CN101433845B - Selectively hydrogenating catalyst and preparation method thereof - Google Patents
Selectively hydrogenating catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides an unsaturated hydrocarbon selective hydrogenation catalyst and a preparation method thereof. The catalyst uses alumina as a carrier and palladium as an active ingredient, and is characterized by comprising the following components by weight percentage: 0.1 to 1.0 percent of the palladium, 0.3 to 8.0 percent of a rare earth metal, 0.1 to 5.0 percent of alkaline-earth metal, 0 to 3.0 percent of fluorine which can also be contained in the catalyst, and the rest is the alumina carrier, based on the total weight of the catalyst. The alumina carrier is theta or mix-crystal type Al2O3, and the priority is given to the theta crystal type. In the invention, the catalyst palladium is preferably distributed in a secondary outer layer of the catalyst. The catalyst has certain impurity resistance and coking resistance, is applicable to a section of selective hydrogenation process in full distillate cracked gasoline and unsaturated hydrocarbon selective hydrogenation process in other distillate oils.
Description
Technical field
The invention relates to a kind of selective hydrocatalyst and preparation method thereof, more specifically say so about full-cut fraction pyrolysis gasoline (C
5～C
9Cut) Catalysts and its preparation method of selective hydrogenation.
Background technology
Full-cut fraction pyrolysis gasoline is meant the C of ethylene cracker by-product
5～C
9Gasoline fraction, its output accounts for 50～80% of ethylene yield.The drippolene one-stage hydrogenation has two kinds of technologies, and a kind of is earlier full distillation gasoline to be cut out C
5, C
9Cut is to middle cut C
6～C
8Carry out hydrogenation, another kind is not add separation, directly to C
5～C
9Full-cut fraction pyrolysis gasoline carries out hydrogenation.Present most drippolene one-stage hydrogenation device still uses palladium catalyst.
It is the palladium catalyst of carrier that the drippolene one-stage hydrogenation generally adopts with the aluminium oxide, and palladium content is between 0.15～0.50%, and this type of method for preparing catalyst is more, and in order to improve catalyst performance, the modification to carrier has been paid attention in research in recent years.CN1071443A discloses and has been used for the one-stage selective hydrogenation of gasoline splitting catalyst, active component is a palladium, carrier is a, θ mixed phase aluminium oxide, be lamella catalyst, the palladium content that with the carrier is benchmark is 0.28～0.30 heavy %, and reaction temperature rising is low, diolefin hydrogenation selectivity height, anti-preferably arsenic ability is arranged, and this catalyst is mainly used in drippolene C
6～C
8Cut fraction hydrogenation.CN1429889A discloses a kind of catalyst of selective hydrogenation, by the palladium of 0.15～0.5 heavy %, alkaline earth oxide and the carrier A l of 0.1～3.0 heavy %
2O
3Form Al
2O
3Carrier specific surface 50～150m
2/ g, specific pore volume 0.35～0.55ml/g, the hole of pore radius 5.0～10.0nm accounts for more than 70% of total pore volume.Carrier adopts alkaline earth oxide to carry out surface modification earlier, again the load active component palladium.This catalyst is applicable to the one-stage selective hydrogenation of gasoline splitting process.CN1179788C discloses a kind of selective hydrocatalyst, and this catalyst comprises carrier, active component palladium and rare earth metal, reaches promoter metal such as bismuth, silver.It is characterized in that: the percentage by weight of active component palladium is 0.008～0.3%, and the palladium layer thickness is 5～30 μ m, and the weight percent content of silver, potassium and transition metal component is 0.01～2%, and the percentage by weight of rare earth metal component is 0.05～3%.Described carrier is selected from Al
2O
3, TiO
2Or SiO
2, it is shaped as gear shape, strip or spherical.CN1175931C discloses a kind of load type palladium-aluminium oxide catalyst and preparation method thereof, and it relates to a kind of applying the Sq rare earth oxide in advance, and through 900～1000 ℃ of hard burned Al
2O
3Be carrier, the about 60～130m of specific area
2/ g, average pore radius is about 10～14nm, is active component with the palladium, and loading is 0.15～0.25% (wt), adopts the dipping method preparation.
