CN102989454B - Containing the carbon two front-end hydrogenation Catalysts and its preparation method of bimodal pore size distribution carrier - Google Patents
Containing the carbon two front-end hydrogenation Catalysts and its preparation method of bimodal pore size distribution carrier Download PDFInfo
- Publication number
- CN102989454B CN102989454B CN201110267207.1A CN201110267207A CN102989454B CN 102989454 B CN102989454 B CN 102989454B CN 201110267207 A CN201110267207 A CN 201110267207A CN 102989454 B CN102989454 B CN 102989454B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- carrier
- palladium
- silver
- pore size
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
A kind of carbon two front-end hydrogenation Catalysts and its preparation method containing bimodal pore size distribution carrier.This carbon two front-end hydrogenation catalyst, in catalyst quality 100 parts, 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, it is characterized in that the carrier of catalyst is a kind of alumina support of bimodal pore size distribution, 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.Invention also discloses the preparation method of this hydrogenation catalyst.
Description
Technical field
The present invention relates to Catalysts and its preparation method, be specifically related to a kind of carbon two front-end hydrogenation Catalysts and its preparation method.
Background technology
Often containing impurity such as a small amount of acetylene, propine and allene in the cracking gas produced in cracking petroleum hydrocarbon vapor process, their existence can affect high-efficiency polyethylene and polypropylene catalyst that in follow-up workshop section, homogeneous polymerization and polymerization process use to some extent.By the requirement of the aft-loaded airfoil operations such as polyethylene, EP rubbers, polypropylene, in polymer grade ethylene, the molar fraction of acetylene must lower than 5ppm, and ethylene glycol also requires that the molar fraction of acetylene in ethene is lower than 1ppm in producing.Catalysis selective hydrogenation method be industrial most widely used general, be also a kind of method the most effectively removing acetylene, propine and allene (MAPD), the catalyst adopted mostly is alumina load precious metals pd catalyst.
At selec-tive 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 be 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 on selective acetylene hydrocarbon hydrogenation catalyst can cause the hydrogenation activity of catalyst and selective decline, shortens life cycle, causes catalyst frequent regeneration, affect the service life of catalyst, thus cause the raising of production cost.
Acetylene selective hydrogenation is divided into front-end hydrogenation and back end hydrogenation two kinds, so-called front-end hydrogenation refers to the relative domethanizing column position of acetylene hydrogenation reactor with back end hydrogenation, acetylene hydrogenation reactor is front-end hydrogenation before being positioned at domethanizing column, acetylene hydrogenation reactor is back end hydrogenation after being positioned at domethanizing column, wherein, front-end hydrogenation technological process is divided into again front-end deethanization front-end hydrogenation and predepropanization front-end hydrogenation two kinds.Hydrogenation technique is different, and the raw material composition entering reactor is also different, and the material that wherein maximum difference is to enter in front-end hydrogenation technique reactor contains a large amount of hydrogen and more CO.Due to the hydrogen (about 20-50mol%) containing high concentration in hydrogenation reaction material and CO (300 ~ 5000ppm (mol)), and hydrogen and CO fluctuation range are greatly, therefore 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 to 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 selec-tive hydrogenation except the selective and active key of alkynes catalyst and be to improve the pore structure of carrier.For the problems referred to above, the method usually by improving carrier calcination temperature obtains the eurypyloue α of tool-Al
2o
3carrier, but be limited with this surface-sensitive degree reducing catalyst carrier.
Prior art also attempts the performance improving catalyst by preparing complex carrier, but, for carbon two front-end hydrogenation catalyst complex carrier only CN00136874.5 to be improved the performance of catalyst by the complex carrier preparing aluminium oxide and titanium oxide, this carrier aperture is distributed in 50nm and 1000nm and occurs bimodal.This carrier, for the preparation of hydrogenation catalyst, effectively can improve the anticoking capability 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.For the preparation of carbon two front-end hydrogenation catalyst, there is the defect being not suitable with catalyst requirement than table and pore-size distribution, cause catalyst activity component Pd decentralization lower in the carrier of other bimodal pore size distribution, or the acid higher shortcoming of catalyst surface.
