CN102989517A - Doublet aperture distribution alumina carrier and its preparation method - Google Patents
Doublet aperture distribution alumina carrier and its preparation method Download PDFInfo
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- CN102989517A CN102989517A CN201110267803XA CN201110267803A CN102989517A CN 102989517 A CN102989517 A CN 102989517A CN 201110267803X A CN201110267803X A CN 201110267803XA CN 201110267803 A CN201110267803 A CN 201110267803A CN 102989517 A CN102989517 A CN 102989517A
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Abstract
The invention discloses a doublet aperture distribution alumina carrier. The physical properties of the carrier comprise a bulk density of 0.7-1.1g/ml, a pore volume of 0.3-0.6ml/g, a specific surface area of 3-40m<2>/g and an average aperture of 80-400nm; and the apertures of the carrier have two peaks respectively at 80-160nm and 400-590nm. The invention also discloses a preparation method of the carrier, and a hydrogenation catalyst containing the carrier.
Description
Technical field
The present invention relates to carrier and preparation method thereof, be specifically related to alumina support that has bimodal pore size distribution and preparation method thereof.
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 and 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.
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) titanium dioxide of 10～99.9% weight, and b) aluminium oxide of 0～60% weight, silica and/or titanium dioxide, 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 invention is to seek a kind of carrier, its pore-size distribution is suitable for preparing the front-end hydrogenation catalyst, 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 provides the preparation method of this carrier.
Macropore alumina supporter disclosed in this invention has following physical property: bulk density 0.7～1.1g/ml, pore volume 0.3～0.6ml/g, specific area 3～40m
2/ g, average pore size 80～400nm, preferred 120～350nm; Carrier occurs bimodal at 80～160nm and 400～590nm place.
Carrier of the present invention, the hole that the aperture is lower than 10nm accounts for 0～4% of total pore volume, the hole of 10～200nm accounts for 35～90% of total pore volume, and greater than 200nm but account for 10～60% of total pore volume 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.
Alumina support disclosed in this invention owing to have bimodal pore size distribution, occurs bimodal at 80～160nm and 400～590nm respectively.The hole of 80～160nm, its aperture is larger, and the passage of reaction and diffusion can be provided for the selection hydrogenation of acetylene, propine, allene, 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 400～590nm, 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.Carrier of the present invention has suitable bimodal distribution, 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.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 improved 5 ℃, catalyst activity did not still descend, and the excellent properties of above-mentioned catalyst mainly is because alumina support is distributed in due to the suitable pore diameter range.
The contained carrier of catalyst of the present invention has larger aperture 80～400nm, and occur bimodal at 80～160nm and 400～590nm 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
2With the aqueous slkali neutralization, generate the hydroxide co-precipitation, filter, then add the expanding agent of 3～15wt% of hydroxide butt weight, kneading and compacting, drying is at 1000～1350 ℃ of roasting 2～8h, preferred 4～6h obtains carrier of the present invention, and wherein M is Na or K, preferred Na.
Specifically, the preparation method of carrier disclosed in this invention is: MAlO
2Under 25～100 ℃ of conditions, be neutralized to neutrality with alkaline solution, generate precipitation of hydroxide, stirred 5～20 hours so that hydroxide generates uniform crystalline phase particle, filter flush away M
+And Cl
-Then ion adds the expanding agent of 3～15wt% of mixed hydroxides 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 sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and the carbon black one or more.
Alkaline solution of the present invention is selected from NaOH, KOH, Na
2CO
3And NH
3In one or more, preferred NaOH, KOH.
The invention discloses the another kind of preparation method of this carrier: aluminium oxide, expanding agent blending, add the expanding agent of 3～15wt% of alumina weight, the even aftershaping of kneading, drying, 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 ℃.
Carrier disclosed in this invention can be used for selective hydrocatalyst, for example can be used for Pd-Ag hydrogenation catalyst, Pd-Cu hydrogenation catalyst.
Because there are essential distinction in preparation method and the prior art of carrier of the present invention, be specific bimodal pore size distribution thereby make carrier aperture of the present invention, and the formation of bimodal pore size distribution are not owing to component all is that aluminium oxide causes.
Description of drawings
The aluminium oxide bimodal pore size distribution figure of Fig. 1: embodiment 1 occurs bimodal at 120nm and 450nm.
The aluminium oxide bimodal pore size distribution figure of Fig. 2: embodiment 2 occurs bimodal at 155nm and 570nm.