In the prior art, the catalyst of employing is general active higher, and reasonable diolefin hydrogenation effect is arranged.But, complicated and changeable along with cracking stock, some drippolene raw material proportion increases, and contains impurity such as arsenic, water and heavy metal in the raw material, causes the oil quality variation, causes catalyst coking, poisoning, influences catalyst service life.Under the more situation of impurity content, often catalyst activity is high more, easy more poisoning.The anti-impurity performance of palladium catalyst of the prior art has much room for improvement.
Summary of the invention
The full fraction hydrogenating Catalysts and its preparation method of drippolene that the purpose of this invention is to provide a kind of practicality.This catalyst is compared with existing catalyst at anti-impurity aspect of performance and is made moderate progress.
The invention provides a kind of selective hydrocatalyst, with the palladium is active component, with the aluminium oxide is carrier, it is characterized in that the gross weight with catalyst is that this catalyst of benchmark consists of: rare-earth oxide, rare earth metal content is 0.1～6.0%, preferred 0.3～5.0%, rare earth metal is selected from lanthanum and/or cerium; Alkaline earth oxide, alkaline earth metal content are 0.1～4.0%, preferred 0.2～3.0%; Active component palladium content is 0.1～1.0%.Also can contain fluorine in addition, fluorine content is 0～3.0%, preferred 0.1～2.0%; Surplus is an alumina support; Alumina support is a θ crystal formation or based on the mixing crystal formation of θ crystal formation, the θ crystal formation accounts for more than 80%, and the alumina support average pore radius is 10～16nm; The specific area of catalyst is 50～90m
2/ g, pore volume are 0.51～0.80ml/g, and the outer surface of catalyst has the carrier layer of 0.02～0.2mm, palladium to be distributed in the inferior outer of catalyst, palladium layer thickness 0.1～0.5mm.
Catalyst carrier of the present invention is an aluminium oxide, the shape of employed carrier can be spherical, tooth is spherical, strip, ring-type etc., preferred tooth are spherical.The specific area of carrier is preferably 50～90m
2/ g is preferably 55～80m
2/ g; Pore volume is preferably 0.35～0.80ml/g, is preferably 0.40～0.70ml/g; The carrier average pore radius is preferably 10～16nm; Alumina support is a θ crystal formation or based on the mixed crystal formation of θ crystal formation, the θ crystal formation preferably accounts for vehicle weight more than 80%, preferably θ, α mixed crystal, and this carrier sintering temperature height, carrier surface acidity is low, helps improving catalyst anti-coking performance.
The active component that the present invention adopts is a precious metal palladium, and the quality percentage composition of palladium is 0.1～1.0%, preferably palladium content is 0.2～0.5%.In the present invention, palladium preferably is distributed in time outer in the catalyst, catalyst outermost layer thickness be 0～0.2mm carrier layer (preferably 0.02～0.2mm), be the palladium layer secondly, palladium layer thickness 0.1～0.5mm.
Diolefin content height in the full fraction drippolene, mainly be cyclopentadiene and dicyclopentadiene, easily in the catalyst surface coking, for slowing down catalysqt deactivation, prolonging life of catalyst, the carrier of catalyst will have bigger pore volume and aperture, and pore volume should be greater than 0.4ml/g, and average pore radius should be greater than 10.0nm, carrier surface area can not be too big, and catalyst activity is suitable.By in catalyst preparation process, adding co-catalyst and active component synergy, can improve catalyst performance, as introduce rare earth oxide and can improve the alumina support performance, at high temperature still good specific surface area can be kept, and the dispersity of palladium can be improved; Suitably add alkaline earth oxide and fluoride and can improve catalyst surface character, help improving the catalyst hydrogenation performance, improve the catalyst poison resistance.
The present invention also provides a kind of above-mentioned Preparation of catalysts method:
Preparation of Catalyst adopts infusion process, and the carrier that will contain rare earth and/or alkaline-earth metal immerses and contains in palladium bichloride or the palladium nitrate aqueous solution, flood that drop goes out after 15～40 minutes, 100～150 ℃ of dryings 3～6 hours down, 450～550 ℃ of following roastings 3～6 hours.