CN97114892.9 discloses a kind of method of hydroaromatic compound in the presence of a catalyst, wherein contain the carrier material of 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, carrier hole size distribution can be roughly bimodal pore size distribution, in its embodiment, pore size distribution about 600nm and roughly 200nm demonstrate maximum.US7507845B1, discloses a kind of carrier, has bimodal pore distribution: the aperture of the first pores is 0.01 ~ 5 μm, and the aperture of the second pores is 5 ~ 30 μm; First pores content is lower than 50%, and the second pores content is higher than 50%; Catalyst water absorption rate scope is that to record than table be 0.3 ~ 4.0m for 0.2 ~ 0.8cc/g, BET
2/ g, pore volume is 0.2 ~ 0.8ml/g.Above two kinds of carriers are for the preparation of carbon two front-end hydrogenation catalyst, and because specific area is too small, be unfavorable for the dispersion of active component Pd, prepared catalyst activity and selectivity is all poor.
CN00124057.9 discloses a kind of catalyst with two-peak hole radius distribution, titanium dioxide containing a) 10 ~ 99.9% weight, and b) aluminium oxide of 0 ~ 60% weight, silica and/or titanium dioxide, and at least one element of IA race or IIA race in the periodic table of elements of c) 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 the summation of percentage by weight is 100.In this catalyst, the hole of 70 ~ 100% 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 catalyst disclosed in 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 are for the preparation of carbon two front-end hydrogenation catalyst, and because specific surface area of catalyst is comparatively large, cause its surface acidity higher, catalyst anticoking capability is poor.
The Gao Xiao of mink cell focus processing National Key Laboratory of China University Of Petroleum Beijing discloses ZrO
2-Al
2o
3the preparations and applicatio (" Industrial Catalysis " the 16th volume the 3rd phase in 2008) of catalyst carrier, describes 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 prepared by this article method is comparatively large, and acidity is comparatively strong, and minimum specific area is 190m
2/ g.
, there is the defect being not suitable with catalyst requirement than table and pore-size distribution, cause catalyst activity component Pd decentralization lower in the carrier of the bimodal pore size distribution in prior art in carbon two front-end hydrogenation catalyst, or the acid higher shortcoming of catalyst surface.
Summary of the invention
The object of the present invention is to provide a kind of carbon two front-end hydrogenation catalyst containing the carrier that pore-size distribution is suitable for, this catalyst have hydrogenation activity high, selective good, green oil generating amount is low, can when hydrogen and CO content higher use, and there is stronger resistant to hydrogen gas and CO to fluctuate ability.Another object of the present invention there is provided the preparation method of hydrogenation catalyst.
Carbon two front-end hydrogenation catalyst disclosed in this invention, in catalyst quality 100 parts, comprises 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; The carrier of catalyst is the alumina support with bimodal pore size distribution, and this 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, preferably 120 ~ 350nm; Carrier occurs bimodal at 80 ~ 160nm and 400 ~ 590nm place.
The alumina support mesoporous with bimodal pore size distribution of the present invention accounts for 0 ~ 4% of total pore volume lower than the hole of 10nm, the hole of 10 ~ 200nm accounts for 35 ~ 90% of total pore volume, be greater than 200nm but the hole being less than or equal to 1000nm accounts for 10 ~ 60% of total pore volume, the hole that aperture is greater than 1000nm accounts for 0 ~ 3% of total pore volume.
In order to obtain activity and selectivity catalyst all preferably, Pd and Ag bimetallic chosen by catalyst disclosed in this invention is active component.If do not add silver, catalyst selective poor, but if the addition of silver is too high, 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 alkali metal and/or base earth metal promoter composition 0.03 ~ 0.8 part, preferably 0.03 ~ 0.5 part; Wherein preferably 0.03 ~ 0.5 part, alkali metal and/or alkaline-earth metal, preferably alkali metal potassium.By adding alkali metal, alkaline-earth metal, change the acidity of catalyst surface, catalyst surface coking is reduced, catalyst performance index keeps good in the long period, especially selectively significantly improves.
