CN102206132B - Selective hydrogenation method for C3 fraction - Google Patents
Selective hydrogenation method for C3 fraction Download PDFInfo
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- CN102206132B CN102206132B CN201110086151XA CN201110086151A CN102206132B CN 102206132 B CN102206132 B CN 102206132B CN 201110086151X A CN201110086151X A CN 201110086151XA CN 201110086151 A CN201110086151 A CN 201110086151A CN 102206132 B CN102206132 B CN 102206132B
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Abstract
The invention relates to a selective hydrogenation method for a C3 fraction. The method is characterized in that: an adiabatic bed reactor is provided with a Pd-Ag catalyst, the Pd-Ag catalyst contains Al2O3 used as a carrier, 0.2-0.4% of Pd and preferable 0.05-0.2% of Ag based on 100wt% of the catalyst, the specific surface area of the catalyst is 15-100 m<2>/g, the pore volume of the catalyst is 0.3-0.6 mL/g, and the catalyst forms an organic polymer metal complex during preparation process; and the hydrogenation process conditions are as follows: the inlet temperature of the fixed bed reactor is 10-50 DEG C, the reaction pressure is 2.5-3.5 MPa, the liquid phase volume space velocity is 5-100 h<-1> and the mol ratio of hydrogen to propyne and propadiene is (1-5):1. The selective hydrogenation method provided by the invention improves the hydrogenation activity and selectivity, greatly broadens the reaction space velocity range, greatly improves the running safety and efficiency of an apparatus and greatly improves economical benefits of the apparatus.
Description
Technical field
The present invention relates to a kind of selection method of hydrotreating, particularly a kind of C 3 fraction selective hydrogenation except the method for acetylene.
Background technology
Obtaining of high-purity propylene is the prerequisite that polypropylene is produced, and the key of high-purity propylene production is propine (MA) and the propadiene (PD) of removing in the C3 fraction, the general method of selecting hydrogenation that adopts.
Present hydrogenation technique mainly adopts liquid-phase hydrogenatin, because the propine in carbon three components and propadiene (MA+PD) have stronger polymerization tendency, easily forms coking at catalyst surface.Cause thus catalyst activity reduction, make hydrogenated products off quality, the operation life of catalyzer shortens.
There is not the C3 fraction hydrogenation technique flow process of pre-hydrogenation, be in the order hydrogenation flow process method of C3 fraction, splitting gas is through washing, oil wash, after alkali cleaning and carbon four separated, at first by the methane tower, its cat head was carbon one cut and hydrogen, tower reactor is carbon two and C3 fraction, pass through again deethanizing column, separation of carbon two and C3 fraction, the composition of its tower reactor is carbon three hydrogenating materials, most of composition is propylene, all the other are a small amount of propane, propine and propadiene, and C3 fraction enters fixedly the adiabatic reactor reactor and carries out liquid-phase hydrogenatin and remove alkynes and diolefine, propylene is 70～90% (mol) in the reactor inlet raw material, propane 10～30% (mol).Propine (MA)+propadiene (PD) is 0.2～8.0% (mol).The common processing condition of this technique hydrogenation reaction are: 10～50 ℃ of reactor inlet temperatures, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 10～60h
-1, (mol)=1～2 of hydrogen/(MA+PD).
The C3 fraction hydrogenation technique flow process of pre-hydrogenation is being arranged, be in the technical process of predepropanization front-end hydrogenation, splitting gas is through oil wash, washing, and after the alkali cleaning, at first by the predepropanization tower, comprise carbon one and hydrogen in the cut of its cat head, C-2-fraction and C3 fraction, tower reactor are the cut that overweights carbon three, and the cut of cat head enters carbon two hydrogenators, wherein carbon one cut and hydrogen volume content are 35～50%, C-2-fraction 35～50%, C3 fraction 10～20%, carbon two hydrogenators of this technique are generally three sections, one, second-stage hydrogenation reactor is mainly used in removing of acetylene, and the 3rd section reactor carries out propine, removing of propadiene.This unit generally adopts gas phase hydrogenation technique, and propine, propadiene decreasing ratio be more than 50%, and through after this flow process, reaction mass separates the C3 fraction after the separation enters carbon three after cooling liquid-phase hydrogenatin through C3 fraction and carbon one C-2-fraction again.Because most of propine propadiene is converted, the hydrogenation load is relatively low, and selectivity of catalyst is had higher requirement.
