CN102989453A - C2 front-end hydrogenation catalyst and preparation method - Google Patents
C2 front-end hydrogenation catalyst and preparation method Download PDFInfo
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- CN102989453A CN102989453A CN2011102670771A CN201110267077A CN102989453A CN 102989453 A CN102989453 A CN 102989453A CN 2011102670771 A CN2011102670771 A CN 2011102670771A CN 201110267077 A CN201110267077 A CN 201110267077A CN 102989453 A CN102989453 A CN 102989453A
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Abstract
The invention relates to a C2 front-end hydrogenation catalyst and a preparation method, 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 taking the mass of the carrier as 100%, the carrier comprises 1-95% of alumina, 5-60% of zirconia and 5-60% 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 50 to 300nm; and the carrier has two peaks when the pore size is 40 to 120nm and 200 to 400nm. The invention also discloses the preparation method of the hydrogenation catalyst.
Description
Technical field
The present invention relates to Catalysts and its preparation method, relate to specifically a kind of carbon two front-end hydrogenation Catalysts and its preparation methods.
Background technology
Often contain the impurity such as a small amount of acetylene, propine and allene in the cracking gas that produces in the cracking petroleum hydrocarbon vapor process, their existence can affect homogeneous polymerization and the employed high-efficiency polyethylene of polymerization process and polypropylene catalyst in the follow-up workshop section to some extent.By the requirement of the rear manufacturing procedures such as polyethylene, EP rubbers, polypropylene, the molar fraction of acetylene must be lower than 5ppm in the polymer grade ethylene, requires also in the ethylene glycol production that the molar fraction of acetylene is lower than 1ppm in the ethene.The catalysis selective hydrogenation method be industrial most widely used general, also be the most effective a kind of method that removes acetylene, propine and allene (MAPD), the catalyst that adopts mostly is alumina load precious metals pd catalyst.
Selecting hydrogenation except in the acetylene reaction, also have more side reaction in traditional catalyst use procedure: ethylene hydrogenation generates ethane; The easy hydrogenation dimerization of acetylene that is adsorbed on the 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 the selective acetylene hydrocarbon hydrogenation catalyst, shortens life cycle, causes the 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 afterwards for front-end hydrogenation, acetylene hydrogenation reactor are positioned at domethanizing column before being positioned at domethanizing column, wherein, the 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 the front-end hydrogenation technique contains a large amount of hydrogen and more CO.Owing to contain hydrogen (approximately 20-50mol%) and the CO (300～5000ppm (mol)) of high concentration in the hydrogenation reaction material, and hydrogen and CO fluctuation range are 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 just be to improve the selective and active of selective hydrogenation catalyst, reduce catalyst to the sensitivity of hydrogen and CO concentration, select the selective and active key of acetylene hydrogenation catalyst to be to improve the pore structure of carrier and improve front-end hydrogenation.For the problems referred to above, usually obtain the eurypyloue α-Al of tool by the method that improves the carrier sintering temperature
2O
3Carrier, but be limited with this surface-sensitive degree that reduces catalyst carrier.
Prior art also attempts to improve by the preparation complex carrier performance of catalyst, but, for the complex carrier of carbon two front-end hydrogenation catalyst only CN00136874.5 improve the performance of catalyst by the complex carrier of preparation aluminium oxide-titanium oxide, this carrier aperture is distributed in 50nm and 1000nm occurs bimodal.This carrier can effectively improve the anti-coking performance of carbon two front-end hydrogenation catalyst for the preparation of 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 exists ratio table and pore-size distribution to be not suitable with the defective of catalyst requirement for the preparation of carbon two front-end hydrogenation catalyst, causes catalyst activity component Pd decentralization lower, perhaps the higher shortcoming of catalyst surface acidity.
CN97114892.9 disclose a kind of in the presence of catalyst 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 are 0.2～0.8ml/g.More than two kinds of carriers for the preparation of carbon two front-end hydrogenation catalyst because specific area is too small, be unfavorable for the dispersion of active component Pd, prepared catalyst activity and selectivity is all relatively poor.
