CN105732285A - Selective hydrogenation method for C3 fraction - Google Patents
Selective hydrogenation method for C3 fraction Download PDFInfo
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Abstract
The invention relates to a selective hydrogenation method for a C3 fraction. The C3 fraction is subjected to selective hydrogenation in an adiabatic bed reactor to remove propyne and propadiene in the C3 fraction. A Pd-Ni-series catalyst is arranged in the adiabatic bed reactor. During preparation of the catalyst, an alumina-series carrier is combined with a bipyridine derivative having a hydroxyl group, wherein a metal complex is formed from the hydroxyl bipyridine derivative combined with the carrier and an active component. The method improves activity and selectivity of the catalytic reaction and greatly broadens space velocity range to 5-60/h, greatly increases the operation safety and efficiency of an apparatus, and greatly increases the economic benefit of the apparatus. The catalyst has excellent impurity interference resistance and is especially suitable for the C3 hydrogenation apparatus being high in impurity contents such as sulfur and arsenic.
Description
Technical field
The present invention relates to a kind of a kind of method selecting method of hydrotreating, particularly C 3 fraction selective hydrogenation to remove propine, allene.
Background technology
The acquisition of high-purity propylene is the premise that polypropylene produces, and that high-purity propylene produces it is crucial that the propine (MA) removed in C3 fraction and allene (PD), is generally adopted the method selecting to be hydrogenated with.
Current hydrogenation technique mainly adopts liquid-phase hydrogenatin, owing to the MAPD (propine and allene) in carbon three component has stronger polymerization to be inclined to, easily forms coking at catalyst surface.Thus causing catalyst activity reduction, make hydrogenated products off quality, the service life of catalyst shortens.
C3 fraction hydrogenation technique flow process at not pre-hydrogenation, namely in the order hydrogenation flow process method of C3 fraction, cracking gas is through washing, oil wash, after alkali cleaning and carbon four separate, first pass through methane tower, its tower top is carbon one fraction and hydrogen, tower reactor is carbon two and C3 fraction, then through ethane tower, separation of carbon two and C3 fraction, the composition of its tower reactor is C_3 hydrogenation raw material, major part composition is propylene, all the other are a small amount of propane, propine and allene, C3 fraction enters fixing adiabatic reactor reactor and carries out liquid-phase hydrogenatin elimination alkynes and alkadienes, in reactor inlet raw material, propylene is 70～90% (mol), propane 10～30% (mol).Propine (PD)+allene (MA) is 0.2～8.0% (mol).The usual process conditions of this technique hydrogenation reaction are: reactor inlet temperature 10～50 DEG C, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 5～60h-1, hydrogen/(MA+PD) (mol)=1～2.
In the C3 fraction hydrogenation technique flow process having pre-hydrogenation, namely in the technological process of predepropanization front-end hydrogenation, cracking gas is through oil wash, after washing and alkali cleaning, first pass through predepropanization tower, the fraction of its tower top includes carbon one and hydrogen, C-2-fraction and C3 fraction, tower reactor is attached most importance to C3 fraction, the fraction of tower top enters Acetylene converter, wherein carbon one fraction and hydrogen volume content are 35～50%, C-2-fraction 35～50%, C3 fraction 10～20%, the Acetylene converter of this technique is generally three sections, one, second-stage hydrogenation reactor is mainly used in the elimination of acetylene, 3rd section of reactor carries out propine, the elimination of allene.This unit is generally adopted gas phase hydrogenation technique, and propine, allene removal efficiency are more than 50%, and after this flow process, reaction mass separates then through C3 fraction and carbon one C-2-fraction, and the C3 fraction after separation enters the liquid-phase hydrogenatin of carbon three after cooling.Owing to major part propine allene is converted, hydrogenation load is relatively low, and selectivity of catalyst has higher requirement.
Generally, at C3In fraction selective hydrogenation process, there is following reaction:
Primary response
MAPD+H2→CH3CH=CH2(1)
Side reaction
MAPD+2H2→CH3CH―CH3(2)
2C3H4+H2→C6H8(3)
CO+R*H+nH2→RCOHn(4)
At the initial stage that catalyst runs, the activity of catalyst is better, but when selectivity of catalyst is undesirable, owing to reaction temperature rising is too high, local response is excessively violent, it is easy to cause temperature runaway, has a strong impact on the safe operation of device.
Traditional C_3 hydrogenation catalyst adopts catalyst to be with Al2O3For carrier, with Pd for active component, Ag is for helping active component in addition, and the specific surface area of catalyst is 20～100m2/g.The preparation method of catalyst is to adopt infusion process.The impact being subject to impregnation liquid surface tension and solvation effect in the dipping and dried process of catalyst is especially apparent, and metal active constituent presoma is deposited on carrier surface with aggregate form.Additionally, distribution between Pd and Ag is undesirable, catalyst activity is wayward, selectivity of catalyst relies primarily on the dispersity of catalyst aperture and active component and controls, owing to, in catalyst preparation process, the dispersion of active component is affected by quantity and the solvation of carrier surface group, and the scattered randomness of catalyst activity component is big, preparation poor repeatability, therefore the effect of catalytic reaction is undesirable.