Usually, at C
3In the fraction selective hydrogenation process, there is following reaction:
Main reaction
MAPD+H
2→CH
3CH＝CH
2 (1)
Side reaction
MAPD+2H
2→CH
3CH-CH
3 (2)
2C
3H
4+H
2→C
6H
8 (3)
CO+R*H+nH
2→RCOH
n (4)
At the initial stage of catalyzer operation, the activity of catalyzer is better, but when selectivity of catalyst was undesirable, because reaction temperature rising is too high, local reaction was too violent, is easy to cause temperature runaway, has a strong impact on the safe operation of device.
Traditional carbon three hydrogenation catalysts are with Al
20
3Be carrier, take Pd as active ingredient, add Ag for helping active ingredient, the specific surface area of catalyzer is 20～100m
2/ g.The preparation method of catalyzer adopts pickling process.The impact that is subject to steeping fluid surface tension and solvation effect in the dipping of catalyzer and drying treatment process is especially obvious, and the metal active constituent presoma is deposited on carrier surface with aggregate form.In addition, Pd and Ag interaction are not obvious, selectivity of catalyst mainly relies on the dispersion state of catalyzer aperture and active ingredient to control, because in the catalyst preparation process, the dispersion of active ingredient is affected by the quantity of carrier surface group and solvation, the randomness that the catalyst activity component is disperseed is large, the preparation poor repeatability, so the effect of catalyzed reaction is undesirable.
CN98810096 discloses a kind of method of catalytic distillation, to remove the PDMA in the C3 fraction, that shortening and rectifying separation process are united two into one, because thermal exchange is abundant in this process, be difficult for occuring temperature runaway, the a small amount of oligopolymer that generates in this process simultaneously also is easy to be taken out of, can reduce much in the coking degree of catalyst surface.The method is had relatively high expectations to the filling of catalytic distillation tower, and the distribution of fluid can have a significant impact separating effect.The method has also increased the difficulty of operation simultaneously.
Summary of the invention
The object of the present invention is to provide a kind of method of C 3 fraction selective hydrogenation, C3 fraction as hydrogenating materials can be respectively from two kinds of flow processs, a kind of is order hydrogenation flow process, another kind is Front-end depropanization and front-end hydrogenation, C3 fraction enters the adiabatic reactor reactor and selects hydrogenation, to remove propine and propadiene wherein, it is characterized in that the Pd-Ag series catalysts is housed in the adiabatic reactor reactor, the Pd-Ag series catalysts refers to Al
2O
3Be carrier, take the quality of catalyzer as 100%, wherein Pd content is 0.2～0.4%; Ag content is for being 0.05～0.2%, and the specific surface area of catalyzer is 15～100m
2/ g, pore volume are 0.3～0.6ml/g; This catalyzer has formed the organic polymer metal complex in preparation process, its hydrogenation technique condition is: 10～50 ℃ of adiabatic reactor reactor inlet temperatures, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 5～100h
-1, hydrogen/(propine+propadiene) mol ratio is 1～5: 1.
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 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.
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.
The method of hydrotreating that the present invention proposes is 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.Along with the raising of Pd, Ag compound with regular structure degree, the quantity of the hydrogen that the catalyst body phase is adsorbed significantly reduces, and the trend of propine propadiene generation deep hydrogenation reduces greatly, and the catalyzed reaction selectivity is significantly improved.
The inventor also finds, when adopting method of the present invention to carry out hydrogenation reaction, reactor is joined the scope of hydrogen and can significantly be widened, can be with hydrogen/(MA+PD) (mol) from present 1～2: 1 brings up to 1～5: 1, because hydrogen/(MA+PD) expansion of scope, reduce the possibility of leaking alkynes, increased the stability of device operation, greatly facilitated technological operation.
Among the present invention, when C3 fraction during from order hydrogenation flow process, its hydrogenation technique condition is preferably: 10～50 ℃ of adiabatic reactor reactor inlet temperatures, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 5～100h
-1, (mol)=1～5 of hydrogen/(MA+PD): 1.General propylene is 70～90% (mol) in the reactor inlet raw material, propane 10～30% (mol).Propine (PD)+propadiene (MA) is 0.2～8.0% (mol).The adiabatic reactor reactor that uses is generally one section or two reactor.
