CN102989452B - C2 front-end hydrogenation catalyst containing composite carrier and preparation method - Google Patents
C2 front-end hydrogenation catalyst containing composite carrier and preparation method Download PDFInfo
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- CN102989452B CN102989452B CN201110267101.1A CN201110267101A CN102989452B CN 102989452 B CN102989452 B CN 102989452B CN 201110267101 A CN201110267101 A CN 201110267101A CN 102989452 B CN102989452 B CN 102989452B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a C2 front-end hydrogenation catalyst containing a composite carrier, the C2 front-end hydrogenation catalyst comprises the following components by taking the mass of the carrier as 100%, 0.02-0.15 parts of palladium and silver, the mass ratio of silver to palladium is 9-1:1, by taking element mass of palladium and silver, the carrier of the catalyst is an alumina-titanium oxide composite carrier with two peaks distribution. by calculating the carrier mass as 100%, the carrier comprises 1-95% of alumina and 5-99% of titanium oxide, and the carrier has the following physical properties: the bulk density is 0.7 to 1.1g/ml, the pore volume is 0.2 to 0.6ml/g, the specific surface area is 3 to 60m<2>/g, the average pore size is 80 to 400nm, 20-370nm preferably; and the carrier has two peaks when the pore size is 60 to 130nm and 400 to 800nm. The invention also discloses the preparation method of the hydrogenation catalyst.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method, be specifically related to a kind of salic-Catalysts and its preparation method that titanium oxide composite oxides are carrier.
Background technology
In the cracking gas producing in cracking petroleum hydrocarbon vapor process, often contain the impurity such as a small amount of acetylene, propine and allene, their existence can affect high-efficiency polyethylene and the polypropylene catalyst that in follow-up workshop section, homogeneous polymerization and polymerization process are used to some extent.By the requirement of the rear manufacturing procedures such as polyethylene, EP rubbers, polypropylene, in polymer grade ethylene, the molar fraction of acetylene must be lower than 5ppm, and ethylene glycol also requires the molar fraction of acetylene in ethene lower than 1ppm in producing.Catalysis selective hydrogenation method be industrial most widely used general, be also a kind of method that the most effectively removes acetylene, propine and allene (MAPD), the catalyst adopting mostly is alumina load precious metals pd catalyst.
Selecting hydrogenation except in acetylene reaction, in traditional catalyst use procedure, also there is more side reaction: ethylene hydrogenation generates ethane; The easy hydrogenation dimerization of acetylene being adsorbed on catalyst surface generates the unsaturated C such as 1,3-butadiene
4hydrocarbon, continues reaction and generates C
6～C
24deng high polymer (green oil).Green oil sticks to hydrogenation activity and selective decline that can cause catalyst on selective acetylene hydrocarbon hydrogenation catalyst, shortens life cycle, causes catalyst frequent regeneration, affects the service life of catalyst, thereby causes the raising of production cost.
Acetylene selective hydrogenation is divided into two kinds of front-end hydrogenation and back end hydrogenations, so-called front-end hydrogenation refers to the relative domethanizing column of acetylene hydrogenation reactor position with back end hydrogenation, acetylene hydrogenation reactor is back end hydrogenation for front-end hydrogenation, acetylene hydrogenation reactor are positioned at domethanizing column afterwards before being positioned at domethanizing column, wherein, front-end hydrogenation technological process is divided into again two kinds of front-end deethanization front-end hydrogenation and predepropanization front-end hydrogenations.Hydrogenation technique is different, and the raw material that enters reactor forms also difference, and wherein maximum difference is that the material that enters reactor in front-end hydrogenation technique contains a large amount of hydrogen and more CO.Due to the hydrogen that contains high concentration in hydrogenation reaction material (approximately 20-50mol%) and CO (300～5000ppm (mol)), and hydrogen and CO fluctuation range large, so higher to the requirement of the activity and selectivity of hydrogenation catalyst.In fact, improve the key that front-end hydrogenation removes the separation process of acetylene and be just to improve the selective and active of selective hydrogenation catalyst, reduce the sensitivity of catalyst to hydrogen and CO concentration, and improve front-end hydrogenation, select the selective and active key of acetylene hydrogenation catalyst to be to improve the pore structure of carrier.For the problems referred to above, conventionally by improving the method for carrier sintering temperature, obtain the eurypyloue α-Al of tool
20
3carrier, but the surface-sensitive degree that reduces catalyst carrier with this is limited.