CN00124057.9 discloses a kind of catalyst that two-peak hole radius distributes that has, contain a) zirconium dioxide-titanium oxide of 10～99.9% weight, and b) aluminium oxide of 0～60% weight, silica and/or zirconium dioxide-titanium oxide, and c) at least a element of I A family or II 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, and 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
Greater than
20～80%, the BET that accounts for be 100～550m
2/ g.More than 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
3Present ZrO has been introduced in the preparation of catalyst carrier and application (" Industrial Catalysis " the 3rd phase of the 16th volume in 2008)
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 for preparing by this article method is larger, and acidity is stronger, and minimum specific area is 190m
2/ g.
The carrier of bimodal pore size distribution exists ratio table and pore-size distribution to be not suitable with the defective of catalyst requirement for the preparation of carbon two front-end hydrogenation catalyst in the prior art, causes catalyst activity component Pd decentralization lower, perhaps the higher shortcoming of catalyst surface acidity.
Summary of the invention
The object of the present invention is to provide a kind of carbon two front-end hydrogenation catalyst that contain the suitable carrier of pore-size distribution, this catalyst have the hydrogenation activity height, selectively good, green oil generating amount is low, can use in the higher situation of hydrogen and CO content, and has stronger anti-hydrogen and CO fluctuation ability.Another object of the present invention has provided the preparation method of hydrogenation catalyst.
Carbon two front-end hydrogenation catalyst disclosed in this invention in 100 parts of catalyst qualities, comprise 0.02～0.15 part of palladium, preferred 0.02～0.10 part; Silver, the mass ratio 9～1: 1, preferred 6～1: 1 of silver and palladium; Palladium, silver are all in the element quality; Carrier wherein in carrier quality 100%, comprises aluminium oxide 1～95%, zirconia 5～60%, and titanium oxide 5～60%, 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 50～300nm, preferred 80～200nm; Carrier occurs bimodal at 40～120nm and 200～400nm place.
The hole that the aluminium oxide-titanium oxide with bimodal distribution in the catalyst of the present invention-zirconia composite carrier mesoporous is lower than 10nm accounts for 0～4% of total pore volume, the hole of 10～100nm accounts for 45～80% of total pore volume, the aperture accounts for 15～50% of total pore volume greater than 100nm less than or equal to the hole of 1000nm, and the aperture accounts for 0～3% of total pore volume greater than the hole of 1000nm.
The aluminium oxide-titanium oxide-zirconia composite carrier with bimodal distribution in the disclosed catalyst of the present invention, in carrier quality 100%, aluminium oxide is preferred 10～90%, and particularly preferably 30～90%, most preferably 30～80%; Zirconia is preferred 5～50%, and most preferably 10～50%; Titanium oxide is preferred 5～50%, and most preferably 10～50%.
In order to obtain all catalyst preferably of activity and selectivity, Pd chosen by catalyst disclosed in this invention and the Ag bimetallic is active component.If do not add silver, catalyst selectively relatively poor, if but the addition of silver is too high, catalyst active relatively poor, so Ag, Pd should satisfy certain ratio in the 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, preferred 0.03～0.5 part; Wherein alkali metal and/or alkaline-earth metal are preferred 0.03～0.5 part, preferably alkali metal potassium.By adding alkali metal, alkaline-earth metal, changed the acidity of catalyst surface, so that the catalyst surface coking reduces, the catalyst performance index keeps good in the long period, especially selectively obviously improves.
In addition, catalyst disclosed in this invention can also add rare earth element as auxiliary component, and preferred 0.02～0.6 part, lanthanum most preferably; 0.02～0.6 part of addition, preferred 0.03～0.5 part.Further reduce the surface acidity of catalyst by adding rare earth element, improve catalyst anti-coking performance.