CN98810096 discloses a kind of method of catalytic distillation, to remove the PDMA in C3 fraction, it is that catalytic hydrogenation and rectification separation process are united two into one, owing to heat exchange is abundant in this process, it is not susceptible to temperature runaway, the a small amount of oligomer simultaneously generated in this process, is also easy to be carried over, and the coking degree at catalyst surface can reduce a lot.The filling of catalytic distillation tower is required higher by the method, and separating effect can be had a significant impact by the distribution of fluid.The method too increases the difficulty of operation simultaneously.
CN103801293A discloses a kind of selective hydrogenation catalyst, and it includes carrier and the main active component Pd being carried on carrier and helps active component A g, Bi, it is characterised in that: adopting XPS analysis, the ratio of catalyst surface Pd and O atom number percentage composition is 4 × 10-4～30 × 10-4, the ratio of Ag and O atom number percentage composition is 15 × 10-4～60 × 10-4；The weight ratio helping active component Bi and main active component Pd is 0.01～5.When this catalyst is for selective hydrogenation, there is the active and good selectivity of good catalysis simultaneously.
CN103785484A discloses a kind of hydrogenation catalyst, this hydrogenation catalyst includes tooth spherical alumina support and load VI B race metal component on described tooth spherical alumina support and VIII race's metal component, wherein, the pore volume of described tooth spherical alumina support is 0.4-0.7mL/g, and specific surface area is 180-280m2/g.The preparation method that present invention also offers this hydrogenation catalyst, and a kind of hydrorefined method of light oil.Hydrogenation catalyst provided by the invention is used for coking gasoline hydrogenation refining device, it is possible to give full play to the Hydrogenation of catalyst, and the pressure drop effectively maintaining hydrogenation plant system is stable, extends the service cycle of hydrogenation plant.
CN103657671A relates to a kind of diolefin hydrogenate catalyst and method for making and application.It is by a kind of VIII race's metal, a kind of+3 valency metals, a kind of IA race metal, a kind of Group IVB metal, the SiO of a kind of Group IIB metal, two kinds of group vib metals and aequum2-Al2O3The mixed metal oxide catalyst of composition, it is characterized in that, count with oxide and with catalyst for benchmark, SiO containing VIII race's metal of 10-40 weight % ,+3 valency metals of 5-30 weight %, the IA race metal of 0.1-8 weight %, the IV B race metal of 0.1-8 weight %, the II B race metal of 0.1-30 weight %, two kind of VI B race metal of 5-50 weight % and 10-30 weight % in this catalyst2-Al2O3Composition.Catalyst provided by the invention is not easy coking, and anti-poisoning capability is strong, and the catalyst runs cycle is long.
The preparation method that CN103769158A discloses a kind of hydrogenation catalyst.This catalyst is Cu-Al-Zn-M-O catalyst, and wherein M is one or more in Ba, Mn, Mg, Ti, Cr.The inventive method adopt two step parallel flow precipitation namely containing Cu, Al solution and precipitant, carry out what parallel-flow precipitation prepared at different conditions containing Cu, Zn, M solution and precipitant.Gained catalyst for BDO process, improves the reactivity of catalyst and selectivity and stability suitable in dimethyl maleate Hydrogenation.
The preparation method that CN103623874A discloses a kind of carbon two selective hydrogenation catalyst.Including: 1) in a water bath, water-soluble cellulose ether is dissolved in deionized water, and mix with catalyst activity component saline solution, and regulate pH value for neutrality, stirring；Wherein deionized water, catalyst activity component, water-soluble cellulose ether weight ratio be=1:(0.0001～0.001): (0.0001～0.005)；2) load；3) dry, roasting.In the present invention, water-soluble cellulose ethers can form monodispersed Pd nano particle in the solution as effective stabilizer, is loaded to by infusion process and forms more active center on carrier.The inventive method improves the activity of catalyst and the selectivity of hydrogenation products, enhances dispersibility and the utilization rate of palladium, reduces the load capacity of palladium.
CN103418396A discloses a kind of hydrogenation catalyst and preparation thereof and application, described catalyst contains containing alcohol molding aqua oxidation alumina supporter, the load at least one non-noble metal slaine being selected from VIII race on this carrier and at least one slaine being selected from VI B race metal, count with oxide and with catalyst for benchmark, VIII race's tenor is 2 weight %～10 weight %, and VI B race tenor is 15 weight %～45 weight %.The preparation method of this catalyst includes preparation containing alcohol molding aqua oxidation alumina supporter at least one non-noble metal slaine being selected from VIII race of load and at least one slaine being selected from VI B race metal on this carrier, is dried afterwards.Compared with existing technical method, hydrogenation catalyst provided by the invention not only has the refining performance of hydrocarbon oil hydrogenation of excellence, and preparation method is simple, production cost is low simultaneously.