Prior art also attempts to improve by preparing complex carrier the performance of catalyst, but, for the complex carrier of carbon two front-end hydrogenation catalyst only CN00136874.5 by preparing the complex carrier of aluminium oxide and titanium oxide, improve the performance of catalyst, this carrier aperture is distributed in 50nm and 1000nm occurs bimodal.This carrier, for the preparation of hydrogenation catalyst, can effectively improve the anti-coking performance of carbon two front-end hydrogenation catalyst, but larger aperture occurs at 1000nm, and the excessive catalyst activity that causes in a part of aperture of catalyst reduces.The carrier of other bimodal pore size distribution, for the preparation of carbon two front-end hydrogenation catalyst, exists ratio table and pore-size distribution to be not suitable with the defect of catalyst requirement, causes catalyst activity component Pd decentralization lower, or the higher shortcoming of catalyst surface acidity.
CN97114892.9 disclose a kind of under catalyst exists the method for hydroaromatic compound, the carrier material that has wherein comprised this catalyst, the average pore size of carrier material is at least about 50nm, and preferably at least about 100nm, and its surface area (BET) is not more than 30m
2/ g.US7507845B1, discloses a kind of carrier, has bimodal pore distribution: the aperture in first kind hole is 0.01～5 μ m, and the aperture in Equations of The Second Kind hole is 5～30 μ m; First kind hole content is lower than 50%, and Equations of The Second Kind hole content is higher than 50%; Catalyst water absorption rate scope is 0.2～0.8cc/g, and it is 0.3～4.0m that BET records than table
2/ g, pore volume is 0.2～0.8ml/g.Above two kinds of carriers, for the preparation of carbon two front-end hydrogenation catalyst, because specific area is too small, are unfavorable for the dispersion of active component Pd, and prepared catalyst activity and selectivity is all poor.
CN00124057.9 discloses a kind of catalyst that two-peak hole radius distributes that has, contain a) titanium dioxide of 10～99.9% weight, and b) aluminium oxide of 0～60% weight, silica and/or titanium dioxide, and c) at least one element of HuoII A family of I A family in the periodic table of elements of 0.1～10% weight, a kind of element of transition group III, a kind of element of transition group VIII, lanthanum and/or tin, condition is that the summation of percentage by weight is 100.In this catalyst, 70～100% hole is less than 20nm or in the scope of 40～5000nm, its specific area is at least 70m
2/ g.The total pore volume 0.45～0.96ml/g of its carrier of the disclosed catalyst of US2009062557A1, average pore size is
be greater than
20～80%, the BET that accounts for be 100～550m
2/ g.Above two kinds of carriers, for the preparation of carbon two front-end hydrogenation catalyst, because specific surface area of catalyst is larger, cause its surface acidity higher, catalyst anti-coking poor performance.
The height of China University Of Petroleum Beijing mink cell focus processing National Key Laboratory discloses ZrO dawn
2-Al
2o
3the preparation of catalyst carrier and application (< < Industrial Catalysis > > the 16th the 3rd phase of volume in 2008), introduced current ZrO
2-Al
2o
3the preparation situation of complex carrier, comprises dipper precipitation method, alkoxide sol-gel method and coprecipitation.The composite oxide carrier specific area preparing by this article method is larger, and acidity is stronger, and minimum specific area is 190m
2/ g.
In prior art, the carrier of bimodal pore size distribution, for the preparation of carbon two front-end hydrogenation catalyst, exists ratio table and pore-size distribution to be not suitable with the defect of catalyst requirement, causes catalyst activity component Pd decentralization lower, or the higher shortcoming of catalyst surface acidity.
Summary of the invention
The object of the present invention is to provide a kind of carbon that contains the suitable carrier of pore-size distribution two front-end hydrogenation catalyst, this catalyst have hydrogenation activity high, selectively good, green oil generating amount is low, can use higher in the situation that at hydrogen and CO content, and has stronger anti-hydrogen and CO fluctuation ability.Another object of the present invention has been to provide the preparation method of hydrogenation catalyst.
Carbon two front-end hydrogenation catalyst containing complex carrier disclosed in this invention, in 100 parts of catalyst qualities, comprise 0.02～0.15 part of palladium, preferably 0.02～0.10 part; Silver, silver and the mass ratio 9～1: 1 of palladium, preferably 6～1: 1; Palladium, silver are all in element quality; Carrier wherein, in carrier quality 100%, comprises aluminium oxide 1～95%, titanium oxide 5～99%, and this carrier has following physical property: bulk density 0.7～1.1g/ml, pore volume 0.2～0.6ml/g, specific area 3～60m
2/ g, average pore size 80～400nm, preferred 120～370nm, carrier occurs bimodal at 60～130nm and 400～800nm place.