Among the present invention, when C3 fraction during from Front-end depropanization and front-end hydrogenation, its hydrogenation technique condition is preferably: 10～50 ℃ of adiabatic reactor reactor inlet temperatures, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 5～100h
-1, (mol)=1～5 of hydrogen/(MA+PD): 1.General propylene is 70～90% (mol) in the reactor inlet raw material, propane 10～30% (mol).Propine (MA) is 0.05～0.2% (mol), and propadiene (PD) is 0.05～0.2% (mol).The reactor that uses is generally first stage reactor.
Described Al
2O
3Carrier is preferably γ, δ, θ, α or several mixing crystal formation wherein.Al
2O
3Carrier can be sphere, bar shaped, cloverleaf pattern, Herba Galii Bungei shape or tooth ball-type etc.
Catalyzer provided by the present invention can be prepared by following methods:
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 more specifically preparation method that catalyzer is recommended among the present invention 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 high molecular side-chain radical, and ion that again can complexing Pd, Ag after reaction is with the above-mentioned solution 1～4h that refluxes, be cooled to 20～35 ℃, use deionized water wash, drying.
The organic polymer that has reactive group on the described side chain, refer to that the organic macromolecule 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 can be 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)-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; 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.
Also can prepare first functionalized polymer with in the above-mentioned A process, prepare again functionalized polymer/Al
2O
3Presoma.
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 0.2～0.4%, Ag content preferably 0.05～0.2% 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 finds, adopt method of the present invention after, the selectivity of reaction improves, reactor inlet temperature also can suitably improve, thereby can improve the liquid phase volume air speed, from the 60h of traditional method of hydrotreating
-1Bring up to 100h
-1, can reduce reactor size, reduce the energy waste of heat transfer process.Method of the present invention can improve the selectivity of reaction, reduces the risk of catalyticreactor temperature runaway, is of great significance improving the device Operation safety.
Description of drawings
Fig. 1 is the order hydrogenation flow process C3 fraction hydrogenation technique schema that does not have pre-hydrogenation.
Among the figure: the 1-oil scrubber; The 2-water wash column; The 3-interchanger; The 4-soda-wash tower; The 5-demethanizing tower; The 6-deethanizing column; The 7-depropanizing tower; 8-carbon three hydrogenators.
Fig. 2 is the Front-end depropanization and front-end hydrogenation C3 fraction hydrogenation technique schema that pre-hydrogenation is arranged.
Among the figure: the 1-oil scrubber; The 2-water wash column; The 3-interchanger; The 4-soda-wash tower; The 6-deethanizing column; 8-carbon three hydrogenators; 9---the predepropanization tower; 10---carbon two hydrogenators.
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.
Selectivity=1-[Δ propane/Δ (propine+propadiene)]
The preparation of catalyzer:
A, functionalized poly vinylchlorid (PVC)/Al
2O
3Preparation
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 100m
2/ g, pore volume are the column Al of 0.60ml/g
2O
3Carrier 250g.
PVC10g is dissolved in the 400ml tetrahydrofuran (THF) (THF) fully, above-mentioned carrier impregnation in mentioned solution, is left standstill after the stirring and makes PVC be deposited on Al
2O
3The surface, drying.Obtain 260gPVC/Al
2O
3Product.
Add the 80g Dyhard RU 100 in 500ml distilled water, after stirring is dissolved it fully, add again 260g PVC/Al
2O
3Backflow 120min is cooled to room temperature, and to neutral, drying obtains functionalized PVC/Al with deionized water wash
2O
3In mole number, reactive group Cl mole number=59.5 in complexing agent Dyhard RU 100 mole number/polymer.
B, (Pd-Ag)-polymer/Al
2O
3The preparation of presoma
Take by weighing 1.65gPd (NO
3)
2, 0.8gAg NO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing prepared functionalized-polymer/Al
2O
3Presoma 260g is with functionalized-polymer/Al
2O
3Join Pd (NO
3)
2, AgNO
3Mixing solutions in, stir 30min, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-polymer/Al
2O
3Presoma.Mole number=16.67 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 2h in air atmosphere obtain oxidation state (Pd-Ag)/Al
2O
3Catalyzer.Be positioned over before the use in the fixed-bed reactor, use H
2At 150 ℃ of temperature, air speed 100h
-112h is processed in time reduction, obtains palladium-silver catalyst.Recording this catalyst P d content is that 0.3%, Ag content is 0.2%,
Comparative Examples 1
The preparation of catalyzer
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 100m
2/ g, pore volume are 0.60ml/g
3Column Al
2O
3Carrier 250g.