CN201110086151.X discloses a kind of method of C 3 fraction selective hydrogenation, the catalyst that the method adopts, and with Pd for main active component, with aluminium oxide for carrier, adds promoter silver.By adsorbing specific macromolecular compound on carrier, macromolecule wrapped layer is formed at carrier surface certain thickness, with with the compound of function base and high molecular weight reactive, can with the function base of active component complexation so as to have, on carrier surface function base, complex reaction is there is, it is ensured that active component is in order and high degree of dispersion by active component.Adopting this patented method, the specific macromolecular compound of carrier adsorption carries out chemisorbed by the hydroxyl of aluminium oxide and macromolecule, and the amount of carrier adsorption macromolecular compound is subjected to the hydroxyl value quantitative limitation of aluminium oxide；Not strong with the complexing of Pd through the macromolecule of functionalization, do not reach requirement sometimes up to activity component load quantity, impregnation liquid is gone back residual fraction active component, cause catalyst cost to improve；Adopt the method to prepare C_3 hydrogenation catalyst and there is also the shortcoming that technological process is complicated.
In recent years, part ethylene unit is due to raw material in poor quality, its carbon three selects hydrogenation plant to contain the impurity such as certain As, S, and with Pd be active component, Ag be auxiliary agent bimetal supported catalyst for the type device, the impurity effect catalyst activities such as As, S, catalysqt deactivation can be caused, thus bringing device leakage alkynes risk time serious.
Summary of the invention
A kind of method that it is an object of the invention to provide C 3 fraction selective hydrogenation, C3 fraction enters adiabatic reactor reactor and carries out selecting hydrogenation, to remove propine therein and allene, it is characterised in that refer to equipped with Pd-Ni series catalysts with Al in adiabatic reactor reactor2O3Being carrier, with the quality of catalyst for 100%, wherein Pd content is 0.2～0.6%, and Ni content is 0.05～0.3%, and the specific surface area of catalyst is 15～100m2/ g, pore volume is 0.3～0.6ml/g；This catalyst, in preparation process, is combined with hydroxyl-bipyridyl by alumina series carrier, and active component forms metal complex with hydroxyl-bipyridyl；Its hydrogenation process conditions is: adiabatic reactor reactor inlet temperature 10～50 DEG C, reaction pressure 2.5～3.5MPa, liquid phase volume air speed 5～100h-1, hydrogen/(propine and allene) mol ratio is 1～5:1.The feature of the Pd-Ni series catalysts used in the present invention is: this catalyst is the PdNi-hydroxyl-bipyridyl/Al adopting the present invention2O3Prepared by the method for precursor.
The catalyst preparation process recommended, at least includes: loaded to by hydroxyl dipyridyl derivatives on alumina series carrier, and the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Ni forms complex ion.
The hydroxyl dipyridyl derivatives of the present invention, preferably hydroxyl 2,2,-dipyridyl derivatives, hydroxyl 3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives, can there is good complex reaction with Pd, Ni in two nitrilo at hydroxyl unnecessary after being combined with aluminium oxide and ortho position because of it.
Defining the catalyst type of use in the present invention, such catalyst selectivity and traditional catalyst have bigger difference.
Principles of the invention is: in selective hydrogenation reaction, along with the catalyst activity component Pd, the Ni that use form alloy, the quantity of the hydrogen that caltalyst phase is adsorbed is greatly reduced, propine, allene generation deep hydrogenation trend be substantially reduced, catalyst selectivity significantly improves.
The acquisition of this catalyst preferably includes following steps: by hydroxyl bipyridyl organic solution, impregnates Al2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Ni2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor.At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
Carrier of the present invention is alumina series carrier, it is preferred to aluminium oxide, or mainly contains Al2O3Wherein doped with other hopcalite, other oxide is silicon oxide, titanium oxide, magnesium oxide and/or calcium oxide.Described aluminium oxide is γ, δ, θ, α or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
In the present invention, carrier can be spherical, cylindrical, annular, bar shaped, cloverleaf pattern, Herba Galii Bungei shape etc..
Catalyst preparing of the present invention can adopt procedure below to implement, and this process can be divided into 3 steps to carry out.
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By the organic solution of hydroxyl dipyridyl derivatives and Al2O3It is carrier mixing, makes solution be absorbed, at 20 DEG C～60 DEG C temperature, react 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor.The molal quantity of hydroxyl-bipyridyl/(Pd+Ni) is preferably 1～100；Organic solution volume is preferably equal to or greater than the 80% of carrier cumulative volume.
B.PdNi-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Ni, adds the bipyridyl/Al of step A resulting tape hydroxyl at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle, dry at 60 DEG C～150 DEG C, obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor.
The ratio of the molal quantity of Ni and the molal quantity of Pd is preferably 0.4～5, regulates pH value and is preferably 1.5～4.0；The volume of the mixed-cation solution of Pd, Ni is hydroxyl-bipyridyl/Al preferably2O3The 60%～200% of precursor cumulative volume.
C. the preparation of catalyst
PdNi-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdNi-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
Adding solvent in step to make hydroxyl-bipyridyl be completely dissolved, to be conducive to macromolecule absorption on carrier, solvent can be ethanol and ether.The addition of solvent is how many, mainly to control institute's solubilizer and macromolecule can be made to be completely dissolved.
In stepb, the solution of palladium-nickel can be the soluble salt solutions of palladium, nickel, as being Pd (NO3)2、NiNO3Mixed solution.In described mixed solution, palladium, nickel salt consumption are can make Pd, Ni content of final catalyst.
In step C, roasting preferably carries out in having oxygen atmosphere, sintering temperature of the present invention preferably 300 DEG C～600 DEG C.