In addition, catalyst disclosed in this invention can also add rare earth element as auxiliary component, preferably 0.02 ~ 0.6 part, most preferably lanthanum; Addition 0.02 ~ 0.6 part, preferably 0.03 ~ 0.5 part.Reducing the surface acidity of catalyst by adding rare earth element further, improving catalyst anticoking capability.
Alumina support disclosed in this invention, owing to having bimodal pore size distribution, occurs bimodal at 80 ~ 160nm and 400 ~ 590nm respectively.The hole of 80 ~ 160nm is compared to existing selective hydrogenation catalyst carrier, aperture is larger, the passage that can reaction is provided for the selec-tive hydrogenation of acetylene, propine, allene and spread, and due to its aperture larger, be conducive to the rapid diffusion of hydrogenation products ethene, propylene, thus the selective of catalyst can be improved further.Existing bimodal pore distribution carrier is compared in the hole of 400 ~ 590nm, aperture is relatively little, and this can be avoided excessive aperture to cause the reduction of catalyst activity, can ensure enough ducts simultaneously, make the unsaturated C such as the accessory substance 1,3-butadiene produced in hydrogenation process
4hydrocarbon, and green oil is diffused into catalyst surface rapidly, avoids them to be polymerized the coking causing catalyst further, thus improves the service life of catalyst.Meanwhile, the catalyst prepared due to carrier of the present invention has macroporous structure, and surface acidity is low, and when the load of activity component metal palladium is used for carrying out hydrogenation to alkynes and alkadienes at the catalyst that carrier surface is obtained, green oil generating amount is few, and hydrogenation selectivity is good.Improve the ability that catalyst preventing from heavy metal is poisoning simultaneously, extend the service life of catalyst further.Due to carrier aperture distribution of the present invention and composition, the catalyst making it prepare reduces H
2with the sensitivity of CO, be particularly suitable for H in reaction mass
2content is that the front-end hydrogenation selec-tive hydrogenation of 20% ~ 50%mol, CO content, 300 ~ 5000ppm is except alkynes technique.The catalyst obtained by carrier of the present invention is not only selective good, and in industrial side line evaluating apparatus, it is selective reaches more than 50%, and has very high activity, at reaction velocity 8000 ~ 16000h
-1condition under acetylene removal can be made to being less than 1ppm, and after evaluation time reaches 1000h, when catalytic reaction improves 5 DEG C, catalyst activity does not still decline, and the excellent properties of above-mentioned catalyst is mainly because alumina support is distributed in caused by suitable pore diameter range; Other carriers can not have this excellent effect.
Carrier contained by catalyst of the present invention has larger aperture 80 ~ 400nm, and occur bimodal at 80 ~ 160nm and 400 ~ 590nm respectively, because carrier has the feature of larger aperture and bimodal pore distribution of the present invention, while making catalyst have greater activity, also there is the feature of selective height, anticoking capability excellence.
The invention discloses the preparation method of catalyst: first preparation has the alumina support of bimodal pore size distribution, then carrier impregnation is entered in the solution containing one or more in palladium, silver and auxiliary agent, filtration, washing, dry, roasting, obtain catalyst of the present invention.
The preparation method of the carrier in catalyst of the present invention, comprises the steps: under agitation by MAlO
2with aqueous slkali neutralization, generate hydroxide co-precipitation, filter, then add the expanding agent of 3 ~ 15wt% of hydroxide butt weight, kneading and compacting, dry, at 1000 ~ 1350 DEG C of roasting 2 ~ 8h, preferably 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 DEG C of conditions, be neutralized to neutrality with alkaline solution, generate precipitation of hydroxide, stir and within 5 ~ 20 hours, make hydroxide generate uniform crystalline phase particle, filter, wash away M
+and Cl
-ion, then adds the expanding agent of 3 ~ 15wt% of mixed hydroxides weight, kneading and compacting, 100 ~ 150 DEG C of dryings, 1000 ~ 1400 DEG C of roasting 2 ~ 8h preferably 4 ~ 6h.
The shaping customary way that adopts of the present invention carries out, and as methods such as compressing tablet, spin, extrusions, is preferably extrusion, spin method.