Aluminium oxide-titanium oxide-Zirconia carrier disclosed in this invention owing to have bimodal pore size distribution, occurs bimodal at 40～120nm and 200～400nm respectively.The hole of 40～120nm can provide for the selection hydrogenation of acetylene, propine, allene the passage of reaction and diffusion, and because its aperture is larger, is 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 200～400nm, the aperture less, 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 the 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.Simultaneously, because the catalyst that carrier of the present invention prepares has macroporous structure, surface acidity is low, when active component, Metal Palladium for example is when loading on catalyst that carrier surface makes and being used for that alkynes and alkadienes carried out hydrogenation, green oil generating amount is few, and hydrogenation selectivity is good.Simultaneously, because the existence of zirconia, titanium oxide in the complex carrier has improved the ability that the catalyst preventing from heavy metal is poisoned, further prolonged the service life of catalyst.Because carrier aperture of the present invention distributes and forms, and has made its Catalysts for Reducing for preparing to H
2With the sensitivity of CO, be particularly suitable for H in the reaction mass
2Content is 20%～50%mol, and the front-end hydrogenation of CO content 300～5000ppm is selected acetylene hydrogenation technique.The catalyst that is 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 so that acetylene be removed to less than 1ppm, and after evaluation time reaches 1000h, when catalytic reaction improves 5 ℃, catalyst activity does not still descend, and the excellent properties of above-mentioned catalyst mainly is because aluminium oxide-zirconium oxide-titanium oxide complex carrier is distributed in due to the 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 50～300nm, and occur bimodal at 40～120nm and 200～400nm respectively, because carrier has larger aperture and the characteristics of bimodal pore distribution of the present invention, so that catalyst when having greater activity, also has the characteristics of selective height, anti-coking excellent performance.
The invention also discloses the preparation method of this carrier, comprise the steps: under stirring condition MAlO
2And TiCl
4, ZrCl
4Solution mixes, then neutralize with aqueous slkali, generate the co-precipitation of aluminium zirconium titanium hydroxide, filter, then add the expanding agent of 3～15wt% of mixed hydroxides weight, kneading and compacting, drying, at 1000～1350 ℃ of roasting 2～8h, preferred 4～6h obtains carrier of the present invention, wherein M is Na or K, preferred Na.
Specifically, the preparation method of carrier disclosed in this invention is: MAlO
2And ZrCl
4, TiCl
4Solution mixes under 25～100 ℃ of conditions, then is neutralized to neutrality with alkaline solution, generates the precipitation of hydroxide of aluminium zirconium titanium, stirs 5～20 hours so that aluminium zirconium titanium hydroxide generates uniform crystalline phase particle, filters flush away M
+And Cl
-Then ion adds the expanding agent of 3～15wt% of mixed hydroxides butt weight, kneading and compacting, 100～150 ℃ of dryings, 1000～1400 ℃ of preferred 4～6h of roasting 2～8h.
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 all can be this area routines, for example can be selected from one or more in sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and the 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, zirconia, titanium oxide, expanding agent blending, the expanding agent that adds 3～15wt% of aluminium oxide, zirconia, titanium oxide mixed oxide butt weight, the even aftershaping of kneading, dry, at 1000～1400 ℃, roasting 2～8 hours is preferred 4～6 hours.
Blending method of the present invention prepares in the process of carrier, and drying condition is recommended 100～150 ℃.
In the method for preparing catalyst disclosed in this invention carrier impregnation entered to contain one or more the solution in palladium, silver and the auxiliary agent, refer to that palladium, silver and auxiliary component can flood or the step impregnation carrier synchronously, this is the general methods of those skilled in the art, for example discloses this technology in CN200810223451.6.Preparation method disclosed by the invention, do not limit synchronously or the dipping that distributes, recommending the pH value of maceration extract is 1.0～5.0, and the carrier behind the dipping is washed rear 80～250 ℃ of dryings 2～20 hours after filtration, 350～650 roastings 2～10 hours, obtain catalyst of the present invention.