Take by weighing 1.65gPd (NO
3)
2, 0.8gAg NO
3, measure 0.5ml nitric acid, be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, stir 30min, dry rear at 550 ℃ of roasting temperature 2h, obtain Pd-Ag/Al
2O
3Catalyzer.Be positioned over before the use in the fixed-bed reactor, use H
2Gas is 150 ℃ of temperature, and 12h is processed in reduction, obtains high-dispersion loading type palladium-silver catalyst.Recording this catalyst P d content is that 0.3%, Ag content is 0.2%.
The reduction of catalyzer
Reducing gas: hydrogen, reduction air speed: 100h
-1, 150 ℃ of temperature keep 12h.
Its C3 fraction is from order hydrogenation flow process, and as shown in Figure 1, but adiabatic reactor reactor reaction bed is two sections, and raw material forms as shown in table 1.
Table 1 hydrogenating materials forms
| Hydrogenating materials | C 3H 4(MA) | C 3H 4(PD) | C 3H 6 | C 3H 8 |
| Content (v/v%) | 4.8 | 3.2 | 82.0 | 10.0 |
Reaction conditions:
Two sections adiabatic reactor reactor hydrogenation techniques, liquid phase feed volume space velocity: 5h
-1, working pressure: 2.5MPa, reactor catalyst loadings: 400ml, hydrogen/(MA+PD) (mol)=1.5: 1,40 ℃ of first stage reactor temperature ins, 50 ℃ of second stage reactor temperature ins.Examination afterreaction result through 500 hours is as shown in table 2.
Table 2 examination in 500 hours afterreaction result
| | Embodiment | 1 catalyzer | Comparative Examples 1 catalyzer |
| One section temperature in (℃) | 40 | 40 | |
| One section temperature rise (℃) | 40 | 52 | |
| One section C 3H 4Residual volume (v/v%) | 0.12 | 0.54 | |
| One-stage hydrogenation selectivity (%) | 93 | 75 | |
| Two sections temperature ins (℃) | 50 | 50 | |
| Two sections temperature rises (℃) | 10 | 16 | |
| Two sections C 3H 4Residual volume (v/v%) | 0.0001 | 0.00019 | |
| Secondary hydrogenation selectivity (%) | 70 | 35 |
The catalyzer preparation:
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 0.38ml/g
3Spherical Al
2O
3Carrier 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, adds above-mentioned weighing carrier in this solution, leaves standstill 60min after fully stirring, and drying behind the separation solvent obtains SAN/Al
2O
3
With SAN/Al obtained above
2O
3, join in the 500ml deionized water, add the 28.8g quadrol, backflow 300min takes out product after the cooling, and washing is to neutral, and drying obtains functionalized SAN/Al
2O
3In mole number, reactive group CN mole number=23.96 in complexing agent quadrol mole number/polymer.
B, (Pd-Ag) polymer polymer/Al
2O
3The preparation of presoma
Take by weighing 3.14gPd (NO
3)
2, 0.4gAgNO
3, measure 0.5ml nitric acid, be mixed with the mixing solutions of 1200ml, take by weighing prepared functionalized-SAN/Al
2O
3Presoma 251.1g is with functionalized-polymer/Al
2O
3Join Pd (NO
3)
2, AgNO
3Mixing solutions in, stir 60min, inclining raffinate, with above-mentioned product with deionized water wash to neutral, obtain (Pd-Ag)-polymer/Al
2O
3Presoma.Mole number=1.33 of reactive group CN mole number in the polymer/(Pd+Ag).
The preparation of C, catalyzer
With the presoma of above-mentioned preparation, 500 ℃ of roasting 4h obtain (Pd-Ag)/Al in air atmosphere
2O
3Catalyzer. recording this catalyst P d content is that 0.4%, Ag content is 0.1%.
The reduction of catalyzer: reducing gas is hydrogen, reduction air speed: 100h
-1, 80 ℃ of temperature keep 8h.
Comparative Examples 2
The catalyzer preparation
Take by weighing Φ 2.5mm, specific surface area is 50m
2/ g, pore volume are 0.38ml/g
3Spherical Al
2O
3Carrier 250g.
Take by weighing 3.14gPd (NO
3)
2Being dissolved in the 1O0ml 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 0.4gAgNO
3, measure 0.5ml nitric acid and be mixed with 130ml solution.Above-mentioned carrier is joined in the solution of having prepared, stir 60min, inclining raffinate, dry rear at 500 ℃ of roasting temperature 4h, obtains (Pd-Ag)/Al
2O
3Catalyzer. recording this catalyst P d content is that 0.4%, Ag content is 0.1%.