The kind of expanding agent of the present invention and consumption can be all this area routines, such as, 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
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, dry, at 1000 ~ 1400 DEG C, roasting 2 ~ 8 hours preferably 4 ~ 6 hours.
Blending method of the present invention is prepared in the process of carrier, and drying condition recommends 100 ~ 150 DEG C.
In method for preparing catalyst disclosed in this invention, carrier impregnation is entered the solution containing one or more 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, such as, in CN200810223451.6, disclose this technology.Preparation method disclosed by the invention, do not limit synchronous or step impregnation, the pH value of recommending maceration extract is 1.0 ~ 5.0, the carrier after dipping wash after filtration after 80 ~ 250 DEG C of dryings 2 ~ 20 hours, 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 of palladium, silver, auxiliary agent respectively wiring solution-forming on carrier.When step impregnation, also by after two or more in component synchronously dipping, more remaining component can be flooded, such as: can by step impregnation auxiliary agent again after active component Pd, Ag synchronously dipping; Can by impregnation aids synchronous after active component Pd, Ag step impregnation; Also Ag and other carriers can flooded step by step or synchronously by after one or more in active component Pd and auxiliary agent synchronously dipping.The present invention does not enumerate mode during various element and the dipping of step impregnation.
Single-steeping or flood several times after the soluble-salt of palladium, silver, auxiliary agent can be made mixed solution by the synchronous dipping in the preparation method of catalyst disclosed by the invention, flood again after repeatedly adopting dipping, dry, roasting during dipping, the cyclic process that dry, roasting is such, generally all adopt the most frequently used dipping method in every respect, the present invention is not limited especially.
When adopting step impregnation method, preferably recommend to adopt the following step operation:
The first step is with containing palladium solution impregnating carrier, and it is favourable for carrying out flooding with the solution of the absorbent maximum of carrier institute, the catalyst of last calcining should be made to contain 0.02 ~ 0.15 part of palladium in solution containing the amount of palladium.Adopt and contain the salting liquid that palladium solution can be palladium bichloride, palladium nitrate, palladium.After by palladium salt solution impregnation, 80 ~ 250 DEG C of dryings 2 ~ 20 hours;
When second step is by silver-colored solution impregnation, Ag-containing solution can be silver nitrate, silver perchlorate, silver nitrate is preferably selected to prepare, can be specifically: the alumina support with bimodal pore distribution structure of complete for load palladium is immersed in the acid solution of silver salt, 10 ~ 120min is flooded at 10 ~ 100 DEG C of temperature, 80 ~ 250 DEG C of dryings after 2 ~ 20 hours, 350 ~ 650 roasting 2 ~ 10 hours.
As also added alkali metal, alkaline-earth metal or rare earth metal in catalyst, after the above-mentioned carrier calcination containing palladium and silver cools, then immerse alkali metal, alkaline-earth metal or rare earth metal again obtain dipping 10 ~ 120min in the aqueous solution of soluble-salt, 80 ~ 250 DEG C of dryings after 2 ~ 20 hours, within 2 ~ 10 hours, obtain catalyst in 350 ~ 650 roasting.
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.
Because the preparation method of carrier in catalyst of the present invention and prior art exist essential distinction, thus make carrier aperture of the present invention be specific bimodal pore size distribution, and the formation of bimodal pore size distribution is not because component is all that aluminium oxide causes.
Accompanying drawing explanation
Fig. 1: the aluminium oxide bimodal pore size distribution figure of embodiment 1, occur bimodal at 120nm and 450nm.
Fig. 2: the aluminium oxide bimodal pore size distribution figure of embodiment 2, occur bimodal at 155nm and 570nm.
Fig. 3: the aluminium oxide bimodal pore size distribution figure of embodiment 3, occur bimodal at 175nm and 580nm.
Detailed description of the invention
Embodiment describes in further detail of the present invention, but the present invention is not by the restriction of these embodiments.
1, analytical method
(1) specific area of carrier, pore volume, pore-size distribution GB/T21650.1 mercury injection method and gas determination of adsorption method solid material pore-size distribution and porosity. part 1: mercury injection method.
(2) the mensuration gas chromatography of the industrial ethene trace acetylene of acetylene content: GB/T3995-93.