Step impregnation among the preparation method of catalyst disclosed by the invention refers to step impregnation behind the soluble-salt difference wiring solution-forming of palladium, silver, auxiliary agent to carrier.When step impregnation, also in the component two or more synchronously behind the dipping, can be flooded remaining component again, for example: can be with the synchronous step impregnation auxiliary agent again behind the dipping of active component Pd, Ag; Can auxiliary agent will be flooded synchronously behind active component Pd, the Ag step impregnation; Also can with in active component Pd and the auxiliary agent one or more synchronously behind the dipping at substep or flood synchronously Ag and other carriers.The present invention does not enumerate the various elements of step impregnation and the mode in when dipping one by one.
Synchronous dipping among the preparation method of catalyst disclosed by the invention can be made the soluble-salt of palladium, silver, auxiliary agent behind the mixed solution single-steeping or dipping several times, again dipping, dry, the such cyclic process of roasting after employing dipping, drying, the roasting when repeatedly flooding, generally all adopt in every respect the most frequently used dipping method, the present invention is not limited especially.
When adopting the step impregnation method, preferred recommend adoption the following step operation:
The first step is with containing the palladium solution impregnating carrier, with carrier the solution of absorbent maximum to flood be favourable, the amount that contains palladium in the solution should be so that the catalyst of last calcining contains 0.02～0.15 part of palladium.Employing contains the salting liquid that palladium solution can be palladium bichloride, palladium nitrate, palladium.With after the palladium salt solution impregnation, 80～250 ℃ of dryings 2～20 hours;
Second step is during with silver-colored solution impregnation, Ag-containing solution can be silver nitrate, silver perchlorate, preferably select silver nitrate to prepare, specifically can be: 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, under 10～100 ℃ of temperature, flood 10～120min, 80～250 ℃ of dryings after 2～20 hours, 350～650 roastings 2～10 hours.
As also adding alkali metal, alkaline-earth metal or rare earth metal auxiliary component in the catalyst, then flood 10～120min in above-mentioned containing in the aqueous solution that immerses again alkali metal, alkaline-earth metal or rare earth metal promoter soluble salt after palladium cools off with silver-colored carrier roasting, after 2～20 hours, 2～10 hour obtain catalyst in 350～650 roastings 80～250 ℃ of dryings.
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.
Description of drawings
The aluminium oxide-titanium oxide of Fig. 1: embodiment 1-zirconia composite carrier bimodal pore size distribution figure occurs bimodal at 60nm and 220nm.
The aluminium oxide-titanium oxide of Fig. 2: embodiment 2-zirconia composite carrier bimodal pore size distribution figure occurs bimodal at 95nm and 310nm.
The aluminium oxide-titanium oxide of Fig. 3: embodiment 3-zirconia composite carrier bimodal pore size distribution figure occurs bimodal at 105nm and 355nm.
The specific embodiment
Embodiment describes in further detail of the present invention, but the present invention is not subjected 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 by weighing a certain amount of carrier and pack in the graduated cylinder, vibrate 3～10 minutes, measure the volume of carrier, the weight of carrier is the carrier bulk density divided by the volume of carrier.
2, primary raw material
Embodiment 1
Under agitation, contain 1286gNaAlO
2Solution and contain the ZrCl of 378g
4, 475g TiCl
4Solution mixes 50 ℃ of conditions, and then with the neutralization of NaOH solution, the co-precipitation of aluminium zirconium titanium hydroxide was stirred 10 hours so that aluminium zirconium titanium hydroxide generates uniform fine particle, filtration and with distilled water flush away Na
+And Cl
-Ion adds 7.65% citric acid as expanding agent, and the rectangular of Φ 4mm made in extrusion molding after mediating, and 1200 ℃ of roastings 5 hours, obtains aluminium oxide-zirconium oxide-titanium oxide complex carrier, wherein α-Al behind 120 ℃ of dry 4h
2O
3And TiO
2, ZrO
2Weight ratio is 8: 1: 1, bulk density 0.88g/ml, and pore volume 0.497ml/g, specific area is 17.1m
2/ g, carrier has bimodal distribution, average pore size 90nm at 60nm and 220nm place.Carrier aperture distributes as follows: being lower than 10nm is 0%; 10～100nm is 74.30%; Be 25.3% greater than 100nm less than or equal to 1000nm; Be 0.2% greater than 1000nm.The carrier aperture distribution map sees Fig. 1 for details.