Complex carrier in catalyst of the present invention, its mesoporous accounts for 0～4% of total pore volume lower than the hole of 10nm, the hole of 10～100nm accounts for 15～80% of total pore volume, the hole that is greater than 100nm but is less than or equal to 1000nm accounts for 20～85% of total pore volume, and the hole that aperture is greater than 1000nm accounts for 0～3% of total pore volume.
Aluminium oxide-titanium oxide complex carrier in catalyst disclosed in this invention, in carrier quality 100%, aluminium oxide preferably 10～90%, particularly preferably 30～90%, most preferably 50～90%; Titanium oxide preferably 10～90%, more preferably 10～70%, most preferably 10～50%.
In order to obtain all good catalyst of activity and selectivity, Pd chosen by catalyst disclosed in this invention and Ag bimetallic is active component.If do not add silver, catalyst selectively poor, if but the addition of silver is too high, and the activity of catalyst is poor, so Ag, Pd should meet certain ratio in catalyst, its weight ratio is 9～1: 1.
Catalyst disclosed in this invention can contain 0.03～0.8 part of alkali metal and/or base earth metal promoter composition, preferably 0.03～0.5 part; Wherein alkali metal and/or alkaline-earth metal are preferably 0.03～0.5 part, preferably alkali metal potassium.By adding alkali metal, alkaline-earth metal, changed the acidity of catalyst surface, catalyst surface coking is reduced, catalyst performance index keeps good in the long period, especially selective obvious raising.
In addition, catalyst disclosed in this invention can also add rare earth element as auxiliary component, and preferably 0.02～0.6 part, lanthanum most preferably; 0.02～0.6 part of addition, preferably 0.03～0.5 part.By adding rare earth element further to reduce the surface acidity of catalyst, improve catalyst anti-coking performance.
Catalyst disclosed in this invention, because carrier has bimodal pore size distribution, occurs bimodal at 60～130nm and 400～800nm respectively.The hole of 60～130nm is than existing selective hydrogenation catalyst carrier, aperture is larger, the passage of reaction and diffusion can be provided for the selection hydrogenation of acetylene, propine, allene, and because its aperture is larger, be conducive to the rapid diffusion of hydrogenation products ethene, propylene, thereby can further improve the selective of catalyst.Existing bimodal pore distribution carrier is compared in the hole of 400～800nm, aperture is relatively little, and this can be avoided excessive aperture to cause the reduction of catalyst activity, can guarantee enough ducts simultaneously, make the unsaturated C such as accessory substance 1,3-butadiene that produce in hydrogenation process
4hydrocarbon, and green oil is diffused into rapidly catalyst surface, avoids their further polymerizations to cause the coking of catalyst, thereby improved the service life of catalyst.Meanwhile, the catalyst preparing due to carrier of the present invention has macroporous structure, and surface acidity is low, and when active component palladium being loaded on to catalyst that carrier surface makes and be used for alkynes and alkadienes to carry out hydrogenation, green oil generating amount is few, and hydrogenation selectivity is good.Meanwhile, due to the existence of titanium oxide in complex carrier, improve the poisoning ability of catalyst preventing from heavy metal, further extended the service life of catalyst.Because carrier aperture of the present invention distributes and forms, made its Catalysts for Reducing preparing to H
2with the sensitivity of CO, be particularly suitable for H in reaction mass
2content is 20%～50%mol, and the front-end hydrogenation of CO content 300～5000ppm is selected acetylene hydrogenation technique.The catalyst being made by carrier of the present invention is not only selectively good, and in industrial side line evaluating apparatus, it selectively can reach more than 50%, and has very high activity, at reaction velocity 8000～16000h
-1condition under can be less than 1ppm so that acetylene is removed to, and reach after 1000h at evaluation time, when catalytic reaction improves 5 ℃, catalyst activity does not still decline, and the excellent properties of above-mentioned catalyst is mainly because aluminium oxide-titanium oxide complex carrier is distributed in due to suitable pore diameter range; Other complex carriers can not have this excellent effect.
The contained carrier of catalyst of the present invention has larger aperture 80～400nm, and at 60～130nm and 400～800nm, occur bimodal respectively, because carrier has larger aperture and the feature of bimodal pore distribution of the present invention, when making catalyst there is greater activity, also there is the feature of selective height, anti-coking excellent performance.
The invention discloses the preparation method of catalyst: first preparation has the aluminium oxide-titanium oxide complex carrier of bimodal distribution, then carrier impregnation is entered containing in one or more the solution in palladium, silver and auxiliary agent, filtration, washing, dry, roasting, obtain catalyst of the present invention.