The aluminium oxide bimodal pore size distribution figure of Fig. 3: embodiment 3 occurs bimodal at 175nm and 580nm.
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 NaAlO
2Solution under 50 ℃ of conditions, with the neutralization of NaOH solution, the hydroxide co-precipitation is stirred 10 hours so that 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 the aluminium oxide macropore carrier behind 120 ℃ of dry 4h.Bulk density 0.92g/ml wherein, pore volume 0.432ml/g, specific area is 22.4m
2/ g, carrier has bimodal distribution, average pore size 190nm at 120nm and 450nm place.It is as follows that carrier aperture distributes: be 1% less than 10nm; 10～200nm is 73.30%; The aperture is 25.5% greater than 200nm but less than or equal to 1000nm; The aperture is 0.2% greater than 1000nm.
Getting 10ml, to contain palladium ion concentration be 0.047g/ml palladium nitrate solution and 990ml water, after fully mixing, and dipping 1000g carrier, 120 ℃ of dryings 5 hours, 450 ℃ of roastings obtained one in 4 hours and soak catalyst.Getting 10ml silver ion concentration is 0.08g/ml liquor argenti nitratis ophthalmicus and 990ml water, and after fully mixing, dipping one soaks catalyst, 120 ℃ of dryings 5 hours, and 450 ℃ of roastings obtained finished catalyst S-1 in 3 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst is table 2, table 3 as a result.
Embodiment 2
850g aluminium oxide, 20g citric acid and 30g carbon black stir in mechanical agitator, and the rectangular of Φ 4.2mm made in extrusion molding, then 110 ℃ of dryings 5 hours 1250 ℃ of roastings 4 hours, obtain alumina support, pore volume 0.389ml/g, bulk density 0.97g/ml, specific area is 13.1m
2/ g; Carrier has bimodal distribution, average pore size 260nm at 155nm and 570nm place; It is as follows that carrier aperture distributes: be 0% less than 10nm; 10～200nm is 73.16%; The aperture is 26.66% greater than 200nm but less than or equal to 1000nm; The aperture is 0.18% greater than 1000nm.
Getting 10ml, to contain palladium ion concentration be 0.042g/ml palladium nitrate solution and 990ml water, after fully mixing, and dipping 1000g carrier, 150 ℃ of dryings 4 hours, 450 ℃ of roastings obtained one in 5 hours and soak catalyst.Getting 10ml silver ion concentration is in the 0.11g/ml liquor argenti nitratis ophthalmicus, adds 990ml water, and after fully mixing, dipping one soaks catalyst, 100 ℃ of dryings 6 hours, and 500 ℃ of roastings obtained finished catalyst S-2 in 2 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2, table 3.
Comparative Examples 1
Adopt common alumina support, 1250 ℃ of roastings 5 hours, obtain α-Al
2O
3Carrier records its pore volume 0.43ml/g, bulk density 0.91g/ml, and specific area is 15.2m
2/ g, average pore size 110nm.Getting 10ml, to contain palladium ion concentration be 0.047g/ml palladium nitrate solution and 990ml water, after fully mixing, and impregnated carrier, 120 ℃ of dryings 5 hours, 450 ℃ of roastings obtained one in 4 hours and soak catalyst.Getting 10ml silver ion concentration is in the 0.08g/ml liquor argenti nitratis ophthalmicus, adds and 990ml water, and after fully mixing, dipping one soaks catalyst, 120 ℃ of dryings 5 hours, and 450 ℃ of roastings obtained finished catalyst D-1 in 3 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2, table 3.
Comparative Examples 2
Adopt common alumina support, 1300 ℃ of roastings 4 hours, obtain α-Al2O3 carrier, record its pore volume 0.45ml/g, bulk density 0.98g/ml, specific area is 12.4m2/g, average pore size 220nm.Getting 10ml, to contain palladium ion concentration be 0.042g/ml palladium nitrate solution and 990ml water, after fully mixing, and impregnated carrier, 150 ℃ of dryings 4 hours, 450 ℃ of roastings obtained one in 5 hours and soak catalyst.Getting 10ml silver ion concentration is 0.11g/ml liquor argenti nitratis ophthalmicus and 990ml water, and after fully mixing, dipping one soaks catalyst, 100 ℃ of dryings 6 hours, and 500 ℃ of roastings obtained finished catalyst D-2 in 2 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2, table 3.
Can find out from the comparing result of catalyst, adopt the activity and selectivity of the catalyst of carrier preparation of the present invention all to be higher than prior art α-Al
2O
3The catalyst of carrier preparation.