Can contain the alkaline-earth metal soluble-salt in the palladium chloride aqueous solution in the said method.
Each addition of forming satisfies the desired compositing range of catalyst of the present invention with final products and is as the criterion, and the present invention is special requirement addition separately not, to add or the amount to the catalyst of flooding meets the demands and gets final product.
The carrier that contains rare earth and/or alkaline-earth metal can adopt will have the θ crystal formation or based on the mixing crystal formation alumina support of θ crystal formation, with containing rare earth or also contain the maceration extract pre-preg of alkaline-earth metal soluble-salt simultaneously, and 300～600 ℃ of following roastings 2～6 hours.
The carrier that contains rare earth and/or alkaline-earth metal among the present invention can also contain fluorine simultaneously, to have the θ crystal formation or based on the mixing crystal formation alumina support of θ crystal formation, with containing rare earth, fluorine or also contain the maceration extract pre-preg of alkaline-earth metal soluble-salt simultaneously, and 300～600 ℃ of following roastings 2～6 hours.
The carrier that contains rare earth and/or alkaline-earth metal among the present invention can also be by adding rare earth oxide or its predecessor, alkaline earth oxide (as magnesium, calcium or barium etc.) or its predecessor, inorganic fluorine compounds before the carrier moulding, the carrier moulding is after roasting obtains the θ crystal formation or based on the mixing crystal formation alumina support of θ crystal formation.
The preparation method of alumina support is very ripe, adopts universal method to make, and the present invention is not limited especially.As being: at Al
2O
3Add peptizing agent in the dry glue powder, extrusion aid, pore creating material and an amount of water are pinched into plasticity material group in kneader, and through the extruding aftershaping, as obtaining difformities such as φ 2～φ 4 tooth balls, strip, ring-type, drying, roasting promptly make alumina support.The carrier specific surface that this catalyst adopts is preferably 50～80m
2/ g, pore volume 0.3～0.8ml/g, particularly pore radius account for more than 70% of whole pore volume in the pore volume between 10～20nm.Seek out the θ crystal formation or based on the mixing crystal formation alumina support of θ crystal formation, general carrier need be through 1000～1200 ℃ of roastings 3～10 hours, this also is the routine techniques that non-normal open is used.The carrier roasting can make carrier remove volatile components by thermal decomposition, forms stable pore structure, specific surface, crystal formation and mechanical strength.Catalyst carrier sintering temperature of the present invention is preferably 1000～1180 ℃, and roasting time is preferably 3～6 hours.
Peptizing agent can be selected one or more in inorganic acid, organic acid, the polyacid for use, and as being general nitric acid, phosphoric acid, acetic acid, citric acid etc., addition is generally 1～10% of total weight of carrier.Recommend among the present invention to contain acetic acid in the carrier peptizing agent.
Adding extrusion aid and pore creating material can make material group extrude smooth surface easily.And pore-creating as required, can select general sesbania powder, starch, methylcellulose, polyalcohol, carbon dust, citric acid etc. for use, also can be wherein two kinds of uses simultaneously.Addition is generally 1～10% of total weight of carrier.
Catalyst of the present invention need add rare earth oxide or its predecessor, or/and the oxide of cerium can add, also can be immersed in carrier surface as lanthanum when preparing carriers.When add the fashionable soluble-salt that preferably uses rare earth with impregnation method, as adding with nitrate or chloride form, the nitrate of rare earth or chloride addition (in rare earth oxide) are total weight of carrier 0.3～8.0%.
Catalyst of the present invention also need add alkaline earth oxide (as magnesium, calcium or barium etc.) or its predecessor, can add when preparing carriers, also can be immersed in carrier surface.When add the fashionable soluble-salt that preferably uses alkaline-earth metal with impregnation method, as adding with nitrate or chloride form, as selecting in calcium chloride, calcium sulfate, magnesium nitrate, barium chloride, the barium nitrate one or more for use, the addition of alkali salt (in metal oxide) is 0.1～5.0% of a total weight of carrier.