The reduction of catalyzer
Reducing gas: hydrogen, reduction air speed: 100h
-1, 80 ℃ of temperature keep 8h.
Adopt technical process shown in Figure 1, its C3 fraction raw material forms as shown in table 2.
Table 2 hydrogenating materials forms
| Hydrogenating materials | C 3H 4(MA) | C 3H 4(PD) | C 3H 6 | C 3H 8 |
| Content (v/v%) | 0.6 | 0.4 | 69.0 | 30 |
Single hop reactor hydrogenation technique, liquid phase feed volume space velocity: 50h
-1, working pressure: 3.5MPa, reactor catalyst loadings: 300ml, hydrogen/(MA+PD) (mol)=5: 1,25 ℃ of reactor inlet temperatures.Examination afterreaction result through 1000 hours is as shown in table 4.
Table 4 examination in 1000 hours afterreaction result
Embodiment 3:
The preparation of catalyzer:
A, functionalized poly vinylchlorid (PVC) preparation
Take by weighing PVC 5g and be dissolved in fully among the 400mlTHF, add the 40g Dyhard RU 100, backflow 120min is cooled to room temperature, and it is for subsequent use to obtain functionalized PVC after the washing.In mole number, reactive Cl group mole number=5.94 in complexing agent Dyhard RU 100 mole number/polymer.
B, (Pd-Ag)-high-molecular complex/Al
2O
3The preparation of presoma
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 15m
2/ g, pore volume are 0.3ml/g
3Column Al
2O
3Carrier 250g.
Take by weighing 1.75gPd (NO
3)
2, 0.24gAgNO
3, measure 6ml nitric acid, join in the above-mentioned functionalized PVC solution, stir 5min, obtain (Pd-Ag)-PVC.
With 250g Al
2O
3Carrier adds in the mixing solutions, leave standstill 1h after fully stirring after, with above-mentioned product with deionized water wash to neutral.Obtain (Pd-Ag)-polymer/Al
2O
3Presoma.Mole number=9.5 of the CN of functional group mole number on the functionalized rear macromolecular chain/(Pd+Ag).
The preparation of C, catalyzer
With the presoma of above-mentioned preparation, 450 ℃ of roasting 6h 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=1: 1 mixed gas, 120 ℃ of temperature, reduction air speed: 200h
-1, 12h is processed in reduction.Recording this catalyst P d content is that 0.2%, Ag content is 0.05%.
Comparative Examples 3
The catalyzer preparation
Take by weighing Φ 4.5mm, length is 4.5mm, and specific surface area is 15m
2/ g, pore volume are 0.3ml/g
3Column Al
2O
3Carrier 250g.
Take by weighing 1.75gPd (NO
3)
2, 0.24gAgNO
3, add 6ml nitric acid, prepare to get 87.5ml solution, this solution spraying to be shaken 0.5 hour to above-mentioned carrier, after the drying, 450 ℃ of roasting 6h obtain (Pd-Ag)/Al in air atmosphere
2O
3Catalyzer. recording this catalyst P d content is that 0.2%, Ag content is 0.05%.
The reduction of catalyzer
Be N with mol ratio
2: H
2=1: 1 mixed gas, 120 ℃ of temperature, 12h is processed in reduction, reduction air speed: 200h
-1
Adopt technical process shown in Figure 2, its C3 fraction raw material forms as shown in table 5.
Table 5 hydrogenating materials forms
| Hydrogenating materials | C 3H 4(MA) | C 3H 4(PD) | C 3H 6 | C 3H 8 |
| Content (mol%) | 0.1 | 0.1 | 85.0 | 14.80 |
Reaction process condition: single hop adiabatic reactor reactor process, material air speed: 100h
-1, working pressure: 3.0MPa, loaded catalyst: 200ml.Hydrogen/(MA+PD) (mol)=1: 1.Examination afterreaction result through 600 hours is as shown in table 6.