(3) bulk density: take a certain amount of carrier and load 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, containing NaAlO
2solution under 50 DEG C of conditions, with NaOH solution neutralization, hydroxide co-precipitation, stirs and within 10 hours, makes hydroxide generate uniform fine particle, and filtration also 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 is made in extrusion molding, 1200 DEG C of roastings 5 hours after 120 DEG C of dry 4h, obtains aluminium oxide macropore carrier.Wherein bulk density 0.92g/ml, pore volume 0.432ml/g, specific area is 22.4m
2/ g, carrier has bimodal pore size distribution at 120nm and 450nm place, average pore size 190nm.Carrier aperture distribution is as follows: being less than 10nm is 1%; 10 ~ 200nm is 73.30%; Aperture is greater than 200nm but is less than or equal to 1000nm is 25.5%; It is 0.2% that aperture is greater than 1000nm.Carrier aperture distribution map refers to Fig. 1.
Embodiment 2
850g aluminium oxide, 20g citric acid and 30g carbon black stir in mechanical agitator, and the rectangular of Φ 4.2mm is made in extrusion molding, 110 DEG C of dryings 5 hours, then 1250 DEG C 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 pore size distribution at 155nm and 570nm place, average pore size 260nm; Carrier aperture distribution is as follows: being less than 10nm is 0%; 10 ~ 200nm is 73.16%; Aperture is greater than 200nm but is less than or equal to 1000nm is 26.66%; It is 0.18% that aperture is greater than 1000nm.Carrier aperture distribution map refers to Fig. 2.
Embodiment 3
Under agitation, containing 1000gNaAlO
2solution under 50 DEG C of conditions, with KOH solution neutralization, the co-precipitation of aluminium titanium hydroxide, stirs and within 10 hours, makes aluminium titanium hydroxide generate uniform fine particle, and product filtration also washes away Na with deionized-distilled water
+and Cl
-ion, adds 15% polyvinyl alcohol as expanding agent, and spin after mediating, 1350 DEG C of roastings 6 hours after 130 DEG C of dry 2h, obtains α-Al
2o
3carrier, wherein bulk density 1.05g/ml, pore volume 0.307ml/g, specific area is 6.5m
2/ g, carrier has bimodal pore size distribution at 175nm and 580nm place, average pore size 280nm.Carrier aperture distribution is as follows: being less than 10nm is 0%; 10 ~ 200nm is 68.50%; Aperture is greater than 200nm but is less than or equal to 1000nm is 31.36%; It is 0.14% that aperture is greater than 1000nm.Carrier aperture distribution map refers to Fig. 3.
Embodiment 4
1000g aluminium oxide, 100g citric acid stir in mechanical agitator, and the rectangular of Φ 3.8mm is made in extrusion molding, after 150 DEG C of dryings in Muffle furnace dry 6 hours, and then under the condition of 1400 DEG C of air, roasting 6 hours, obtains α-Al
2o
3carrier, pore volume 0.298ml/g, bulk density 1.06g/ml, specific area is 4.7m
2/ g, carrier has bimodal pore size distribution at 188nm and 760nm place, average pore size 370nm; Carrier aperture distribution is as follows: being less than 10nm is 0%; 10 ~ 200nm is 69.70%; Aperture is greater than 200nm but is less than or equal to 1000nm is 30.14%; It is 0.16% that aperture is greater than 1000nm.
Comparative example 1
Adopt common alumina support, 1250 DEG C 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.