Catalyst of the present invention can add inorganic fluorine compounds, adds in the time of can being chosen in preparing carriers or the mode that is immersed in carrier surface adds, when add fashionable ammonium fluoride or the hydrofluoric acid preferably selected for use with impregnation method.
The catalyst activity component is a palladium, adopts immersion process for preparing, and palladium-impregnated also can be flooded altogether with other water soluble salts separately.Palladium can be selected palladium nitrate and palladium bichloride for use; chlorion is residual when adopting the palladium nitrate impregnated carrier can avoid owing to employing palladium bichloride impregnated carrier; palladium impregnating depth on carrier can be regulated by changing the solution pH value; for effectively utilizing palladium; generally palladium is distributed on the carrier outer surface; if but palladium all is exposed to outer surface; when the raw material well cuts more for a long time catalyst poison easily; in the present invention; preferably the palladium layer is in the outmost surface of catalyst, but at inferior outer surface, the outmost surface of catalyst has the carrier layer of 0.02～0.2mm to play the protective layer effect; be canescence, palladium content is very low.The carrier protective layer is directly to contact with impurity and heavy metal compound in the drippolene for fear of active component, to strengthen the anti-poisoning capability of catalyst.The protective layer the inside is the palladium layer, and thickness is 0.1～0.5mm.It is dry more than 3 hours under the catalyst of making is preferably in 100～150 ℃.Be preferably in 450～550 ℃ of following roastings 3～6 hours.
It is stable to use the catalyst rerum natura that the present invention obtains, and active suitable, carrier aperture is big, has good diolefin hydrogenation performance and selectivity, and this catalyst is compared with existing catalyst at anti-impurity performance and anti-coking aspect of performance and made moderate progress, and has practicality.
The specific embodiment
Use raw material source and specification:
Al
2O
3Dry glue powder: the dry glue powder that adopts petrochemical industry Xiang prosperous company in Lanzhou to produce, wherein boehmite accounts for more than 80% of raw material weight.
Commercially available shaping carrier: spherical (Φ 3.5～4.0), specific surface 180～200m
2/ g, pore volume 0.65～0.75mL/g, average pore radius is 6.0～8.0nm.γ crystal formation aluminium oxide.
Agents useful for same in the example except that specifying, is chemically pure reagent.
Iodine number is analyzed: adopt the analysis of lodine chloride method.
The diene value is analyzed: adopt the UOP-326 standard analysis.
Specific surface: BET determination of nitrogen adsorption.
Pore volume: mercury injection method is measured.
Average pore radius: mercury injection method is measured.
Embodiment 1:
The preparation of carrier
The conventional extrusion moulding that employing is known prepares carrier, take by weighing aluminum oxide dry glue powder 200 grams that petrochemical industry Xiang prosperous company in Lanzhou produces, add sesbania powder 8 grams, 4 gram citric acids, 5.5 gram cerous nitrates are dissolved and be mixed into 160～180mL aqueous solution with 3mL acetic acid, water, pour in the alumina powder, mediate, extrusion modling is φ 4.0 tooth spheroid carriers, 110 ℃ of oven dry, 1060 ℃ of roastings 4 hours, get carrier of the present invention then.This carrier specific surface 70m
2/ g, pore volume 0.55ml/g, average pore radius is 12.0nm.Aluminium oxide is θ, α mixing crystal formation, and θ crystal formation aluminium oxide accounts for more than 80%.
Preparation of catalysts
Dissolving 5.0 gram palladium bichlorides are mixed with the 1000mL aqueous hydrochloric acid solution, and add the 20mL10% citric acid, make the palladium bichloride maceration extract.
Take by weighing above-mentioned carrier 100g, immerse 160mL and contain in the aqueous solution of magnesium nitrate, flood 30 minutes, 100～110 ℃ of dryings 3 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.To contain the Mg carrier and immerse in the palladium chloride solution contain 0.3 gram Pd, and evenly shake and heat, drop goes out after about 15 minutes, 100～110 ℃ dry 5 hours down, 500 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst A of the present invention.This catalyst weight percentage composition is Pd 0.30%, and Ce 1.2%, and Mg 0.35%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.03mm, palladium layer thickness 0.23mm with shell.