Table 6 examination in 600 hours afterreaction result
Can find out from above embodiment, adopt method of the present invention after, the selectivity of C3 fraction hydrogenation reaction increases substantially, the scope of hydrogen/MAPD is expanded greatly, from traditional 1～3: 1 expands to 1～5: 1, so that hydrogenation reaction easy handling more is difficult for occuring to leak alkynes and excessive hydrogenation.When moving in the long period, the activity of catalyzer is also well kept.Can also see from embodiment, after employing the method, because catalytic reaction activity and selectivity improve, the air speed scope of reaction is also extended greatly, and minimum air speed can arrive 5/h, ranges up to 100/h, can increase substantially device Operation safety and efficient, the economic benefit of device can increase substantially.
Claims (15)
1. selective hydrogenation method of C 3 fractions, C3 fraction enters the adiabatic reactor reactor and selects hydrogenation, to remove propine and propadiene wherein, it is characterized in that the Pd-Ag series catalysts is housed in the adiabatic reactor reactor, and the Pd-Ag series catalysts refers to Al
2O
3Be carrier, take the quality of catalyzer as 100%, wherein Pd content is that 0.2～0.4%, Ag content is 0.05～0.2%, and the specific surface area of catalyzer is 15～100m
2/ g, pore volume are 0.3～0.6ml/g; 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 the organic macromolecule side-chain radical, the complexing agent of ion that again can complexing Pd, Ag after reaction; Its hydrogenation technique condition is: 10～50 ℃ of adiabatic reactor reactor inlet temperatures, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 5～100h
-1, hydrogen/(propine and propadiene) mol ratio is 1～5:1.
2. selection method of hydrotreating according to claim 1 is characterized in that catalyzer is to Pd-Ag-polymer/Al by 380～550 ℃
2O
3Presoma carries out that roasting 2～6h obtains.
3. selection method of hydrotreating according to claim 2 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 is characterized in that C3 fraction is from order hydrogenation flow process.
7. selection method of hydrotreating according to claim 1 is characterized in that C3 fraction is from Front-end depropanization and front-end hydrogenation.
8. selection method of hydrotreating according to claim 1 is characterized in that the acquisition of catalyzer comprises the steps:
With the organic 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.
9. selection method of hydrotreating according to claim 1 is characterized in that Al
2O
3Crystal formation be that θ, α or its mix crystal formation.
10. selection method of hydrotreating according to claim 8, 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.
11. selection method of hydrotreating according to claim 8, 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: first by complexing agent with the organic polymer grafted functional after, be carried on again on the support of the catalyst, prepare functionalized-polymer/Al
2O
3Presoma.
12. selection method of hydrotreating according to claim 8 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.
13. selection method of hydrotreating according to claim 12, it is characterized in that on the functionalized rear macromolecular chain functional group's mole number/(Pd+Ag) mole number is 100～1.
14. selection method of hydrotreating according to claim 12 is characterized in that in mole number, the reactive group mole number is 100～1 in complexing agent mole number/polymer.
15. selection method of hydrotreating according to claim 12 is characterized in that the mole number of complexing agent mole number/(Pd+Ag) is 10000～1.
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| CN103864559B (en) * | 2014-03-07 | 2016-08-17 | 中石化上海工程有限公司 | C3 fraction selective hydrogenation method |
| CN105732262B (en) * | 2014-12-11 | 2018-03-09 | 中国石油天然气股份有限公司 | A kind of method of ethene selection hydrofinishing |
| CN105732259B (en) * | 2014-12-11 | 2018-03-13 | 中国石油天然气股份有限公司 | A kind of selective hydrogenation method of C 3 fractions |
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| CN105732284B (en) * | 2014-12-12 | 2018-07-13 | 中国石油天然气股份有限公司 | The selection method of hydrotreating of C3 fraction |
| CN105732268B (en) * | 2014-12-12 | 2018-05-04 | 中国石油天然气股份有限公司 | The method of hydrotreating of trace acetylene in a kind of methanol-to-olefins device |
| CN105732286B (en) * | 2014-12-12 | 2018-07-13 | 中国石油天然气股份有限公司 | A kind of selection method of hydrotreating of C3 fraction |
| CN105732285B (en) * | 2014-12-12 | 2018-07-10 | 中国石油天然气股份有限公司 | Selective hydrogenation method of C 3 fractions |
| CN105753627B (en) * | 2014-12-19 | 2018-03-09 | 中国石油天然气股份有限公司 | A kind of selective hydrogenation method of C 3 fractions |
| CN106928004B (en) * | 2015-12-31 | 2019-09-03 | 中国石油天然气股份有限公司 | A kind of selective hydrogenation method of C 3 fractions |
| CN108250017A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of method of C 3 fraction selective hydrogenation |
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