Comparative example 2
Adopt common alumina support, 1300 DEG C of roastings 4 hours, obtain α-Al
2o
3carrier, records its pore volume 0.45ml/g, bulk density 0.98g/ml, and specific area is 12.4m2/g, 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 DEG C, then add identical aluminum sulfate solution 20min continuously with the speed of 1.4kg/min, simultaneously by adding sodium aluminate aqueous solution (Al
2o
3content is 23.5%) make pH value reach 8.5 and remain in the scope of 8.3 ~ 8.6, make solution temperature remain on 33 DEG C by the chuck recirculated cooling water of described still simultaneously.Then when stir but not reagent adding make the temperature of gained slurries rise to 81 DEG C.Restart to add reagent and be about 40min, make temperature remain on 81 DEG C by the chuck recirculated cooling water of described still simultaneously and pH value is remained in the scope of 8.2 ~ 9.2.Gained slurries are containing the 6.5%Al that has an appointment
2o
3.About 29% of described total aluminium oxide is formed in described first settling step interval.Then described aluminium oxide slurries are filtered and washing, then spraying dry.By described powder water grinding, produce the mixture containing 63% water, extrude, dry at 150 DEG C, roasting at 593 DEG C.The alumina support pore volume obtained 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.Recording main peak value is 15.9nm, and minor peaks is 11.5nm, and specific area is 21.8m
2/ g.
Getting 10ml containing palladium ion concentration is 0.052g/ml palladium nitrate solution, and 10ml silver ion concentration is in 0.19g/ml liquor argenti nitratis ophthalmicus, adds 980ml water, after abundant mixing, dipping 1000g carrier, 130 DEG C of dryings 3 hours, 560 DEG C of roastings obtain finished catalyst D-3 in 5 hours.Get 500ml to load industrial side line device and evaluate its performance, raw material composition as table 1, reaction pressure 3.7 ~ 3.9MPa, reaction velocity 13000h
-1.Evaluating catalyst the results are shown in Table 2, table 3.
Comparative example 4
The method described in CN00136874.5 patent Example 1 is adopted to carry out the preparation of carrier.Under agitation, NAAlO
2solution (116 grams are dissolved in 450 ml waters), then with NaOH solution neutralization, obtains aluminum hydroxide precipitation, stirs and within 24 hours, make aluminium hydroxide generate uniform fine particle, and product filters and uses deionized water distilled water to wash and removes Na
+and Cl
-ion, then the mixed hydroxides 120 DEG C of dryings will obtained, be ground into 120 ~ 180 order fine powders, after kneading, with double screw banded extruder, hydroxide made the rectangular of ф 3mm, 900 DEG C of roastings 2 hours in Muffle furnace after 120 DEG C of dryings, obtain alumina support, bulk density 0.82g/ml, pore volume 0.47ml/g, specific area 37.4 (mercury injection method), carrier aperture is unimodal, average pore size 60nm.
The preparation of catalyst
The carrier with bimodal pore distribution structure above method prepared immerses in the acid solution of palladium salt, 10 ~ 120min is flooded at 10 ~ 100 DEG C of temperature, 80 ~ 250 DEG C of dryings 2 ~ 10 hours, 350 ~ 650 DEG C of roastings 2 ~ 10 hours, immerse after cooling in the aqueous solution of the soluble-salt of Ag and flood 10 ~ 120min, 80 ~ 250 DEG C of dryings 2 ~ 10 hours, 350 ~ 650 DEG C 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 element 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 conditions
Get each 500mL of above catalyst to load industrial side line device and evaluate its performance, raw material composition as table 2, reaction pressure 3.7 ~ 3.9MPa, reaction velocity 13000h
-1.Inlet temperature 45 ~ 90 DEG C.Evaluating catalyst the results are shown in Table 3.
Table 2 raw material forms
Table 3 catalyst 1000h evaluation result
Claims (16)
1. the carbon two front-end hydrogenation catalyst containing bimodal pore size distribution carrier, in catalyst quality 100 parts, catalyst (1) 0.02 ~ 0.15 part of palladium composed of the following components, (2) silver, the mass ratio 9 ~ 1:1 of silver and palladium, palladium, silver are all in element quality, it is characterized in that the carrier of catalyst is the alumina support with bimodal pore size distribution, this 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. catalyst according to claim 1, is characterized in that palladium 0.02 ~ 0.10 part.
3. catalyst 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 and 2, the alumina support mesoporous that it is characterized in that having bimodal pore size distribution accounts for 0 ~ 4% of total pore volume lower than the hole of 10nm, the hole of 10 ~ 200nm accounts for 35 ~ 90% of total pore volume, be greater than 200nm but the hole being less than or equal to 1000nm accounts for 10 ~ 60% of total pore volume, the hole that aperture is greater than 1000nm accounts for 0 ~ 3% of total pore volume.
