotreating greatly, and the growing amount of green oil also reduces significantly in the hydrogenation process.Because the reduction of green oil makes the activity of such catalysts center do not covered by by product, catalyst activity and selectivity are able to good maintenance.
Claims (18)
1. C-2-fraction process for selective hydrogenation, the fixed-bed reactor that are used for hydrogenation are positioned at after the demethanizing tower, carbon two from the front-end deethanization tower in the ethylene unit is added material, through add be press-fitted hydrogen after, enter the adiabatic reactor reactor and select hydrogenation, it is characterized in that: the Pd-Ag series catalysts is housed, in the fixed-bed reactor with Al
2O
3Or Al
2O
3With other hopcalite be carrier, be 100% in the quality of catalyzer, wherein Pd content is 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
-1
2. method of hydrotreating according to claim 1 is characterized in that catalyzer is to make palladium and silver form the organic polymer metal complex with organic polymer by complexing agent, obtains Pd-Ag-polymer/Al
2O
3Presoma; At 380～550 ℃ to Pd-Ag-polymer/Al
2O
3Presoma carries out roasting, and the time is that 2～6h obtains.
3. method of hydrotreating according to claim 2 is characterized in that complexing agent is both can carry out functionalization with high molecular side-chain radical, again ionic complexing agent that can complexing Pd, Ag after reaction.
4. method of hydrotreating according to claim 3 is characterized in that the contained functional group of complexing agent is amido or two amidos.
5. method of hydrotreating according to claim 2, it is characterized in that containing on the organic macromolecule side chain can with the group of complexing agent reaction.
6. method of hydrotreating according to claim 2, 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.
7. 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 palladium-Yin solution of having prepared 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.
8. method of hydrotreating according to claim 1 is characterized in that Al
2O
3Crystal formation be γ, δ, θ, α or wherein several mixing crystal formations.
9. method of hydrotreating according to claim 7, when it is characterized in that Preparation of Catalyst, by complexing agent with the organic polymer grafted functional group and load on the support of the catalyst, be meant: 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.
10. method of hydrotreating according to claim 7, when it is characterized in that Preparation of Catalyst, by complexing agent with the organic polymer grafted functional group and load on the support of the catalyst, be meant: earlier by complexing agent with the organic polymer grafted functionalization after, be carried on again on the support of the catalyst, prepare functionalized-polymer/Al
2O
3Presoma.
11. method of hydrotreating according to claim 7 is characterized in that the acquisition of catalyzer comprises the steps: that the Preparation of catalysts method 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 above-mentioned solution, leave standstill and make organic polymer be deposited on Al
2O
3The surface, drying; Add the complexing agent backflow 0.5～3OOmin that contains functional group again, prepare functionalized-polymer/Al
2O
3Presoma;
B.Pd-Ag-high-molecular complex/Al
2O
3The preparation of presoma
Preparation palladium-Yin solution, and, take by weighing the functionalized-polymer/Al that has prepared with inorganic acid for adjusting pH value 1～4
2O
3Presoma joins the solution of preparing palladium-Yin on the precursor, and 20～35 ℃ flood 5～60min down, and washing, drying obtain Pd-Ag-high-molecular complex/Al
2O
3Presoma;
C. Preparation of catalysts
With the presoma of above-mentioned preparation, 380～550 ℃ of roasting 2～6h obtain Pd-Ag/Al
2O
3Catalyzer.
12. method of hydrotreating according to claim 11, it is characterized in that on the macromolecular chain of functionalized back functional group's mole number/(Pd+Ag) mole number is 100～1.
13. method of hydrotreating according to claim 11 is characterized in that in mole number, the reactive group mole number is 100～1 in complexing agent mole number/polymer.
14. method of hydrotreating according to claim 11 is characterized in that the mole number of complexing agent mole number/(Pd+Ag) is 10000～1.
15. method of hydrotreating according to claim 1 is characterized in that hydrogen/acetylene volume ratio is 0.8～4.
16. method of hydrotreating according to claim 1 is characterized in that adiabatic reactor reactor reaction bed number is two sections or three sections beds.
17. method of hydrotreating according to claim 16, when it is characterized in that adiabatic reactor reactor reaction bed number is two sections, first section reactor hydrogen/acetylene volume ratio is that 1～1.5, second section reactor hydrogen/acetylene volume ratio is 2～4.
18. method of hydrotreating according to claim 16, when it is characterized in that adiabatic reactor reactor reaction bed number is three sections, first section reactor hydrogen/acetylene volume ratio is 0.8～1.2, second section 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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| CN108250031A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of acetylene hydrogenation method of two back end hydrogenation technique of carbon |
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