The invention also discloses the preparation method of this carrier, comprise the steps: under stirring condition MAl0
2and TiCl
4solution mixes, then with aqueous slkali, neutralize, generate the co-precipitation of aluminium titanium hydroxide, filter, then add the expanding agent of 3～15wt% of mixed hydroxides weight, kneading and compacting, dry, at 1000～1350 ℃ of roasting 2～8h, preferably 4～6h obtains carrier of the present invention, wherein M is Na or K, preferably Na.
Specifically, the preparation method of carrier disclosed in this invention is: MAl0
2and TiCl
4solution mixes under 25～100 ℃ of conditions, then with alkaline solution, is neutralized to neutrality, generates the precipitation of hydroxide of aluminium titanium, stirs and within 5～20 hours, makes aluminium titanium hydroxide generate uniform crystalline phase particle, filters, and washes away M
+and Cl
-ion, then adds the expanding agent of 3～15wt% of mixed hydroxides butt weight, kneading and compacting, and 100～150 ℃ are dry, and 1000～1400 ℃ of roasting 2～8h are 4～6h preferably.
Moulding of the present invention can adopt customary way to carry out, as the methods such as compressing tablet, spin, extrusion all can, be preferably extrusion, spin method.
The kind of expanding agent of the present invention and consumption can be all this area routines, for example, can be selected from one or more in sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and carbon black.
Alkaline solution of the present invention is selected from NaOH, KOH, Na
2cO
3and NH
3and so on alkali carry out, preferred NaOH, KOH.
The invention discloses the another kind of preparation method of this carrier: aluminium oxide, titanium oxide, expanding agent blending, the expanding agent that adds 3～15wt% of aluminium oxide and titanium oxide mixed oxide butt weight, the even aftershaping of kneading, dry, at 1000～1400 ℃, roasting 2～8 hours preferably 4～6 hours.
Blending method of the present invention is prepared in the process of carrier, and drying condition is recommended 100～150 ℃.
In method for preparing catalyst disclosed in this invention, carrier impregnation is entered containing one or more the solution in palladium, silver and auxiliary agent, refer to that palladium, silver and auxiliary component can synchronously flood or step impregnation carrier, this is the general methods of those skilled in the art, for example, in CN200810223451.6, disclose this technology.Preparation method disclosed by the invention, do not limit the synchronous or dipping that distributes, recommending the pH value of maceration extract is 1.0～5.0, and the carrier after dipping is dried 2～20 hours at 80～250 ℃ after washing after filtration, 350～650 roasting 2～10 hours, obtain catalyst of the present invention.
Step impregnation in the preparation method of catalyst disclosed by the invention, refers to step impregnation after the soluble-salt difference wiring solution-forming of palladium, silver, auxiliary agent to carrier.When step impregnation, also can be by after two or more the synchronous dipping in component, then flood remaining component, for example: can be by the synchronous step impregnation auxiliary agent again after dipping of active component Pd, Ag; Can be by synchronous dipping auxiliary agent after active component Pd, Ag step impregnation; Also can by after one or more the synchronous dippings in active component Pd and auxiliary agent at substep or synchronously flood Ag and other carriers.Mode when the present invention does not enumerate the various elements of step impregnation and floods.
Synchronous dipping in the preparation method of catalyst disclosed by the invention can be made the soluble-salt of palladium, silver, auxiliary agent after mixed solution single-steeping or dipping several times, while repeatedly flooding, adopt after dipping, dry, roasting flood again, be dried, cyclic process that roasting is such, generally all adopt in every respect the most frequently used dipping method, the present invention is not limited especially.
When adopting step impregnation method, preferably recommend adoption the following step operation:
The first step is with containing palladium solution impregnating carrier, and it is favourable with the solution of the absorbent maximum of carrier institute, flood, and the amount containing palladium in solution should make the catalyst of finally calcining contain 0.02～0.15 part of palladium.Adopting containing palladium solution can be the salting liquid of palladium bichloride, palladium nitrate, palladium.With after palladium salt solution impregnation, at 80～250 ℃, be dried 2～20 hours;
Second step is during by silver-colored solution impregnation, Ag-containing solution can be silver nitrate, silver perchlorate, preferably select silver nitrate to prepare, can be specifically: the aluminium oxide-titanium oxide composite oxide carrier with bimodal pore distribution structure of the complete palladium of load is immersed in the acid solution of silver salt, at 10～100 ℃ of temperature, flood 10～120min, at 80～250 ℃ after dry 2～20 hours, 350～650 roasting 2～10 hours.