5. catalyst according to claim 1 and 2, is characterized in that carrier average pore size 120 ~ 350nm.
6. the carbon two front-end hydrogenation catalyst containing bimodal pore size distribution carrier, in catalyst quality 100 parts, catalyst (1) 0.02 ~ 0.15 part of palladium composed of the following components, (2) silver, mass ratio 9 ~ the 1:1 of silver and palladium, (3) alkali metal and/or base earth metal promoter 0.03 ~ 0.8 part, palladium, silver, alkali metal and/or alkaline-earth metal are all in element quality, it is characterized in that the carrier of catalyst is the alumina support with bimodal pore size distribution, this 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.
7. catalyst according to claim 6, is characterized in that catalyst contains alkali metal and/or base earth metal promoter 0.03 ~ 0.5 part.
8. the carbon two front-end hydrogenation catalyst containing bimodal pore size distribution carrier, in catalyst quality 100 parts, catalyst (1) 0.02 ~ 0.15 part of palladium composed of the following components, (2) silver, mass ratio 9 ~ the 1:1 of silver and palladium, (3) 0.02 ~ 0.6 part, auxiliary agent rare earth element, palladium, silver, rare earth are all in element quality, it is characterized in that the carrier of catalyst is the alumina support with bimodal pore size distribution, this 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.
9. catalyst according to claim 8, is characterized in that the rare earth element in catalyst is lanthanum; Addition 0.03 ~ 0.5 part.
10. the carbon two front-end hydrogenation catalyst containing bimodal pore size distribution carrier, in catalyst quality 100 parts, catalyst (1) 0.02 ~ 0.15 part of palladium composed of the following components, (2) silver, mass ratio 9 ~ the 1:1 of silver and palladium, (3) alkali metal and/or base earth metal promoter 0.03 ~ 0.8 part, (4) 0.02 ~ 0.6 part, auxiliary agent rare earth element, palladium, silver, alkali metal and/or alkaline-earth metal, rare earth is all in element quality, it is characterized in that the carrier of catalyst is the alumina support with bimodal pore size distribution, this 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.
The preparation method of catalyst described in 11. 1 kinds of claims 6,8 or 10: preparation has the alumina support of bimodal pore size distribution: by aluminium oxide, expanding agent blending, expanding agent addition is 3 ~ 15% of alumina weight, the even aftershaping of kneading, dry, at 1000 ~ 1400 DEG C, roasting 2 ~ 8 hours; Then carrier impregnation entered in the solution containing palladium, silver, filtration, washing, dry, roasting, obtain catalyst.
12. preparation methods according to claim 11, it is characterized in that expanding agent is selected from sesbania powder, citric acid, methylcellulose, starch, polyvinyl alcohol, PVOH and carbon black one or more.
13. preparation methods according to claim 11, when it is characterized in that catalyst contains auxiliary agent, carrier impregnation enters containing palladium, silver, is selected from alkali metal, alkaline-earth metal or rare earth metal auxiliary agent one or more solution, filter, washing, dry, roasting, obtain catalyst.
14. preparation methods according to claim 13, synchronous or step impregnation when it is characterized in that the solution that carrier impregnation enters containing one or more in palladium, silver and auxiliary agent, the pH value of maceration extract is 1.0 ~ 5.0,80 ~ 250 DEG C of dryings 2 ~ 20 hours after carrier filtration after dipping, washing, 350 ~ 650 DEG C of roastings 2 ~ 10 hours, obtain catalyst.
15. preparation methods according to claim 14, step impregnation when it is characterized in that the solution that carrier impregnation enters containing one or more in palladium, silver and auxiliary agent: (1) is with containing palladium solution impregnating carrier, dry, roasting is the salting liquid 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 alkali metal, alkaline-earth metal or rare earth metal auxiliary agent again, dry, roasting obtains catalyst.