Embodiment 2
Method by embodiment 1 prepares carrier, and adds lanthanum nitrate to replace cerous nitrate when preparing carriers, with carrier 1150 ℃ of roastings 4 hours, this carrier specific surface 56m
2/ g, pore volume 0.51ml/g, average pore radius is 13.8nm.Aluminium oxide is θ, α mixing crystal formation, and θ crystal formation aluminium oxide accounts for more than 80%.
Take by weighing the 100g carrier, immerse 160mL and contain in the acidic aqueous solution of magnesium nitrate and palladium bichloride, take out after about 40 minutes, 100～110 ℃ dry 5 hours down, 550 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst B of the present invention.This catalyst weight percentage composition is Pd 0.26%, and La 1.8%, and Mg 0.25%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.01mm, palladium layer thickness 0.30mm with shell.
Embodiment 3
Method by embodiment 1 prepares carrier, and adds magnesium nitrate in the preparing carriers process, makes final catalyst contain Mg 0.50 (weight) %.With carrier 1000 ℃ of roastings 4 hours, this carrier specific surface 79m
2/ g, pore volume 0.54ml/g, average pore radius is 11.8nm.Aluminium oxide is θ, δ crystal formation, and θ crystal formation aluminium oxide accounts for more than 80%.
Take by weighing the 100g carrier, immerse 140mL and contain in the acidic aqueous solution of palladium bichloride, take out after about 30 minutes, 100～110 ℃ dry 5 hours down, 480 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst C of the present invention.This catalyst weight percentage composition is Pd 0.33%, and Mg 0.5%.Ce?1.0％。Pd is distributed in catalyst time skin, outermost support layer thickness 0.05mm, palladium layer thickness 0.23mm with shell.
Embodiment 4
Method by embodiment 1 prepares carrier, and adds barium nitrate to replace cerous nitrate in the preparing carriers process, makes final catalyst contain Ba 0.80 (weight) %.Take by weighing the 100g carrier, immerse 140mL and contain in the aqueous solution of cerous nitrate, flood 40 minutes, 100～110 ℃ dry 3 hours down, 530 ℃ of following roastings are 3 hours in muffle furnace, baked carrier pressed the method immersion palladium of embodiment 3.Make catalyst D of the present invention.This catalyst weight percentage composition is Pd 0.35%, and Ba 0.80%, and Ce 0.5%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.08mm, palladium layer thickness 0.25mm with shell.
Embodiment 5
Adopt commercially available shaping carrier 200 grams, 1020 ℃ of roastings 4 hours.This carrier specific surface 74m
2/ g, pore volume 0.53ml/g, average pore radius is 10.6nm.Aluminium oxide is the θ crystal formation.
Taking by weighing 100 gram carriers immersion 140mL contains in the aqueous solution of cerous nitrate, flooded 40 minutes, drying is 3 hours under 100～110 ℃, 500 ℃ of following roastings are 3 hours in muffle furnace, to contain method immersion Pd and the Mg of cerium carrier by embodiment 2,100～110 ℃ dry 5 hours down, 550 ℃ of following roastings are 3 hours in muffle furnace.Make catalyst E of the present invention.This catalyst weight percentage composition is Pd 0.28%, and Mg 0.20%, and Ce 0.8%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.02mm, palladium layer thickness 0.20mm with shell.
Embodiment 6
Method by embodiment 1 prepares carrier, and adds barium nitrate in the preparing carriers process, makes to contain Ba 0.6% in the final catalyst, contains Ce 1.8%.This carrier was 1100 ℃ of roastings 4 hours.Carrier specific surface 68m
2/ g, pore volume 0.52ml/g, average pore radius is 12.4nm.Aluminium oxide is the θ crystal formation.