Embodiment 2
700g aluminium oxide, 150g zirconia, 150g titanium oxide, 20g citric acid and 30g carbon black stir in mechanical agitator, extrusion molding, make the rectangular of Φ 4.2mm, 110 ℃ of dryings 5 hours, then 1250 ℃ of roastings 4 hours, obtain aluminium oxide-zirconium oxide-titanium oxide mixed carrier, pore volume 0.421ml/g, bulk density 0.92g/ml, specific area is 12.4m
2/ g (mercury injection method); Carrier has bimodal distribution, average pore size 150nm at 95nm and 310nm place; Carrier aperture distributes as follows: being lower than 10nm is 1%; 10～100nm is 71.16%; Be 27.66% greater than 100nm less than or equal to 1000nm; Be 0.18% greater than 1000nm.The carrier aperture distribution map sees Fig. 2 for details.
Embodiment 3
Under agitation, contain 402gNaAlO
2Solution and contain the ZrCl of 473g
4, 594g TiCl
4Solution mixes 50 ℃ of conditions, and then with the neutralization of KOH solution, the co-precipitation of aluminium zirconium titanium hydroxide was stirred 10 hours so that aluminium zirconium titanium hydroxide generates uniform fine particle, product filtration and with deionized-distilled water flush away Na
+And Cl
-Ion adds 15% polyvinyl alcohol as expanding agent, and spin after mediating 1350 ℃ of roastings 6 hours, obtains aluminium oxide-zirconium oxide-titanium oxide complex carrier, wherein α-Al behind 130 ℃ of dry 2h
2O
3And TiO
2, ZrO
2Weight ratio is 2: 1: 1, bulk density 1.04g/ml, and pore volume 0.337ml/g, specific area is 6.8m
2/ g, carrier has bimodal distribution, average pore size 190nm at 105nm and 355nm place.Carrier aperture distributes as follows: being lower than 10nm is 0%; 10～100nm is 68.04%; Be 31.82% greater than 100nm less than or equal to 1000nm; Be 0.14% greater than 1000nm.The carrier aperture distribution map sees Fig. 3 for details.
Embodiment 4
200g aluminium oxide, 400g zirconia, 400g titanium oxide, 100g citric acid stir in mechanical agitator, extrusion molding, make the rectangular of Φ 3.8mm, after 150 ℃ of dryings in Muffle furnace dry 6 hours, then under the condition of 1400 ℃ of air, roasting 6 hours, obtain aluminium oxide-zirconium oxide-titanium oxide mixed carrier, pore volume 0.309ml/g, bulk density 1.05g/ml, specific area is 4.2m
2/ g, carrier has bimodal distribution, average pore size 210nm at 118nm and 385nm place; Carrier aperture distributes as follows: being lower than 10nm is 0%; 10～100nm is 62.32%; Be 37.52% greater than 100nm less than or equal to 1000nm; Be 0.16% greater than 1000nm.
Embodiment 5
200g aluminium oxide, 400 zirconias, 400 titanium oxide 100g citric acids stir in mechanical agitator, the rectangular of Φ 3.8mm made in extrusion molding, after 150 ℃ of dryings in Muffle furnace dry 6 hours, then under the condition of 1200 ℃ of air, roasting 6 hours obtains aluminium oxide and titanium oxide mixed carrier S-5, pore volume 0.46ml/g, bulk density 0.89g/ml, specific area is 15.4m2/g (mercury injection method), and carrier has bimodal distribution, average pore size 95nm at 70nm and 210nm place; Carrier aperture distributes as follows: 1～10nm is 0%; 10～100nm is 82.29%; 100～1000nm is 17.61%; 1000～10000nm is 0.10%.