As also added alkali metal, alkaline-earth metal or rare earth metal auxiliary component in catalyst, in the aqueous solution of the above-mentioned soluble-salt that immerses again alkali metal, alkaline-earth metal or rare earth metal auxiliary component containing palladium and silver-colored carrier roasting after cooling, flood 10～120min, at 80～250 ℃, after dry 2～20 hours, in 350～650 roasting, within 2～10 hours, obtain catalyst.
Rare earth metal adds with the form of nitric acid rare earth, rare earth chloride, sulfuric acid rare earth; Alkali metal and/or alkaline-earth metal add with the form of nitrate, chlorate, sulfate.
Accompanying drawing explanation
The aluminium oxide-titanium oxide complex carrier bimodal pore size distribution figure of Fig. 1: embodiment 1, occurs bimodal at 90nm and 410nm.
The aluminium oxide-titanium oxide complex carrier bimodal pore size distribution figure of Fig. 2: embodiment 2, occurs bimodal at 110nm and 520nm.
The aluminium oxide-titanium oxide complex carrier bimodal pore size distribution figure of Fig. 3: embodiment 3, occurs bimodal at 125nm and 760nm.
The specific embodiment
Embodiment describes in further detail of the present invention, but the present invention is not subject to the restriction of these embodiment.
1, analytical method
(1) specific area of carrier, pore volume, pore-size distribution GB/T 21650.1 mercury injection methods and gas determination of adsorption method solid material pore-size distribution and porosity. part 1: mercury injection method.
(2) acetylene content: the mensuration gas chromatography of the industrial ethene trace acetylene of GB/T 3995-93.
(3) bulk density: take a certain amount of carrier and pack in graduated cylinder, vibrate 3～10 minutes, measure the volume of carrier, the weight of carrier, divided by the volume of carrier, is carrier bulk density.
2, primary raw material
Embodiment 1
Under agitation, contain 1286gNaAlO
2solution and the TiCl that contains 950g
4solution mixes 50 ℃ of conditions, and then, with the neutralization of NaOH solution, the co-precipitation of aluminium titanium hydroxide, stirs and within 10 hours, make aluminium titanium hydroxide generate uniform fine particle, filters and washes away Na with distilled water
+and Cl
-ion, adds 7.65% citric acid as expanding agent, and after mediating, the rectangular of Φ 4mm made in extrusion molding, after 120 ℃ of dry 4h, 1250 ℃ of roastings 5 hours, obtains aluminium oxide and titanium oxide complex carrier S-1, wherein α-Al
2o
3and TiO
2weight ratio is 8: 2, bulk density 0.87g/ml, and pore volume 0.502ml/g, specific area is 18.9m
2/ g (mercury injection method), carrier has bimodal distribution, average pore size 176nm at 90nm and 410nm place.Carrier aperture distributes as follows: being less than 10nm is 0.19%; 10～100nm is 71.11%; Being greater than 100nm but being less than or equal to 1000nm is 28.5%; Being greater than 1000nm is 0.2%.Carrier aperture distribution map refers to Fig. 1.
Embodiment 2
700g aluminium oxide, 150 titanium oxide, 20g citric acid and 30g carbon black stir in mechanical agitator, extrusion molding, make the rectangular of Φ 4.2mm, 110 ℃ are dried 5 hours, then 1250 ℃ of roastings 4 hours, obtain aluminium oxide and titanium oxide mixed carrier, pore volume 0.419ml/g, bulk density 0.92g/ml, specific area is 14.5m
2/ g; Carrier has bimodal distribution, average pore size 273nm at 110nm and 520nm place; Carrier aperture distributes as follows: being less than 10nm is 0.10%; 10～100nm is 63.06%; Being greater than 100nm, to be less than or equal to 1000nm be 36.66%; Being greater than 1000nm is 0.18%.Carrier aperture distribution map refers to Fig. 2.
Embodiment 3
Under agitation, contain 402gNaAlO
2solution and the TiCl that contains 1187g
4solution mixes 50 ℃ of conditions, and then, with the neutralization of KOH solution, the co-precipitation of aluminium titanium hydroxide, stirs and within 10 hours, make aluminium titanium hydroxide generate uniform fine particle, and product filters and washes away Na with deionized-distilled water
+and Cl
-ion, adds 15% polyvinyl alcohol as expanding agent, and spin after mediating, 1350 ℃ of roastings 6 hours, obtains aluminium oxide and titanium oxide complex carrier, wherein α-Al after 130 ℃ of dry 2h
2o
3and TiO
2weight ratio is 5: 5, bulk density 1.03g/ml, and pore volume 0.357ml/g, specific area is 7.5m
2/ g, carrier has bimodal distribution, average pore size 360nm at 125nm and 760nm place.Carrier aperture distributes as follows: being less than 10nm is 0%; 10～100nm is 58.50%; Being greater than 100nm, to be less than or equal to 1000nm be 41.36%; Being greater than 1000nm is 0.14%.Carrier aperture distribution map refers to Fig. 3.