Take by weighing 100 gram carriers, immerse in the aqueous solution of 140mL fluorinated ammonium, flooded 40 minutes, drying is 3 hours under 100～110 ℃, 400 ℃ of following roastings are 3 hours in muffle furnace, and fluorine-containing carrier is pressed the method load P d of embodiment 3,100～110 ℃ dry 5 hours down, 480 ℃ of following roastings are 3 hours in muffle furnace, make catalyst F of the present invention.This catalyst weight percentage composition is Pd 0.24%, and F 0.5%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.01mm, palladium layer thickness 0.20mm with shell.
Embodiment 7
Prepare carrier and prepare catalyst by the method for embodiment 6 by the method for embodiment 2, make that weight percentage is Ba 0.8% in the final catalyst, contain La 1.0%, Pd 0.26%, F0.3%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.02mm, palladium layer thickness 0.25mm with shell.Make catalyst G of the present invention.
Embodiment 8
Method by embodiment 2 prepares carrier, with carrier 1060 ℃ of roastings 4 hours, this carrier specific surface 74m
2/ g, pore volume 0.53ml/g, average pore radius is 12.4nm.Aluminium oxide is the θ crystal formation.
With 0.3 gram palladium bichloride dissolving with hydrochloric acid, be mixed with 100mL solution, dipping 100g carrier takes out after about 20 minutes, and 100～110 ℃ of dryings 5 hours down, 550 ℃ of following roastings are 4 hours in muffle furnace.Make catalysis H.This catalyst weight percentage composition is Pd 0.24%, and Mg 0.30%.Pd is distributed on the catalyst outer surface with shell, palladium layer thickness 0.15mm.
Comparative example 1
Method by embodiment 2 prepares carrier, and 950 ℃ of following roastings 4 hours, obtaining the δ crystal formation was main aluminium oxide, this carrier specific surface 102m with carrier
2/ g, pore volume 0.53ml/g, average pore radius is 10.2nm.
Take by weighing the 100g carrier, immerse 140mL and contain in the acidic aqueous solution of magnesium nitrate and palladium bichloride, take out after about 40 minutes, 100～110 ℃ dry 5 hours down, 550 ℃ of following roastings are 4 hours in muffle furnace.Make catalyst I.This catalyst weight percentage composition is Pd 0.32%, and La 1.0%, and Mg 0.40%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.03mm, palladium layer thickness 0.2mm with shell.
Comparative example 2
Method by embodiment 1 prepares carrier, method by embodiment 2 prepares catalyst, different is to add bismuth nitrate to replace magnesium nitrate in the process of palladium-impregnated, makes final catalyst bismuth-containing 0.30 (weight) %, and this catalyst weight percentage composition is Pd 0.33%.Ce?1.4％。Pd is distributed in catalyst time skin, outermost support layer thickness 0.06mm, palladium layer thickness 0.28mm with shell.Make catalyst J.
Comparative example 3
Method by embodiment 1 prepares carrier and catalyst.But in the preparing carriers process, do not add cerous nitrate.110 ℃ of oven dry, then 1000 ℃ of roastings 4 hours.This carrier specific surface 72m
2/ g, pore volume 0.54ml/g, average pore radius is 10.6nm.Aluminium oxide is θ, alpha-crystal form.Aluminium oxide accounts for more than 80%.This catalyst weight percentage composition is Pd 0.30%, and Mg 0.35%.Pd is distributed in catalyst time skin, outermost support layer thickness 0.04mm, palladium layer thickness 0.25mm with shell.Make catalyst K.
Comparative example 4
Method by embodiment 1 prepares carrier and catalyst.But in catalyst preparation process, do not add magnesium nitrate.Make catalyst L.
Comparative example 5
Adopt outsourcing carrier 200 grams, 1020 ℃ of roastings 4 hours.This carrier specific surface 74m
2/ g, pore volume 0.53ml/g, average pore radius is 11.4nm.Aluminium oxide is the θ crystal formation.Method by embodiment 8 prepares catalyst, and this catalyst weight percentage composition is Pd 0.30%, and Pd is distributed on the catalyst outer surface with shell, palladium layer thickness 0.15mm.Make catalyst M.This catalyst does not contain rare earth and alkaline earth oxide.
Estimate one.