When catalyst uses, the catalyst that above method can be prepared, use H in the reactor2Carry out reduction treatment, obtain reduction-state catalyst.
In the present invention, complex reaction is the in-situ chemical reaction of complex-metal ion, metal ion is to be attached on macromolecule by chemical reaction but not physical absorption, therefore the atom macromolecule of palladium, nickel is in uniform sequential distribution, in the process of roasting, palladium-nickle atom can carry out oxidation reaction in position, in the process of oxidation reaction, form the oxide eutectic of palladium, nickel.
Adopting the method can overcome the scattered impact on palladium-nickel of impregnation liquid surface tension and solvation effect, preparing catalyst is alloy-type bimetallic catalyst, therefore possesses more excellent selectivity.
Due to Al in the present invention2O3The Al-O key of carrier, by the hydroxyl in hydroxyl-bipyridyl produces strong absorption, therefore can effectively guarantee Al2O3Carrier is to high molecular adsorbance, it is to avoid the loss of hydroxyl-bipyridyl in solution.Simultaneously as be adsorbed on Al2O3The hydroxyl of the hydroxyl-bipyridyl on carrier and nitrilo and active component Pd, the complexing power helping active component Ni are stronger, it can be ensured that active component Pd in solution, help active component Ni by hydroxyl-bipyridyl/Al2O3Adsorbed completely, it is to avoid active component Pd in solution, help the loss of active component Ni, reduced production cost.
Hydroxyl-the bipyridyl introduced in the present invention, because the existence of polymer effect, can make metallic atom reach the scattered effect of high uniformity.
In the present invention, being loaded to by hydroxyl-bipyridyl on alumina series carrier, the cation of the hydroxyl unnecessary again through hydroxyl-bipyridyl and/or nitrilo and Pd, Ni forms complex ion.The solution of configuration palladium-nickel, is impregnated into being loaded with functionalized high molecular predecessor in the palladium-nickel solution prepared, reacts under certain conditions, make palladium, nickel ion be complexed on the macromolecular chain of load simultaneously.The ion of palladium-nickel is attached on macromolecule by chemical reaction, palladium-nickle atom the number combined on each macromolecule is proportional to the quantity of hydroxyl on macromolecule, nitrilo, and the quantity of described hydroxyl-bipyridyl is preferably 1～100 times of (palladium+nickel) amount of ions.In course of reaction, orderly being distributed on macromolecule of palladium, nickel particles.In roasting process, palladium-nickle atom can carry out oxidation reaction in position, catalyst prepared by this method is alloy-type bimetallic catalyst, this preparation method is adopted to overcome impregnation liquid surface tension and the solvation effect scattered adverse effect to palladium-nickel, the catalyst of preparation, it is more conducive to form palladium-nickel alloy, reaches to improve the effect of catalyst activity and selectivity.
In the present invention, the C3 fraction as hydrogenating materials can respectively from two kinds of flow processs, and a kind of for being sequentially hydrogenated with flow process, another kind is Front-end depropanization and front-end hydrogenation.In the present invention, hydrogenation process conditions is preferably: adiabatic reactor reactor inlet temperature 10～50 DEG C, reaction pressure 2.0～3.5MPa, liquid phase volume air speed 5～100h-1, hydrogen/(MA+PD) (mol)=1～5:1.In reactor inlet raw material, general propylene is 70～90% (mol), propane 10～30% (mol), propine (MA) is 0.05～0.2% (mol), and allene (PD) is 0.05～0.2% (mol).The reactor used is generally first stage reactor.
Inventor have found that, after adopting the method for hydrotreating of the present invention, the selectivity of reaction improves, and reactor inlet temperature can also properly increase, such that it is able to improve liquid phase volume air speed, from the 60h of tradition method of hydrotreating-1Bring up to 100h-1, it is possible to reduce reactor size, reduces the energy loss of heat transfer process.The method of the present invention can improve the selectivity of reaction, reduces the risk of catalytic reactor temperature runaway, and the safety improving plant running is had important meaning.
Meanwhile, the inventive method prepares palladium-nickel catalyst, and its alloy structure is more suitably applied to the higher carbon of the impurity contents such as As, S three and selects hydrogenation plant.Under the working condition that the impurity contents such as As, S are higher, still there is hydrogenation activity and the stability of excellence, for, in C_3 hydrogenation device, showing good anti-CO fluctuation ability, be effectively improved plant running stability.
Accompanying drawing explanation
Fig. 1 is that application a kind of of the present invention adopts the C_3 hydrogenation flow chart without pre-hydrogenation technique.
Fig. 2 is a kind of C_3 hydrogenation flow chart adopting pre-hydrogenation technique of the application present invention.
In figure: 1 oil scrubber；2 water scrubbers；3 heat exchangers；4 caustic wash towers；5 domethanizing columns；6 dethanizers；7 depropanizing towers；8 C_3 hydrogenation reactors；9 predepropanization towers；10 Acetylene converter；11 compressors.
Detailed description of the invention
Analysis test method:
Specific surface area: GB/T-5816
Pore volume: GB/T-5816
Bulk density: Q/SY142-2006
Catalyst Pd, Ni assay: using plasma emission spectrometer records this catalyst Pd content and Ni content.Standard GB/T1537-94
Selective calculation method:
Propylene Selectivity S=1-△ propane/△ (propine+allene)
Embodiment 1
Weighing Φ 4.2mm, length is 4.2mm, and specific surface area is 75m2/ g, pore volume is the column δ-Al of 0.63ml/g2O3Carrier 500g.