16. preparation methods according to claim 11, is characterized in that 100 ~ 150 DEG C of dryings, roasting 4 ~ 6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110267207.1A CN102989454B (en) | 2011-09-09 | 2011-09-09 | Containing the carbon two front-end hydrogenation Catalysts and its preparation method of bimodal pore size distribution carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110267207.1A CN102989454B (en) | 2011-09-09 | 2011-09-09 | Containing the carbon two front-end hydrogenation Catalysts and its preparation method of bimodal pore size distribution carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102989454A CN102989454A (en) | 2013-03-27 |
| CN102989454B true CN102989454B (en) | 2016-02-10 |
Family
ID=47918859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110267207.1A Active CN102989454B (en) | 2011-09-09 | 2011-09-09 | Containing the carbon two front-end hydrogenation Catalysts and its preparation method of bimodal pore size distribution carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102989454B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104096572B (en) * | 2013-04-03 | 2016-05-11 | 中国石油天然气股份有限公司 | A kind of selective hydrogenation catalyst that improves anti-coking |
| 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN101066530A (en) * | 2006-05-22 | 2007-11-07 | 林方 | Hydrodemetalizing catalyst and its prepn |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7932408B2 (en) * | 2006-09-29 | 2011-04-26 | Scientific Design Company, Inc. | Catalyst with bimodal pore size distribution and the use thereof |
-
2011
- 2011-09-09 CN CN201110267207.1A patent/CN102989454B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4448896A (en) * | 1981-06-02 | 1984-05-15 | Mitsubishi Chemical Ind., Ltd. | Hydrogenation catalyst for desulfurization and removal of heavy metals |
| CN101066530A (en) * | 2006-05-22 | 2007-11-07 | 林方 | Hydrodemetalizing catalyst and its prepn |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102989454A (en) | 2013-03-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102989452B (en) | C2 front-end hydrogenation catalyst containing composite carrier and preparation method | |
| CN102247896B (en) | Alumina-zirconia composite carrier and preparation method thereof | |
| CN101433842B (en) | Hydrogenation catalyst and preparation method thereof | |
| CN103657670B (en) | Drippolene nickel system selective hydrocatalyst and preparation method thereof | |
| CN102989453B (en) | C2 front-end hydrogenation catalyst and preparation method | |
| CN100398202C (en) | Process for preparing Cu-Zn-Al vapor hydroformylation catalyst and products therefrom | |
| CN103506150B (en) | The catalyst of preparing gasoline by methanol and method for making thereof and application is used for by steam modification | |
| CN102989517B (en) | Alumina support of bimodal pore size distribution and preparation method thereof | |
| CN102294242B (en) | C2 front-end hydrogenation catalyst and preparation method thereof | |
| CN101927169A (en) | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof | |
| WO2015007230A1 (en) | Iron-based hydrogenation catalyst and applications thereof | |
| CN102989454B (en) | Containing the carbon two front-end hydrogenation Catalysts and its preparation method of bimodal pore size distribution carrier | |
| CN102451695A (en) | Preparation method of copper base catalyst for methanol synthesis | |
| CN103769118B (en) | Heavy oil hydrogenation catalyst and preparation method thereof | |
| CN102989516B (en) | Alumina-titanium oxide composite carrier and preparation method | |
| CN105727951A (en) | Selective hydrogenation catalyst and preparation method thereof | |
| CN104028267A (en) | Method for preparing cyclohexane precious metal Ru catalyst by benzene selective hydrogenation | |
| CN102989518B (en) | Alumina-zirconia-titania composite carrier and its preparation method | |
| CN104190424B (en) | A kind of sec-butyl alcohol dehydrogenizing preparing ethyl methyl ketone catalyst and preparation method thereof | |
| CN101618346B (en) | Method for preparing silicon and zirconium containing aluminum oxide carrier | |
| CN112657506A (en) | Preparation method of catalyst for preparing isobutanol from synthesis gas | |
| CN103418379B (en) | Remove the Catalysts and its preparation method of alkadienes in carbon four | |
| CN106423202A (en) | Preparation method of rhodium-ruthenium composite catalyst for preparing ethyl alcohol through acetic acid hydrogenation | |
| CN111841544A (en) | Catalyst for preparing alcohol by aldehyde hydrogenation and preparation method thereof | |
| CN109420507A (en) | A kind of Hydrobon catalyst and preparation method thereof containing macropore alumina supporter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |