CN108786928A - A kind of diesel oil hydrogenation catalyst carrier and preparation method thereof - Google Patents
A kind of diesel oil hydrogenation catalyst carrier and preparation method thereof Download PDFInfo
- Publication number
- CN108786928A CN108786928A CN201710543035.3A CN201710543035A CN108786928A CN 108786928 A CN108786928 A CN 108786928A CN 201710543035 A CN201710543035 A CN 201710543035A CN 108786928 A CN108786928 A CN 108786928A
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- CN
- China
- Prior art keywords
- diesel oil
- catalyst carrier
- carrier
- oil hydrogenation
- hydrogenation catalyst
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Classifications
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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Abstract
The invention discloses a kind of diesel oil hydrogenation catalyst carriers and preparation method thereof, and on the basis of the catalyst carrier, the catalyst carrier includes the solid fiber silk and 5wt%~20wt% modified additives of 5wt~20wt%, and surplus is aluminium oxide.The preparation method is to mix aluminium oxide, modified additive, solid fiber silk, the modified diesel oil hydrogenation catalyst carrier with the medium and small duct of perforation is obtained through overmolding, roasting, wherein, the element of the modified additive is nonmetalloid or group ivb metallic element, and the modified additive is in terms of oxide.The carrier of the present invention has the medium and small duct of perforation, improve 5% or more inner surface of the carrier accessibility, improve the utilization rate of catalyst active center, reduce medium resistance to mass tranfer, increase active metal component in the carrier to disperse, increase modulation of the lengthy and jumbled ability of catalyst simultaneously by modified additive to surface acidity, the hydrodesulfurization, hydrodenitrogeneration and aromatic hydrocarbons for improving diesel oil hydrogenation catalyst are saturated performance.
Description
Technical field
The present invention relates to a kind of diesel oil hydrogenation catalyst carrier, the carrier is refined particularly useful for making diesel oil fraction hydrogenating
Catalyst.
Background technology
As the diesel quality standard that China executes is increasingly strict, the market demand of high quality cleaning diesel oil increases year by year.
Accelerate diesel quality upgrading, production high quality cleaning diesel oil is one of the major tasks of current Petrochemical Enterprises.For existing diesel oil
Hydrogenation plant carries out diesel quality upgrading, and the means that can be taken at present are mainly anti-including reducing unit capacity, raising device
Severity is answered, diesel-fuel end point is reduced and uses high activity diesel oil hydrogenation catalyst.It reduces unit capacity, improve device reaction
The measures such as severity, reduction diesel-fuel end point adversely affect the production cost and production efficiency of device.Therefore, using height
Active diesel oil hydrogenation catalyst is the most effective measure that diesel hydrotreating unit carries out diesel quality upgrading.
Hydrofinishing means are the most effective solutions of diesel oil distillate production ultra-low-sulphur diesel.As crude oil is increasingly bad
The continuous improvement of matter and environmental requirement, to diesel oil hydrofining catalyst, more stringent requirements are proposed, and traditional diesel oil adds
Hydrogen catalyst for refining exposes that catalyst duct is open insufficient, acid distribution is unreasonable, catalysis when producing ultra-low-sulphur diesel
The shortcomings of agent active sites are single, catalyst activity is relatively low, recyclability is not strong.
Carrier plays load active component in Hydrobon catalyst and obtains the important function of high degree of dispersion active component,
Research is modified to carrier to realize the hot spot for becoming research to the deep hydrofinishing of oil product.Traditional diesel oil hydrofining
Catalyst mostly uses greatly γ-Al203For carrier, mainly due to γ-Al203Good, specific surface and hole knot with mechanical stability
The advantages that structure is easy to control, cheap, research also show γ-A1203It can not only play the role of inert carrier, to active phase
Formation also has certain facilitation.But γ-Al203Being used as hydrofining catalyst carrier, there is also apparent defects：On the one hand
The generation for promoting Ni (Co) aluminate with the strong interaction of active component, so as to cause Mo and Co (Ni) units activities center
Intrinsic reactivity reduce, be not easy to form the II class activity phases of high activity；Another aspect γ-Al203Pore-size distribution is wide and only exists weak
Sour position (only L acid is without B acid), is unfavorable for the fracture of C-S keys in DBT (dibenzothiophenes).To produce based on ultra-low-sulphur diesel
Epoch, need to develop new diesel oil hydrofining catalyst carrier or new alumina material modified method.
With going deep into for research, it was recognized that for loaded catalyst, activity of the carrier pore structure to load
Reactants and products in the dispersion degree and reaction process of component are spread in catalyst and mass transfer has important influence, therefore,
Catalyst activity, selectivity, service life etc. are all closely related with the pore structure of carrier.The catalyst carrier prepared using conventional method
Because duct is unfavorable for the diffusion of reactant there are forms such as blind hole, tortuous hole, broken end holes, and easily forms coking carbon distribution and draw
Play catalyst inactivation.For with the more complex aromatic hydrocarbons of larger space steric hindrance class sulfide and molecular structure, catalysis is reduced
The tortuosity in agent duct improves duct connectivity and is had a significant impact to catalyst activity.
ZL 200410091490.7 discloses a kind of Hydrobon catalyst containing molecular sieve, and the carrier of catalyst uses
Aluminium oxide (20.0wt%~80.0wt% of catalyst weight) and ETS-10 molecular sieves (0.5wt% of catalyst weight~
It 50.0wt%) is prepared, by adjusting the aluminium oxide and ETS-10 molecular sieve relative amounts in carrier, and to ETS-10 molecules
Sieve is modified to prepare hydrodesulfurization catalyst support, and the desulphurizing activated of conventional hydrodesulfurization catalyst can be improved.