By 123.03g4,4-dihydroxy-2,2-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 2h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 60 DEG C of dry 10h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2, Ni (NO3)2·6H2O is dissolved in the 600mL deionized water containing appropriate nitric acid, and adjusting pH value is 1.5, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 10min, stands 2h, pours out residual liquid, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=15).Dried roasting 2h in air atmosphere at 550 DEG C of temperature, obtains (Pd-Ni)/Al2O3Catalyst.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst S-1.Recording this catalyst Pd content is 0.42%, and Ni content is 0.28%.
Comparative example 1
Weighing Φ 4.2mm, length is 4.2mm, and specific surface area is 75m2/ g, pore volume is the column δ-Al of 0.63ml/g2O3Carrier 500g.
Weigh appropriate Pd (NO3)2、Ni(NO3)2·6H2O is dissolved in the 300mL deionized water containing appropriate nitric acid, and adjusting pH value is 1.5, is configured to mixed solution.Being joined by above-mentioned carrier in the solution prepared, stir 30min, roasting 2h in air atmosphere at 550 DEG C of temperature, obtains (Pd-Ni)/Al after drying2O3Catalyst.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst D-1.Recording this catalyst Pd content is 0.42%, and Ni content is 0.28%.
Adopting the technological process shown in Fig. 1, as shown in Figure 1, adiabatic reactor reactor reaction bed is two sections, and raw material composition is as shown in table 1.
Table 1 hydrogenating materials forms
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 | S | As |
| Content (V/V%) | 3.8 | 3.7 | 81.0 | 11.5 | 21ppm | 23ppb |
Reaction condition:
Two sections of adiabatic reactor reactor hydrogenation techniques, liquid phase feed volume space velocity: 8h-1, operate pressure: 2.3MPa, reactor catalyst loadings: 500ml, hydrogen/(MA+PD) (mol)=1.4:1, first stage reactor inlet temperature 45 DEG C, second stage reactor inlet temperature 55 DEG C.After the examination of 200 hours shown in reaction result table 2.
Reaction result after table examination in 2200 hours
| Condition | Embodiment 1 catalyst | Comparative example 1 catalyst |
| One section of inlet temperature (DEG C) | 45 | 45 |
| One section of temperature rise (DEG C) | 36 | 30 |
| One section of C3H4Residual volume (V/V%) | 0.39 | 0.96 |
| One-stage hydrogenation selectivity (%) | 85 | 63 |
| Two-stage nitration inlet temperature (DEG C) | 55 | 55 |
| Two-stage nitration temperature rise (DEG C) | 21 | 16 |
| Two-stage nitration C3H4Residual volume (V/V%) | 0.12 | 0.48 |
| Secondary hydrogenation selectivity (%) | 69 | 32 |
Embodiment 2
Weighing Φ 2.6mm, specific surface area is 43m2/ g, pore volume is 0.44ml/g, and bulk density is the tooth spherical θ-Al of 0.68g/ml2O3Carrier 500g.
By 30.37g4,4-dihydroxy-2,2-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 90 DEG C of dry 8h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2, Ni (NO3)2·6H2O is dissolved in the 500mL deionized water containing appropriate nitric acid, and adjusting pH value is 2.5, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid dry 6h at 110 DEG C obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=5).
By the presoma of above-mentioned preparation, 500 DEG C of roasting 4h in air atmosphere.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst S-2.Recording this catalyst Pd content is 0.56%, and Ni content is 0.070%.
Comparative example 2
Weighing Φ 2.6mm, specific surface area is 43m2/ g, pore volume is 0.44ml/g, and bulk density is the tooth spherical θ-Al of 0.68g/ml2O3Carrier 500g.
A, sense polystyrene acrylonitrile (SAN)/Al2O3Preparation
Weighing SAN resin 2.2g, be dissolved in 600ml dimethylformamide (DMF) solvent, under room temperature, stirring makes SAN resin be completely dissolved, add in this solution and above-mentioned weighed carrier, 60min is stood after being sufficiently stirred for, dry after separating solvent, obtain SAN/Al2O3。
By SAN/Al obtained above2O3, joining in 1000ml deionized water, add 57.6g ethylenediamine, backflow 5h, after cooling, take out product, washing, to neutral, dry and obtains functionalized SAN/Al2O3.With molar basis, reactive group CN molal quantity=23.96 in chelating agent ethylenediamine molal quantity/macromolecule.
B, (Pd-Cu)-high-molecular complex/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2、Ni(NO3)2·6H2O is dissolved in the 300mL deionized water containing appropriate nitric acid, and adjusting pH value is 2.5, is configured to mixed solution.Take the functionalized-SAN/Al prepared2O3Presoma, joins Pd (NO3)2、Ni(NO3)2Mixed solution in, stir 60min, pour out residual liquid, will obtain product deionized water wash to neutrality, obtain (Pd-Ni)-polymer/Al after drying2O3Presoma.