Comparative Examples 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 Examples 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 Examples 3
Adopt the preparation method of carrier 1 among the CN200810223451.1 embodiment:
Being prepared as follows of aluminium oxide: with 200kg water and 5kg aluminum sulfate aqueous solution (Al
2O
3Content is 8%) add in the stirred tank, make temperature reach 33 ℃, then add continuously identical aluminum sulfate solution 20min with the speed of 1.4kg/min, simultaneously by adding sodium aluminate aqueous solution (Al
2O
3Content is 23.5%) make the pH value reach 8.5 and remain in 8.3～8.6 the scope, the chuck recirculated cooling water by described still makes solution temperature remain on 33 ℃ simultaneously.Then stirring but do not make the temperature of gained slurries rise to 81 ℃ in the situation of reagent adding.Restart to add the about 40min of reagent, the chuck recirculated cooling water by described still makes temperature remain on 81 ℃ and the pH value is remained in 8.2～9.2 the scope simultaneously.The gained slurries contain 6.5% Al that has an appointment
2O
3About 29% of described total aluminium oxide forms in that described the first settling step is interval.Then with described aluminium oxide dope filtration and washing, then spray-drying.Described powder water is ground, produce the mixture that contains 63% water, extrude, 150 ℃ of lower dryings, 593 ℃ of lower roastings.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 the 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 the main peak value is 15.9nm, and minor peaks is 11.5nm, and specific area is 21.8m
2/ g.
Comparative Examples 4
Adopt carrier and its preparation method described in the CN1361231:
Under agitation, NaAlO
2Solution (116 grams are dissolved in 450 ml waters) and 200 milliliters of TiCl
4Solution (250 gram TiO
2/ liter) mix 40 ℃ of conditions, then with the neutralization of NaOH solution, the co-precipitation of aluminium zirconium titanium hydroxide was stirred 24 hours so that aluminium zirconium titanium hydroxide generates uniform fine particle, and product filters and removes Na with the washing of deionized water distilled water
+And Cl
-Ion, then with the 120 ℃ of dryings of mixed hydroxides that obtain, be ground into 120～180 order fine powders, with double screw banded extruder hydroxide made the rectangular of ф 3mm after mediating, 900 ℃ of roastings 2 hours in Muffle furnace obtain D-4 aluminium oxide and titanium oxide complex carrier (Al after 120 ℃ of dryings
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 of above method preparation is immersed in the acid solution of palladium salt, under 10～100 ℃ of temperature, flood 10～120min, 80～250 ℃ of dryings 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, 80～250 ℃ of dryings 2～10 hours, 350～650 ℃ of roastings 2～10 hours.Same step is adopted in the load of the elements such as K, Ca, Mg, La, Ce.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 synchronously dipping.Concrete loading condition sees Table 1.
Table 1 catalyst preparation condition
Get each 500mL of above catalyst industrial side line device of packing into and estimate its performance, raw material forms such as table 2, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-145～90 ℃ of inlet temperatures.Evaluating catalyst the results are shown in Table 3.
Table 2 raw material forms
Table 3 catalyst 1000h evaluation result
Claims (23)
1. carbon two front-end hydrogenation catalyst, 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 the element quality, the carrier that it is characterized in that catalyst is the aluminium oxide-titanium oxide-zirconia composite carrier with bimodal distribution, in carrier quality 100%, comprise aluminium oxide 1～95%, zirconia 5～60%, titanium oxide 5～60%, 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 50～300nm, carrier occurs bimodal at 40～120nm and 200～400nm place.
2. catalyst according to claim 1 is characterized in that 0.02～0.10 part of palladium.
3. the described catalyst of any one claim according to claim 1 and 2 is characterized in that the mass ratio 6～1: 1 of silver and palladium.
4. catalyst according to claim 1, it is characterized in that having the hole that the aluminium oxide-titanium oxide of bimodal distribution-zirconia composite carrier mesoporous is lower than 10nm and account for 0～4% of total pore volume, the hole of 10～100nm accounts for 45～80% of total pore volume, account for 15～50% of total pore volume greater than 100nm less than or equal to the hole of 1000nm, the aperture accounts for 0～3% of total pore volume greater than the hole of 1000nm.
5. catalyst according to claim 1 is characterized in that having aluminium oxide 10～90% in the aluminium oxide-titanium oxide-zirconia composite carrier of bimodal distribution, zirconia 5～60%, titanium oxide 5～60%.