Embodiment 4
200g aluminium oxide, 800 titanium oxide, 100g citric acid stir in mechanical agitator, extrusion molding, make the rectangular of Φ 3.8mm, 150 ℃ dry after in Muffle furnace dry 6 hours, then under the condition of 1400 ℃ of air, roasting 6 hours, obtain aluminium oxide and titanium oxide mixed carrier S-4, pore volume 0.42ml/g, bulk density 0.93g/ml, specific area is 8.8m
2/ g (mercury injection method), carrier has bimodal distribution, average pore size 330nm at 130nm and 520nm place; Carrier aperture distributes as follows: 1～10nm is 0%; 10～100nm is 22.32%; 100～1000nm is 77.52%; 1000～10000nm is 0.16%.
Embodiment 5
200g aluminium oxide, 800 titanium oxide, 100g citric acid stir in mechanical agitator, extrusion molding, make the rectangular of Φ 3.8mm, 150 ℃ dry after in Muffle furnace dry 6 hours, then under the condition of 1200 ℃ of air, roasting 6 hours, obtain aluminium oxide and titanium oxide mixed carrier S-5, pore volume 0.46ml/g, bulk density 0.88g/ml, specific area is 14.8m
2/ g (mercury injection method), carrier has bimodal distribution, average pore size 230nm at 112nm and 460nm place; Carrier aperture distributes as follows: 1～10nm is 0%; 10～100nm is 42.29%; 100～1000nm is 57.61%; 1000～10000nm is 0.10%.
Comparative example 1
Adopt common alumina support, 1250 ℃ of roastings 5 hours, obtain α-Al
2o
3carrier D-1, records its pore volume 0.43ml/g, bulk density 0.91g/ml, and specific area is 15.2m
2/ g (mercury injection method), most probable average pore size 110nm.
Comparative example 2
Adopt common alumina support, 1300 ℃ of roastings 4 hours, obtain α-Al
2o
3carrier D-2, records its pore volume 0.45ml/g, bulk density 0.98g/ml, and specific area is 12.4m
2/ g (mercury injection method), most probable average pore size 220nm.
Comparative example 3
Adopt the preparation method of carrier 1 in CN200810223451.1 embodiment:
Being prepared as follows of aluminium oxide: by 200kg water and 5kg aluminum sulfate aqueous solution (Al
2o
3content is 8%) add in stirred tank, make temperature reach 33 ℃, then with the speed of 1.4kg/min, add continuously identical aluminum sulfate solution 20min, simultaneously by adding sodium aluminate aqueous solution (Al
2o
3content is 23.5%) make pH value reach 8.5 and remain in 8.3～8.6 scope, the chuck recirculated cooling water by described still makes solution temperature remain on 33 ℃ simultaneously.Then stirring but do not making the temperature of gained slurries rise to 81 ℃ reagent adding in the situation that.Restart to add the about 40min of reagent, the chuck recirculated cooling water by described still makes temperature remain on 81 ℃ and pH value is remained in 8.2～9.2 scope simultaneously.Gained slurries are containing having an appointment 6.5%Al
2o
3.Approximately 29% of described total aluminium oxide forms in described the first settling step interval.Then described aluminium oxide slurries are filtered and washing, then spraying is dry.Described powder water is ground, produce the mixture containing 63% water, extrude, dry at 150 ℃, roasting at 593 ℃.Resulting alumina support D-3 pore volume is 0.95mlg
-1, the ratio that the hole of diameter > 35nm accounts for PV is 2.5%, and main peak value is 16.8nm, and minor peaks is 12nm, N
2surface area is 22.7m
2/ g.Adopting mercury injection method to record main peak value is 15.9nm, and minor peaks is 11.5nm, and specific area is 21.8m
2/ g.