C, catalyst preparing
The presoma of above-mentioned preparation is dried, 500 DEG C of roasting 4h in air atmosphere.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst D-2.Recording this catalyst Pd content is 0.56%, and Ni content is 0.070%.
Adopting the technological process shown in Fig. 1, its C3 fraction raw material composition is as shown in table 3.
Table 3 hydrogenating materials forms
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 | S | As |
| Content (V/V%) | 0.8 | 0.6 | 68.0 | 30.6 | 25ppm | 23ppb |
Single hop reactor hydrogenation technique, liquid phase feed volume space velocity: 40h-1, operate pressure: 3.0MPa, reactor catalyst loadings: 500ml, hydrogen/(MA+PD) (mol)=3:1, reactor inlet temperature 55 DEG C.After the examination of 200 hours, reaction result is as shown in table 4.
Table 4 catalyst is applied to reaction result after C3 fraction hydrogenation is examined for 200 hours
Embodiment 3:
Weighing Φ 4.5mm × 4.5mm, specific surface area is 15.0m2/ g, pore volume is 0.25ml/g, and bulk density is 0.85g/mL, column α-Al2O3Carrier 500g.
By 212.40g6,6'-dihydroxy-3,3'-bipyridyl is dissolved in 650mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 12h, make 6,6'-dihydroxy-3,3'-bipyridyl loads to after on alumina support completely, 120 DEG C of dry 4h, obtains hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2, Ni (NO3)2·6H2O is dissolved in the 600mL deionized water containing appropriate nitric acid, and adjusting pH value is 3.0, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 8h, pours out residual liquid, and remaining solid obtains PdNi-hydroxyl-bipyridyl/Al after dry 8h at 100 DEG C2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=45).
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst S-3.Recording this catalyst Pd content is 0.20%, and Ni content is 0.10%.
Comparative example 3:
The preparation of catalyst:
Weighing Φ 4.5mm × 4.5mm, specific surface area is 15.0m2/ g, pore volume is 0.25ml/g, and bulk density is 0.85g/mL, column α-Al2O3Carrier 500g.
Prepared by A, functionalized poly vinyl chloride (PVC)
Weighing PVC10g and be dissolved completely in 800mlTHF, add 80g dicyandiamide, reflux 120min, is cooled to room temperature, obtains functionalized PVC standby after washing.With molar basis, reactive CI group molal quantity=5.94 in chelating agent dicyandiamide molal quantity/macromolecule.
B, (Pd-Ni)-high-molecular complex/Al2O3The preparation of presoma
Weigh appropriate Pd (NO3)2, Ni (NO3)2·6H2The O 300mL deionized water containing appropriate nitric acid, measures 12ml nitric acid, joins in above-mentioned functionalized PVC solution, stirs 5min, obtains (Pd-Cu)-PVC.
By 500gAl2O3Carrier adds in mixed solution, after standing 1h after being sufficiently stirred for, by above-mentioned product deionized water wash to neutral.Obtain (Pd-Ni)-polymer/Al after drying2O3Presoma.
C, catalyst preparation
By the presoma of above-mentioned preparation, 450 DEG C of roasting 6h in air atmosphere after drying.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst D-3.Recording this catalyst Pd content is 0.20%, and Ni content is 0.10%.
Adopting the technological process shown in Fig. 2, its C3 fraction raw material composition is as shown in table 5.
Table 5 hydrogenating materials forms
Reaction process condition: single stage adiabatic bed bioreactor technique, material air speed: 120/h-1, operate pressure: 2.8MPa, loaded catalyst: 500ml.Hydrogen/(MA+PD) (mol)=1.5:1.After the examination of 200 hours, reaction result is as shown in table 6.
Reaction result after table examination in 6200 hours
Embodiment 4
Weighing Φ 3.5mm, specific surface area is 38m2/ g, pore volume is 0.46ml/g, and bulk density is the tooth spherical θ-Al of 0.73g/ml2O3Carrier 500g.
By 176.42g4,4-dihydroxy-2,2-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 100 DEG C of dry 6h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2, Ni (NO3)2·6H2The O 600mL deionized water containing appropriate nitric acid, adjusting pH value is 3.5, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and remaining solid dry 10h at 90 DEG C obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ni)=20).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst S-4.Recording this catalyst Pd content is 0.49%, and Ni content is 0.28%.
Comparative example 4
Weighing Φ 3.5mm, specific surface area is 38m2/ g, pore volume is 0.46ml/g, and bulk density is the tooth spherical θ-Al of 0.73g/ml2O3Carrier 500g.
Weighing appropriate 4,4-dihydroxy-2,2-bipyridyl is dissolved in 600mL alcoholic solution, by above-mentioned carrier impregnation in above-mentioned solution, after standing 8h, dihydroxy-2,2-bipyridyl is loaded to after on alumina support completely, and 100 DEG C of dry 6h obtain hydroxyl-bipyridyl/Al2O3Precursor.
Weigh appropriate Pd (NO3)2、AgNO3Adding the 600mL deionized water containing appropriate nitric acid, adjusting pH value is 3.5, is configured to mixed solution.By above-mentioned hydroxyl-bipyridyl/Al2O3Precursor joins the solution prepared, and stirs 60min, stands 10h, pours out residual liquid, and remaining solid dry 10h at 90 DEG C obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor (hydroxyl-bipyridyl molal quantity: (Pd+Ag)=20).