Table 1 feedstock oil rerum natura
| The oil product title | C 5-C 9Full fraction drippolene | Proportioning oil |
| Density (20 ℃), g/cm 3 | 0.838 | 0.836 |
| Iodine number (gram iodine/100 gram oil) | 144.15 | 98.74 |
| Diene value (gram iodine/100 gram oil) | 45.88 | 23.60 |
| Boiling range (℃) | 45-198 | 48-198 |
To in autoclave, estimate by catalyst A, B, C, D, E, F, G, H, I, J, K, the L of embodiment 1～8 and comparative example 1～4 preparation.Appreciation condition is: loaded catalyst is 1g, and reaction pressure is 60 ℃ of 2.8MPa, reaction temperatures, 40 minutes reaction time.Full fraction C
5～C
9Drippolene raw material and proportioning oil rerum natura see Table 1, and test adds proportioning oil (feedstock oil: product oil is 1: 1) 60mL, adds arsenic 200ppb in proportioning oil, adds entry 15%.Four batches of oil of each evaluating catalyst, analysis result is averaged, and evaluation result sees Table 2.
Table 2 catalyst is to containing arsenic and water feedstock oil hydrogenation evaluation result
Estimate two
Will be by catalyst A, the M of 5 preparations of embodiment 1 and comparative example, in 300mL adiabatic reactor reaction unit, estimate.Appreciation condition is: loaded catalyst is 100mL, and reaction pressure is 50 ℃ of 2.8MPa, reaction temperatures.Hydrogen-oil ratio (volume ratio) 150, the drippolene raw material is identical with autoclave evaluation raw material.Proportioning oil (feedstock oil: product oil is 1: 3) hydrogenation the results are shown in Table 3.
Table 3 raw material well cuts influences catalyst hydrogenation activity
From table 2, table 3 result of the test as can be seen, in catalyst preparation process, add rare earth oxide and alkaline earth oxide and fluoride etc., can improve the hydrogenation performance of catalyst, improved the adaptive capacity of catalyst the raw material well cuts.
Claims (14)
1. a selective hydrocatalyst is an active component with the palladium, is carrier with the aluminium oxide, it is characterized in that the gross weight with catalyst is a benchmark, this catalyst consists of: rare-earth oxide, rare earth metal content are 0.1～6.0%, and rare earth metal is selected from lanthanum and/or cerium; Alkaline earth oxide, alkaline earth metal content are 0.1～4.0%; Active component palladium content is 0.1～1.0%; Fluorine content is 0～3.0%; Surplus is an alumina support; Alumina support is a θ crystal formation or based on the mixing crystal formation of θ crystal formation, the θ crystal formation accounts for more than 80%, and the alumina support average pore radius is 10～16nm; The specific area of catalyst is 50～90m
2/ g, pore volume are 0.51～0.80ml/g, and the outer surface of catalyst has the carrier layer of 0.02～0.2mm, palladium to be distributed in the inferior outer of catalyst, palladium layer thickness 0.1～0.5mm.
2. catalyst according to claim 1 is characterized in that catalyst middle rare earth tenor is 0.3～5.0%.
3. catalyst according to claim 1 is characterized in that alkaline earth metal content is 0.2～3.0% in the catalyst.
4. catalyst according to claim 1 is characterized in that fluorine content is 0.1～2.0% in the catalyst.
5. catalyst according to claim 1 is characterized in that alumina support is the mixed crystal formation of θ, α in the catalyst, and the θ crystal formation accounts for vehicle weight more than 80%.
6. catalyst according to claim 1, it is characterized in that in the catalyst alumina support for spherical, tooth is spherical, strip or ring-type.
7. one kind according to the described Preparation of catalysts method of claim 1, it is characterized in that Preparation of Catalyst adopts infusion process, the carrier that will contain rare earth and/or alkaline-earth metal immerses and contains in the aqueous solution of palladium bichloride or palladium nitrate, flood that drop goes out after 15～40 minutes, drying was 3～6 hours under 100～150 ℃, 450～550 ℃ of following roastings 3～6 hours.
8. according to the described Preparation of catalysts method of claim 7, it is characterized in that containing in the palladium chloride aqueous solution alkaline-earth metal soluble-salt.