Embodiment 3
Under agitation, contain 1000g NaAlO
2Solution under 50 ℃ of conditions, with the neutralization of KOH solution, the co-precipitation of aluminium titanium hydroxide was stirred 10 hours so that aluminium 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 α-Al behind 130 ℃ of dry 2h
2O
3Carrier, bulk density 1.05g/ml wherein, pore volume 0.307ml/g, specific area is 6.5m
2/ g, carrier has bimodal distribution, average pore size 280nm at 175nm and 580nm place.It is as follows that carrier aperture distributes: be 0% less than 10nm; 10～200nm is 68.50%; The aperture is 31.36% greater than 200nm but less than or equal to 1000nm; The aperture is 0.14% greater than 1000nm.
Get the 1000g carrier, adding 10ml, to contain palladium ion concentration be in the 0.040g/ml palladium nitrate solution, adds 990ml water, after fully mixing, and impregnated carrier, 130 ℃ of dryings 2 hours, 500 ℃ of roastings obtained one in 2 hours and soak catalyst.Adding 10ml silver ion concentration is in the 0.13g/ml liquor argenti nitratis ophthalmicus, adds 990ml water, and after fully mixing, dipping one soaks catalyst, 140 ℃ of dryings 2 hours, and 480 ℃ of roastings obtained finished catalyst I in 3 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2.
Embodiment 4
1000g aluminium oxide, 100g citric acid stir in mechanical agitator, and the rectangular of Φ 3.8mm made in extrusion molding, and after 150 ℃ of dryings in Muffle furnace dry 6 hours, then under the condition of 1400 ℃ of air, roasting 6 hours obtained α-Al
2O
3Carrier, pore volume 0.298ml/g, bulk density 1.06g/ml, specific area is 4.7m
2/ g, carrier has bimodal distribution, average pore size 370nm at 188nm and 760nm place; It is as follows that carrier aperture distributes: be 0% less than 10nm; 10～200nm is 69.70%; The aperture is 30.14% greater than 200nm but less than or equal to 1000nm; The aperture is 0.16% greater than 1000nm.
Getting 10ml, to contain palladium ion concentration be the 0.052g/ml palladium nitrate solution, and 10ml silver ion concentration is in the 0.19g/ml liquor argenti nitratis ophthalmicus, adds 980ml water, after fully mixing, dipping 1000g carrier, 130 ℃ of dryings 3 hours, 560 ℃ of roastings obtained finished catalyst S-4 in 5 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2, table 3.
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 the 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 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.Recording the main peak value is 15.9nm, and minor peaks is 11.5nm, and specific area is 21.8m
2/ g.
Getting 10ml, to contain palladium ion concentration be the 0.052g/ml palladium nitrate solution, and 10ml silver ion concentration is in the 0.19g/ml liquor argenti nitratis ophthalmicus, adds 980ml water, after fully mixing, dipping 1000g carrier, 130 ℃ of dryings 3 hours, 560 ℃ of roastings obtained finished catalyst D-3 in 5 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2, table 3.
Comparative Examples 4
Adopt CN00136874.5 patent working example 1 described method to carry out the preparation of carrier.Under agitation, NAAlO
2Solution (116 grams are dissolved in 450 ml waters) then with the neutralization of NaOH solution, obtains aluminum hydroxide precipitation, stirs 24 hours so that aluminium 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 is made the rectangular of ф 3mm after mediating, 900 ℃ of roastings 2 hours in Muffle furnace obtain alumina support, bulk density 0.82g/ml after 120 ℃ of dryings, pore volume 0.47ml/g, specific area 34.3m
2/ g (BET nitrogen method), 37.4 (mercury injection methods), carrier aperture is unimodal, average pore size 60nm.
Getting 10ml, to contain palladium ion concentration be the 0.052g/ml palladium nitrate solution, and 10ml silver ion concentration is in the 0.19g/ml liquor argenti nitratis ophthalmicus, adds 980ml water, after fully mixing, dipping 1000g carrier, 130 ℃ of dryings 3 hours, 560 ℃ of roastings obtained finished catalyst D-4 in 5 hours.Get the 500ml industrial side line device of packing into and estimate its performance, raw material forms such as table 1, reaction pressure 3.7～3.9MPa, reaction velocity 13000h
-1Evaluating catalyst the results are shown in Table 2, table 3.