By the presoma of above-mentioned preparation, 600 DEG C of roasting 2h in air atmosphere.It is positioned over before using in fixed-bed reactor, uses H2At air speed 400h-1, 120 DEG C of temperature, reduction treatment 8h, obtain loaded catalyst D-4.Recording this catalyst Pd content is 0.49%, and Ni content is 0.28%.
Adopting the technological process shown in Fig. 1, its C3 fraction raw material composition is as shown in table 7.
Table 7 hydrogenating materials forms
| Hydrogenating materials | C3H4(MA) | C3H4(PD) | C3H6 | C3H8 | S | As |
| Content (V/V%) | 0.8 | 0.6 | 69.0 | 29.6 | 25ppm | 21ppb |
Single hop reactor hydrogenation technique, liquid phase feed volume space velocity: 65h-1, operate pressure: 3.0MPa, reactor catalyst loadings: 500ml, hydrogen/(MA+PD) (mol)=3:1, reactor inlet temperature 35 DEG C.After the examination of 200 hours, reaction result is as shown in table 8.
Table 8 catalyst is applied to reaction result after C3 fraction hydrogenation is examined for 200 hours
From above embodiments it can be seen that after adopting the method for the present invention, the activity of C3 fraction hydrogenation reaction, selectivity increase substantially so that hydrogenation reaction more easily operates, and are not susceptible to Lou alkynes and excessive hydrogenation.When the long period is run, the activity of catalyst is also well kept.From embodiment it can further be seen that adopt after the method, owing to catalytic reaction activity and selectivity improve, the space velocity range of reaction also extends significantly, and minimum air speed can arrive 5/h, ranges up to 100/h, can increasing substantially safety and the efficiency of plant running, the economic benefit of device can increase substantially.
Claims (15)
1. a selective hydrogenation method of C 3 fractions, C3 fraction enters adiabatic reactor reactor and carries out selecting hydrogenation, to remove propine therein and allene, it is characterised in that adopt Al equipped with Pd-Ni series catalysts in adiabatic reactor reactor2O3Being carrier, with the quality of catalyst for 100%, wherein Pd content is 0.20～0.60%, and Ni content is 0.05～0.3%, and the specific surface area of catalyst is 15～100m2/ g, pore volume is 0.3～0.6ml/g；This catalyst, in preparation process, is combined with hydroxyl-bipyridyl by alumina series carrier, and the hydroxyl bipyridyl being combined on carrier forms metal complex with active component；Its hydrogenation process conditions is: adiabatic reactor reactor inlet temperature 10～50 DEG C, reaction pressure 2.0～3.5MPa, liquid phase volume air speed 5～100h-1, hydrogen/(propine and allene) mol ratio is 1～5:1.
2. selective hydrogenation method of C 3 fractions according to claim 1, it is characterized in that catalyst preparation process, at least including: loaded to by hydroxyl dipyridyl derivatives on alumina series carrier, the cation of the hydroxyl unnecessary again through hydroxyl dipyridyl derivatives and/or nitrilo and Pd, Ni forms complex ion.
3. selective hydrogenation method of C 3 fractions according to claim 1, it is characterised in that C3 fraction is hydrogenated with flow process from order.
4. selective hydrogenation method of C 3 fractions according to claim 1, it is characterised in that C3 fraction is from Front-end depropanization and front-end hydrogenation.
5. selective hydrogenation method of C 3 fractions according to claim 1, it is characterised in that hydroxyl dipyridyl derivatives, it is preferred to hydroxyl 2,2,-dipyridyl derivatives or hydroxyl 3,3 ,-dipyridyl derivatives, preferably hydroxyl 2,2 ,-dipyridyl derivatives.
6. selective hydrogenation method of C 3 fractions according to claim 1, it is characterised in that the preparation process of catalyst comprises the steps: the organic solution with hydroxyl dipyridyl derivatives, impregnates Al2O3It is carrier, obtains hydroxyl-bipyridyl/Al after drying2O3Precursor, the mixed-cation solution impregnation hydroxyl-bipyridyl/Al of preparation Pd, Ni2O3Precursor, dry at 60 DEG C～150 DEG C, obtain PdNi-hydroxyl-bipyridyl/Al2O3Precursor；At 300～600 DEG C of roasting temperature 2～12h, obtain required catalyst.
7. selective hydrogenation method of C 3 fractions according to claim 1, it is characterised in that Al2O3Be carrier it is Al2O3Or mainly contain Al2O3, wherein also doped with other hopcalite, other oxide is titanium oxide, magnesium oxide and/or calcium oxide；Described aluminium oxide is γ, δ, θ, α or wherein several mixing crystal formations, it is desirable to for θ, α or its mixing crystal formation.
8. selective hydrogenation method of C 3 fractions according to claim 1, it is characterised in that carrier is spherical, cylinder, annular, bar shaped, cloverleaf pattern or Herba Galii Bungei shape.