6. catalyst according to claim 5 is characterized in that having aluminium oxide 30～90% in the aluminium oxide-titanium oxide-zirconia composite carrier of bimodal distribution, zirconia 5～50%, titanium oxide 5～50%.
7. catalyst according to claim 6 is characterized in that having aluminium oxide 30～80% in the aluminium oxide-titanium oxide-zirconia composite carrier of bimodal distribution, zirconia 10～50%, titanium oxide 10～50%.
8. catalyst one of according to claim 1～2 is characterized in that having the aluminium oxide-titanium oxide of bimodal distribution-zirconia composite carrier average pore size 50～250nm.
9. catalyst according to claim 8 is characterized in that having the aluminium oxide-titanium oxide of bimodal distribution-zirconia composite carrier average pore size 80～200nm.
10. described catalyst one of according to claim 1～2 is characterized in that catalyst contains 0.03～0.8 part of alkali metal and/or base earth metal promoter.
11. catalyst according to claim 10 is characterized in that catalyst contains 0.03～0.5 part of alkali metal and/or base earth metal promoter.
12. catalyst one of according to claim 1～2 is characterized in that catalyst contains 0.02～0.6 part in auxiliary agent rare earth element.
13. catalyst according to claim 12 is characterized in that the rare earth element in the catalyst is lanthanum; 0.03～0.5 part of addition.
14. the preparation method of a catalyst claimed in claim 1, first preparation has the aluminium oxide-titanium oxide-zirconia composite carrier of bimodal distribution: under stirring condition with MAlO
2, ZrCl
4, TiCl
4Solution mixes, and then with the aqueous slkali neutralization, generates the co-precipitation of aluminium zirconium titanium hydroxide, filters, and then adds the expanding agent of 3～15wt% of mixed hydroxides weight, kneading and compacting, and drying, 1000～1400 ℃ of roastings, wherein M is Na or K; Then carrier impregnation is entered to contain in the solution of palladium, silver, filtration, washing, dry, roasting obtain catalyst of the present invention.
15. preparation method according to claim 14 is characterized in that this preparation method comprises that first preparation has the aluminium oxide-titanium oxide-zirconia composite carrier of bimodal distribution: MAlO
2, ZrCl
4, TiCl
4Solution mixes under 25～100 ℃ of conditions, then with the alkaline solution neutralization, generates the precipitation of hydroxide of aluminium zirconium titanium, stirs 5～20 hours so that aluminium zirconium titanium hydroxide generates uniform crystalline phase particle, filters flush away M
+And Cl
-Then ion adds the expanding agent of 3～15wt% of mixed hydroxides weight, kneading and compacting, and 100～150 ℃ of dryings are at 1000～1350 ℃ of roasting 2～8h; Then carrier impregnation is entered to contain in the solution of palladium, silver, filtration, washing, dry, roasting obtain catalyst of the present invention.
16. the described preparation method of any one claim is characterized in that roasting 4～6h according to claim 14～15.
17. the described preparation method of any one claim is characterized in that expanding agent is selected from one or more in sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and the carbon black according to claim 14～15; Alkaline solution is selected from NaOH, KOH, Na
2CO
3And NH
3In one or more.
18. preparation method according to claim 14, the preparation method who it is characterized in that having the aluminium oxide-titanium oxide-zirconia composite carrier of bimodal distribution is: with aluminium oxide, zirconia, titanium oxide, expanding agent blending, the expanding agent addition is 3～15% of aluminium oxide, zirconia, titanium oxide mixed oxide weight, the even aftershaping of kneading, dry, at 1000～1400 ℃, roasting 2～8 hours.
19. preparation method according to claim 18 is characterized in that 100～150 ℃ of dryings roasting 4～6 hours.
20. preparation method according to claim 18 is characterized in that expanding agent is selected from one or more in sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and the carbon black.
21. according to claim 14 or the described preparation method of 15 any one claims, when it is characterized in that catalyst contains auxiliary agent, carrier impregnation enters to contain in palladium, silver, the compounding agent solution, filters, washing, dry, roasting, obtains catalyst of the present invention.