Table 1 raw material forms
The contrast of table 2 catalyst 0～1000h performance mean value
| Catalyst | Reaction temperature (℃) | Temperature rise (℃) | Conversion ratio (%) | Selectively (%) |
| Catalyst S-1 | 70.0 | 29.5 | 83.6 | 59.8 |
| Catalyst S-2 | 70.0 | 28.7 | 80.1 | 64.3 |
| Catalyst S-3 | 70.0 | 28.2 | 77.4 | 62.1 |
| Catalyst S-4 | 70.0 | 27.9 | 70.8 | 80.4 |
| Catalyst D-1 | 70.0 | 28.4 | 73.2 | 32.7 |
| Catalyst D-2 | 70.0 | 29.5 | 80.4 | 18.2 |
| Catalyst D-3 | 70.0 | 30.4 | 86.7 | 8.3 |
| Catalyst D-4 | 70.0 | 28.3 | 67.4 | 14.2 |
The contrast of table 3 catalyst 1000～1500h performance mean value
| Catalyst | Reaction temperature (℃) | Temperature rise (℃) | Conversion ratio (%) | Selectively (%) |
| Catalyst S-1 | 72.0 | 27.4 | 70.5 | 47.2 |
| Catalyst S-2 | 72.0 | 26.0 | 76.5 | 46.5 |
| Catalyst S-3 | 74.0 | 25.1 | 73.4 | 48.6 |
| Catalyst S-4 | 74.0 | 25.3 | 69.9 | 62.3 |
| Catalyst D-1 | 76.0 | 24.3 | 60.4 | 18.2 |
| Catalyst D-2 | 78.0 | 24.7 | 61.3 | 9.6 |
| Catalyst D-3 | 79.0 | 25.0 | 42.7 | 3.2 |
| Catalyst D-4 | 85 | 23.0 | 34.6 | 5.6 |
Claims (12)
1. the alumina support of a bimodal pore size distribution is characterized in that carrier has following physical property: bulk density 0.7～1.1g/ml, pore volume 0.3～0.6ml/g, specific area 3～40m
2/ g, average pore size 80～400nm; Carrier occurs bimodal at 80～160nm and 400～590nm place.
2. carrier according to claim 1, it is characterized in that the hole that the aperture is lower than 10nm accounts for 0～4% of total pore volume, the hole of 10～200nm accounts for 35～90% of total pore volume, greater than 200nm but account for 10～60% of total pore volume 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.
3. carrier one of according to claim 1～2 is characterized in that carrier average pore size 120～350nm.
4. the preparation method of a carrier claimed in claim 1: under stirring condition with MAlO
2With the aqueous slkali neutralization, generate the hydroxide co-precipitation of aluminium, filter, then add the expanding agent of 3～15wt% of hydroxide weight, kneading and compacting, drying, 1000～1400 ℃ of roastings, wherein M is Na or K.
5. preparation method according to claim 4 is characterized in that MAlO
2Under 25～100 ℃ of conditions, with the alkaline solution neutralization, generate precipitation of hydroxide, stirred 5～20 hours so that hydroxide generates uniform crystalline phase particle, filter flush away M
+And Cl
-Then ion adds the expanding agent of 3～15wt% of hydroxide weight, kneading and compacting, and 100～150 ℃ of dryings are at 1000～1350 ℃ of roasting 2～8h.
6. the described preparation method of any one claim is characterized in that roasting 4～6h according to claim 4～5.
7. 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 4～5.
8. the described preparation method of any one claim is characterized in that alkaline solution is selected from NaOH, KOH, Na according to claim 4～5
2CO
3And NH
3In one or more.
9. preparation method according to claim 8 is characterized in that alkaline solution is selected from NaOH, KOH.
10. the preparation method of a carrier claimed in claim 1: with aluminium oxide, expanding agent blending, the expanding agent addition is 3～15% of alumina weight, the even aftershaping of kneading, and drying, at 1000～1400 ℃, roasting 2～8 hours.
11. preparation method according to claim 10 is characterized in that 100～150 ℃ of dryings roasting 4～6 hours.
12. preparation method according to claim 11 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.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110267803.XA CN102989517B (en) | 2011-09-09 | 2011-09-09 | Alumina support of bimodal pore size distribution and preparation method thereof |
Applications Claiming Priority (1)
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| CN111686709B (en) * | 2020-01-23 | 2021-06-01 | 中国科学院大连化学物理研究所 | Propane dehydrogenation propylene supported catalyst with specific pore structure and preparation method thereof |
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