9. the arbitrary selective hydrogenation method of C 3 fractions according to claim 1-8, it is characterised in that the preparation process of catalyst comprises the following steps:
A. hydroxyl-bipyridyl/Al2O3The preparation of precursor
By the organic solution of hydroxyl dipyridyl derivatives and Al2O3It is carrier mixing, at 20 DEG C～60 DEG C temperature, reacts 2～24h, take out solid particle, dry at 60 DEG C～150 DEG C, obtain hydroxyl-bipyridyl/Al2O3Precursor；
B.PdNi-hydroxyl-bipyridyl/Al2O3The preparation of precursor
The mixed-cation solution of preparation Pd, Ni, with step A gained hydroxyl-bipyridyl/Al at 30 DEG C～100 DEG C temperature2O3Precursor reaction 2～24h, takes out solid particle, dry at 60 DEG C～150 DEG C, obtains PdNi-hydroxyl-bipyridyl/Al2O3Precursor；
C. the preparation of catalyst
PdNi-hydroxyl-bipyridyl/Al prepared by step B2O3Precursor is at 300～600 DEG C of roasting temperature 2～12h so that PdNi-hydroxyl-bipyridyl/Al2O3Precursor is changed into corresponding metal composite oxide, obtains catalyst.
10. selective hydrogenation method of C 3 fractions according to claim 9, it is characterised in that in step A, the molal quantity of hydroxyl-bipyridyl/(Pd+Ni) is 1～100:1.
11. selective hydrogenation method of C 3 fractions according to claim 9, it is characterised in that in stepb, the mixed solution that mixed-cation solution is Palladous nitrate. and nickel nitrate of Pd, Ni.
12. selective hydrogenation method of C 3 fractions according to claim 9, it is characterised in that in stepb, the ratio of the molal quantity of Ni and the molal quantity of Pd is 0.4～5:1.
13. selective hydrogenation method of C 3 fractions according to claim 9, it is characterised in that the mixed-cation solution ph of Pd, Ni is 1.5～4.0 in stepb.
14. selection method of hydrotreating according to claim 1, it is characterised in that the sulfur-containing impurities not higher than 30ppm can be contained in unstripped gas.
15. selection method of hydrotreating according to claim 1, it is characterised in that in unstripped gas can contain not higher than 30ppb containing arsenic impurities.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107051543A (en) * | 2017-05-08 | 2017-08-18 | 大连圣得环保新材料有限公司 | A kind of acetylene removal hydrogen catalyst and preparation method and application |
| CN108250020A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of selection method of hydrotreating of C3 fraction |
| CN108250024A (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 hydrotreating of C3 fraction |
| CN111423299A (en) * | 2019-01-10 | 2020-07-17 | 北京工商大学 | Photochemical catalytic synthesis method of aryl olefin compound |
| CN114950470A (en) * | 2022-06-30 | 2022-08-30 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application of nickel-based catalyst in selective hydrogenation of propyne and propadiene in propylene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102206132A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C3 fraction |
| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
| CN104098427A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | C3 fraction selective hydrogenation method |
-
2014
- 2014-12-12 CN CN201410773593.5A patent/CN105732285B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102811807A (en) * | 2010-03-19 | 2012-12-05 | 国际壳牌研究有限公司 | Hydrogenation catalyst |
| CN102206132A (en) * | 2011-04-07 | 2011-10-05 | 中国石油天然气股份有限公司 | Selective hydrogenation method for C3 fraction |
| CN104098427A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | C3 fraction selective hydrogenation method |
Non-Patent Citations (6)
| Title |
|---|
| BJORN ELMAN等: "POLYMER-SUPPORTED 2，2’-DIPYRIDYLMETHANE：SYNTHESIS AND FORMATION OF TRANSITION METAL COMPLEXES", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| 何炳林等: "高分子负载加氢催化剂中钯流失的研究 Ⅰ.高分子载体的影响", 《应用化学》 * |
| 史鸿鑫: "《现代化学功能材料》", 31 December 2009 * |
| 杨辉荣、黎碧娜等: "《聚合物试剂和催化剂》", 31 December 1991 * |
| 金关泰: "《高分子化学的理论和应用进展》", 31 March 1995, 中国石化出版社 * |
| 鲁奇林等: "络合催化剂的多相化", 《辽宁师范大学自然科学学报》 * |
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|---|---|---|---|---|
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| CN108250024A (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 hydrotreating of C3 fraction |
| CN107051543A (en) * | 2017-05-08 | 2017-08-18 | 大连圣得环保新材料有限公司 | A kind of acetylene removal hydrogen catalyst and preparation method and application |
| CN107051543B (en) * | 2017-05-08 | 2019-12-17 | 大连圣得环保新材料有限公司 | Dealkynylhydrogen catalyst and preparation method and application thereof |
| CN111423299A (en) * | 2019-01-10 | 2020-07-17 | 北京工商大学 | Photochemical catalytic synthesis method of aryl olefin compound |
| CN111423299B (en) * | 2019-01-10 | 2023-03-10 | 北京工商大学 | Photochemical catalytic synthesis method of aryl olefin compound |
| CN114950470A (en) * | 2022-06-30 | 2022-08-30 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application of nickel-based catalyst in selective hydrogenation of propyne and propadiene in propylene |
| CN114950470B (en) * | 2022-06-30 | 2023-07-25 | 东营科尔特新材料有限公司 | Nickel-based catalyst, preparation method thereof and application thereof in selective hydrogenation of propyne and propadiene in propylene |
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