9. according to the described Preparation of catalysts method of claim 7, the carrier that it is characterized in that containing rare earth and/or alkaline-earth metal is by having the θ crystal formation or based on the mixing crystal formation alumina support of θ crystal formation, with containing rare earth or also contain the maceration extract pre-preg of alkaline-earth metal soluble-salt simultaneously, and make in 2～6 hours method of 300～600 ℃ of following roastings.
10. according to the described Preparation of catalysts method of claim 7, the carrier that it is characterized in that containing rare earth and/or alkaline-earth metal is by having the θ crystal formation or based on the mixing crystal formation alumina support of θ crystal formation, with containing rare earth and fluorine or also contain the maceration extract pre-preg of alkaline-earth metal soluble-salt simultaneously, and make in 2～6 hours method of 300～600 ℃ of following roastings.
11. according to the described Preparation of catalysts method of claim 7, the carrier that it is characterized in that containing rare earth and/or alkaline-earth metal is by adding rare-earth oxide or its predecessor, alkaline earth oxide or its predecessor and/or inorganic fluorine compounds before the carrier moulding, the carrier moulding is after 1000～1180 ℃ of method of roasting acquisitions.
12. according to the described Preparation of catalysts method of claim 11, the predecessor that it is characterized in that rare-earth oxide is selected from one or more in lanthanum nitrate, cerous nitrate, the cerium chloride.
13. according to the described Preparation of catalysts method of claim 11, the predecessor that it is characterized in that alkaline earth oxide is selected from one or more in calcium chloride, calcium sulfate, magnesium nitrate, barium chloride, the barium nitrate.
14., it is characterized in that inorganic fluorine compounds is ammonium fluoride or hydrofluoric acid according to the described Preparation of catalysts method of claim 11.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101147440A CN101433845B (en) | 2008-06-11 | 2008-06-11 | Selectively hydrogenating catalyst and preparation method thereof |
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|---|---|---|---|
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| CN102220159B (en) * | 2010-04-13 | 2014-01-08 | 中国石油化工股份有限公司 | Method for selective hydrogenation of cracked C5 |
| CN102220160B (en) * | 2010-04-13 | 2014-01-08 | 中国石油化工股份有限公司 | Method of selective hydrogenation of alkyne in cracking C5 |
| CN102108537A (en) * | 2011-01-29 | 2011-06-29 | 常州天合光能有限公司 | Solar battery electroplating pretreatement process |
| CN102794159B (en) * | 2011-05-27 | 2014-12-31 | 中国石油化工股份有限公司 | Fluorine-containing hydrated alumina forming composition and preparation method thereof |
| CN116408089A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method and application thereof |
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| US3484421A (en) * | 1965-07-20 | 1969-12-16 | Exxon Research Engineering Co | Two stage hydrogenation process (ii) |
| US5258558A (en) * | 1991-10-21 | 1993-11-02 | Uop | Direct conversion of butyraldehyde to 2-ethylhexanol-1 |
| CN1429889A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Selective hydrogenation catalyst |
| CN1435277A (en) * | 2003-02-21 | 2003-08-13 | 福州大学 | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof |
| CN1623655A (en) * | 2004-10-26 | 2005-06-08 | 福州大学 | Palladium-aluminium oxide catalyst and its preparation process |
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| US3484421A (en) * | 1965-07-20 | 1969-12-16 | Exxon Research Engineering Co | Two stage hydrogenation process (ii) |
| US5258558A (en) * | 1991-10-21 | 1993-11-02 | Uop | Direct conversion of butyraldehyde to 2-ethylhexanol-1 |
| CN1429889A (en) * | 2001-12-30 | 2003-07-16 | 中国石化集团齐鲁石油化工公司 | Selective hydrogenation catalyst |
| CN1435277A (en) * | 2003-02-21 | 2003-08-13 | 福州大学 | Supported palladium catalyst for producing hydrogen peroxide by anthraquinone process and preparing method thereof |
| CN1623655A (en) * | 2004-10-26 | 2005-06-08 | 福州大学 | Palladium-aluminium oxide catalyst and its preparation process |
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