22. preparation method according to claim 21, when it is characterized in that carrier impregnation enters to contain in palladium, silver, the compounding agent solution synchronously or step impregnation, the pH value of maceration extract is 1.0～5.0, carrier behind the dipping filters, after the washing 80～250 ℃ of dryings 2～20 hours, 350～650 roastings 2～10 hours, obtain catalyst of the present invention.
23. preparation method according to claim 22, step impregnation when it is characterized in that carrier impregnation enters to contain palladium, silver, compounding agent solution: (1) is with containing the palladium solution impregnating carrier, dry, roasting contain the salting liquid that palladium solution is palladium bichloride, palladium nitrate, palladium; (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 promoter soluble salt, dry, roasting obtains catalyst again.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096573A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Preparation method of high-coking resistance selective-hydrogenation catalyst |
| WO2015034521A1 (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 |
| US9108188B2 (en) | 2012-03-07 | 2015-08-18 | Chevoron Phillip Chemical Company, LP | Selective hydrogenation catalyst and methods of making and using same |
| CN108246310A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of Fe-Ag selective hydrogenation catalysts and its preparation method and application |
| CN113713835A (en) * | 2020-05-25 | 2021-11-30 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195037A (en) * | 1996-12-20 | 1998-10-07 | 巴斯福股份公司 | Monoclinic zirconium dioxide having large surface area |
| CN1283519A (en) * | 1999-08-06 | 2001-02-14 | Basf公司 | Catalyst having two-peak hole radius distribution |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
| US20090198076A1 (en) * | 2006-09-29 | 2009-08-06 | Scientific Design Company, Inc. | Catalyst with bimodal pore size distribution and the use thereof |
-
2011
- 2011-09-09 CN CN201110267077.1A patent/CN102989453B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1195037A (en) * | 1996-12-20 | 1998-10-07 | 巴斯福股份公司 | Monoclinic zirconium dioxide having large surface area |
| CN1283519A (en) * | 1999-08-06 | 2001-02-14 | Basf公司 | Catalyst having two-peak hole radius distribution |
| US20090198076A1 (en) * | 2006-09-29 | 2009-08-06 | Scientific Design Company, Inc. | Catalyst with bimodal pore size distribution and the use thereof |
| CN101433842A (en) * | 2008-09-27 | 2009-05-20 | 中国石油天然气股份有限公司 | Hydrogenation catalyst and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9108188B2 (en) | 2012-03-07 | 2015-08-18 | Chevoron Phillip Chemical Company, LP | Selective hydrogenation catalyst and methods of making and using same |
| US9144787B2 (en) | 2012-03-07 | 2015-09-29 | Chevron Phillips Chemical Company Lp | Selective hydrogenation catalyst and methods of making and using same |
| US9636659B2 (en) | 2012-03-07 | 2017-05-02 | Chevron Phillips Chemical Company Lp | Selective hydrogenation catalyst and methods of making and using same |
| CN104096573A (en) * | 2013-04-03 | 2014-10-15 | 中国石油天然气股份有限公司 | Preparation method of high-coking resistance selective-hydrogenation catalyst |
| CN104096573B (en) * | 2013-04-03 | 2016-08-03 | 中国石油天然气股份有限公司 | A kind of high anti-coking selective hydrogenation catalyst preparation method |
| WO2015034521A1 (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 |
| CN105555404A (en) * | 2013-09-06 | 2016-05-04 | 切弗朗菲利浦化学公司 | Selective hydrogenation catalyst and methods of making and using same |
| JP2016533891A (en) * | 2013-09-06 | 2016-11-04 | シェブロン フィリップス ケミカル カンパニー エルピー | Selective hydrogenation catalyst and method for producing and using the same |
| CN108246310A (en) * | 2016-12-29 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of Fe-Ag selective hydrogenation catalysts and its preparation method and application |
| CN113713835A (en) * | 2020-05-25 | 2021-11-30 | 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 |
| 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 |
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