Comparative example 4
Adopt carrier and its preparation method described in CN1361231:
Under agitation, NaAlO
2solution (116 grams are dissolved in 450 ml waters) and 200 milliliters of TiCl
4solution (250 grams of TiO
2/ liter) 40 ℃ of conditions, mix, then, with the neutralization of NaOH solution, the co-precipitation of aluminium titanium hydroxide, stirs and within 24 hours, makes aluminium titanium hydroxide generate uniform fine particle, and product filters and uses the washing of deionized water distilled water to remove Na
+and Cl
-ion, then 120 ℃ of the mixed hydroxides obtaining be dry, pulverize into 120～180 order fine powders, after kneading, with double screw banded extruder, hydroxide is made to the rectangular of ф 3mm, 120 ℃ dry after 900 ℃ of roastings 2 hours in Muffle furnace, obtain D-4 aluminium oxide and titanium oxide complex carrier (Al
2o
3/ TiO
2=1: 1), bulk density 0.8g/ml, pore volume 0.4ml/g, specific area 22.1m2/g (BET nitrogen method), 33.6 (mercury injection methods), carrier has bimodal distribution at 50nm and 1000nm place, most probable average pore size 240nm, average pore size 58nm, bulk density 0.80g/ml.
The preparation of catalyst
The carrier with bimodal pore distribution structure prepared by above method immerses in the acid solution of palladium salt, at 10～100 ℃ of temperature, flood 10～120min, at 80～250 ℃, be dried 2～10 hours, 350～650 ℃ of roastings 2～10 hours, immerse after cooling in the aqueous solution of soluble-salt of Ag and flood 10～120min, at 80～250 ℃, be dried 2～10 hours, 350～650 ℃ of roastings 2～10 hours.The load of the elements such as K, Ca, Mg, La, Ce adopts same step.Active component Pd with help the elements such as active component A g, Cu, K, Ca, Mg, La, Ce to soak separately, also can immerse simultaneously.Adopt embodiment 1～4 to adopt step impregnation, embodiment 5 adopts synchronous dipping.Concrete loading condition is in Table 1.
Table 1 catalyst preparation condition
Get each 500mL of above catalyst and pack industrial side line device into and evaluate its performance, raw material forms as table 2, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1.45～90 ℃ of inlet temperatures.Evaluating catalyst the results are shown in Table 3.
Table 2 raw material forms
Table 3 catalyst 1000h evaluation result
Claims (22)
1. carbon two front-end hydrogenation catalyst containing complex carrier, in 100 parts of catalyst qualities, comprise (1) 0.02～0.15 part of palladium, (2) silver, the mass ratio 9～1:1 of silver and palladium, palladium, silver are all in element quality, the carrier that it is characterized in that catalyst is the aluminium oxide-titanium oxide complex carrier with bimodal distribution, in carrier quality 100%, comprises aluminium oxide 1～95%, titanium oxide 5～99%, carrier has following physical property: bulk density 0.7～1.1
x/ ml, pore volume 0.2～0.6ml/g, specific area 3～60m
2/ g, average pore size 80～400nm, carrier occurs bimodal at 60～130nm and 400～800nm place.
2. catalyst according to claim 1, is characterized in that 0.02～0.10 part of palladium.
3. according to the catalyst described in claim 1 or 2 any one claims, it is characterized in that the mass ratio 6～1:1 of silver and palladium.
4. catalyst according to claim 1, the aluminium oxide-titanium oxide complex carrier mesoporous that it is characterized in that having bimodal distribution accounts for 0～4% of total pore volume lower than the hole of 10nm, the hole of 10～100nm accounts for 15～80% of total pore volume, the hole that is greater than 100nm but is less than or equal to 1000nm accounts for 20～85% of total pore volume, and the hole that aperture is greater than 1000nm accounts for 0～3% of total pore volume.
5. catalyst according to claim 1, is characterized in that aluminium oxide 10～90%, titanium oxide 10～90%.
6. catalyst according to claim 5, is characterized in that aluminium oxide 30～90%, titanium oxide 10～70%.
7. catalyst according to claim 6, is characterized in that aluminium oxide 50～90%, titanium oxide 10～50%.
8. according to the catalyst described in claim 1 or 2 any one claims, it is characterized in that catalyst contains 0.03～0.8 part of alkali metal and/or base earth metal promoter.
9. catalyst according to claim 8, is characterized in that catalyst contains 0.03～0.5 part of alkali metal and/or base earth metal promoter.
10. according to the catalyst described in claim 1 or 2 any one claims, it is characterized in that catalyst contains 0.02～0.6 part, auxiliary agent rare earth element.
11. catalyst according to claim 10, is characterized in that the rare earth element in catalyst is lanthanum; 0.03～0.5 part of addition.
12. according to the catalyst of one of claim 1～2, it is characterized in that carrier average pore size 120～370nm.
The preparation method of 13. 1 kinds of catalyst claimed in claim 1, first preparation has the aluminium oxide-titanium oxide complex carrier of bimodal distribution: under stirring condition by MAlO
2and TiCl
4solution mixes, and then with aqueous slkali neutralization, generates the co-precipitation of aluminium titanium hydroxide, filters, and then adds the expanding agent of 3～15wt% of mixed hydroxides weight, kneading and compacting, and dry, 1000～1400 ℃ of roastings, wherein M is Na or K; Then carrier impregnation is entered in the solution containing palladium, silver, filtration, washing, dry, roasting, obtain catalyst.
14. preparation methods according to claim 13, is characterized in that MAlO
2and TiCl
4solution mixes under 25～100 ℃ of conditions, then, with alkaline solution neutralization, generates the precipitation of hydroxide of aluminium titanium, stirs and within 5～20 hours, makes aluminium titanium hydroxide generate uniform crystalline phase particle, filters, and washes away M
+with Cl-ion, then add the expanding agent of 3～15wt% of mixed hydroxides weight, kneading and compacting, 100～150 ℃ are dry, at 1000～1350 ℃ of roasting 2～8h; Then carrier impregnation is entered in the solution containing palladium, silver, filtration, washing, dry, roasting, obtain catalyst.
15. according to the preparation method described in claim 13～14 any one claim, it is characterized in that roasting 4～6h.
16. according to the preparation method described in claim 13～14 any one claim, it is characterized in that expanding agent is selected from one or more in sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and carbon black; Alkaline solution is selected from NaOH, KOH, Na
2cO
3and NH
3in one or more.
17. preparation methods according to claim 13, the preparation method who it is characterized in that having the aluminium oxide-titanium oxide complex carrier of bimodal distribution is: by aluminium oxide, titanium oxide, expanding agent blending, expanding agent addition is 3～15% of aluminium oxide and titanium oxide mixed oxide weight, the even aftershaping of kneading, dry, at 1000～1400 ℃, roasting 2～8 hours.
18. preparation methods according to claim 17, is characterized in that being dried at 100～150 ℃ roasting 4～6 hours.
19. preparation methods according to claim 17, is characterized in that expanding agent is selected from one or more in sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and carbon black.
20. preparation methods according to claim 13, while it is characterized in that catalyst contains auxiliary agent, carrier impregnation enters containing in palladium, silver, compounding agent solution, and filtration, washing, dry, roasting, obtain catalyst.
21. preparation methods according to claim 20, synchronous or step impregnation while it is characterized in that carrier impregnation enters containing palladium, silver and auxiliary agent, the pH value of maceration extract is 1.0～5.0, carrier after dipping is dried 2～20 hours at 80～250 ℃ after filtering, washing, 350～650 roasting 2～10 hours, obtain catalyst.
22. preparation methods according to claim 21, step impregnation while it is characterized in that carrier impregnation enters containing palladium, silver and compounding agent solution: (1) is with containing palladium solution impregnating carrier, dry, roasting are the solution of palladium bichloride, palladium nitrate, palladium containing palladium solution; (2) use silver-colored solution impregnation, dry, roasting, Ag-containing solution is selected from silver nitrate and/or silver perchlorate; (3) immerse the aqueous solution of the soluble-salt of auxiliary agent, dry, roasting obtains catalyst again.
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| CA2922259A1 (en) * | 2013-09-06 | 2015-03-12 | Chevron Phillips Chemical Company Lp | Selective hydrogenation catalyst containing bimodal support and methods of making and using same |
| CN108927156A (en) * | 2018-07-18 | 2018-12-04 | 北京化工大学 | A kind of alkynes selective hydrogenation support type alloy catalyst and preparation method thereof |
| CN109772291B (en) * | 2019-03-13 | 2020-07-10 | 西南化工研究设计院有限公司 | Selective hydrogenation and dealkynization catalyst and preparation method and application thereof |
| CN113694941A (en) * | 2020-05-20 | 2021-11-26 | 中国石油化工股份有限公司 | Supported metal catalyst and preparation method and application thereof |
| CN113713835B (en) * | 2020-05-25 | 2024-02-20 | 中国石油化工股份有限公司 | Hydrogenation catalyst based on composite oxide carrier and preparation method and application thereof |
| CN113926463B (en) * | 2020-06-29 | 2024-03-29 | 中国石油化工股份有限公司 | Acrolein catalyst and preparation method and application thereof |
| CN113477249A (en) * | 2021-06-21 | 2021-10-08 | 润和科华催化剂(上海)有限公司 | Catalyst for preparing ethylene by selective hydrogenation of acetylene, preparation method and application |
| CN114405493A (en) * | 2021-12-20 | 2022-04-29 | 西安凯立新材料股份有限公司 | Preparation method of high-strength large-aperture alumina-titanium oxide composite carrier |
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