105772109 A of CN disclose a kind of support preparation method：First by the short grained Y molecules of high silica alumina ratio
Sieve carries out ammonium nitrate contact and exchanges；Then the Y molecular sieve of exchange is subjected to modified zirconia, obtains modified zirconia Y molecular sieve；The zirconium is changed
Property Y molecular sieve mixed with boehmite, extrusion aid, binder, then extrusion drying roasting again, is prepared plus hydrogen is de-
The carrier of sulfur catalyst.The carrier for the Hydrobon catalyst that the invention provides has modified zirconia Y molecular sieve, what which prepared
The desulphurizing activated height of Hydrobon catalyst, desulfurization effect are good；And Hydrobon catalyst prepared by the carrier is for adding hydrogen de-
Reaction of Salmon-Saxl, the yield of diesel oil is 100% or more.
103480408 A of CN disclose a kind of diesel oil distillate oil hydrogenation catalysts containing rare earth and its preparation and application；It should
Catalyst is made of rare earth modified USY molecular sieve, amorphous silicon aluminium, macroporous aluminium oxide and hydrogenation active component, wherein adding
Hydrogen activity group is divided into group VIII metal, containing rare earth modified USY molecular sieve 5-60wt%, 5- containing amorphous silicon aluminium in catalyst
80wt%, the 0.1-10wt% of metal containing group VIII, surplus is macroporous aluminium oxide；The catalyst, which has, preferably adds hydrogen, isomery
It, can be significantly under the reaction condition relatively mitigated when handling FCC hydrofining diesel oil distillates with arenes selectivity open loop activity
Cetane number is improved, condensation point is reduced, improves product quality, and keep 95% or more diesel yield, the addition of rare earth element improves
The activity of catalyst and service life, the aromatic hydrocarbons deep hydrogenation saturation of second segment is then selected in being modified particularly suitable for diesel oil two-stage hydrogenation
The open loop of selecting property.
102284300 A of CN disclose a kind of poor ignition quality fuel hydrogenation catalyst and preparation method；The catalyst is with W-Mo-
Ni-P is active component, using alkali metal, alkaline-earth metal or rare earth metal as auxiliary agent, using sial as carrier, by weight percentage, alkali
Metal, alkaline-earth metal or rare earth metal are 0.2~10%, WO3For 5%~25%, MoO3It is 2~9% for 8~20%, NiO, P
It is 1.0~5%, surplus is sieve and silica-sesquioxide carrier；It, should for evaluating the miscella that feedstock oil is catalytic cracking and coker gas oil
Catalyst shows good reactivity and stability in condition and stability test, can remove in mixed diesel inferior
90% or more sulphur, nitrogen.
102211029 A of CN disclose a kind of preparation method of diesel hydrogenation for removal sulphur sulfide catalyst, with W metal or
Co and Mo and Ru is active component, Al2O3For carrier, the ethylenediamine solution of ammonium molybdate is configured, after carrier impregnation is added, is added
The KBH of 0.1mol/L4Solution, Mo: B molar ratio is 1: 4, after gained precipitation washing, dries and is urged in 110 DEG C of baking ovens
Agent precursor；The ethylenediamine mixed solution for configuring nickel nitrate and nitric acid ruthenium, into solution catalyst precursor is added carries out etc.
Volume impregnation, naturally dry, 120 DEG C of drying roast at 450 DEG C, vulcanize to urge at 350 DEG C under H2S atmosphere gained precipitation again
Agent；It is 3~20% by catalyst weight ratio Mo；Ni or Co is 3~10%；Ru is 0.1~3%；Al2O3For surplus；Catalyst
With high hydrodesulfurization activity, it to be used for hydrofinishing and raw material prerefining hydrodesulfurization.
CN200810113646.5 discloses a kind of diesel oil hydrofining catalyst, and the catalyst is by carrier and active component
It constitutes, the active component is one or more in vib metals and group VIII metal, wherein the carrier is by having
SAPO-5, SAPO-11 of one-dimensional channels, the one or more and γ-Al of ZSM-22, ZSM-23 molecular screen2O3Composition.The invention
The preparation method of above-mentioned catalyst is also further disclosed on the basis of disclosing above-mentioned diesel oil hydrofining hydrogenation catalyst.Make
The diesel oil hydrofining catalyst being prepared with above-mentioned preparation method can prevent diesel oil distillate cracking, realize poor ignition quality fuel
While aromatic hydrogenation is saturated, effectively realizes and desulfurization and denitrogenation are carried out to poor ignition quality fuel.
CN200910188174.4 discloses a kind of body phase ultra-deep hydrodesulfuration catalyst and preparation method thereof.The catalysis
Agent composition includes composite oxides NixWyOz, MoO3, aluminium oxide and micropore and mesoporous composite molecular screen.This method is in Ni, W
Be added suitable water-soluble nitrogenous compound in Al precipitation processes, after plastic, composite molecular screen slurries are added, through aging, then
With MoO3After mashing, it is made through molding, activation.This method not only improves the pore structure of catalyst, and more metals is made to live
Property position be exposed to the surface of catalyst, improve the utilization rate of active metal, but also make composite molecular screen and hydrogenation activity gold
Belong to uniform, fully contact, and preferably coordinate with hydrogenation active metals, gives full play to the performance of composite molecular screen, reach bavin
The effect of oily ultra-deep desulfurization, especially in processing macromolecular content more distillate, effect becomes apparent from, can be by diesel oil
Sulfur content drops to 10 μ g/g or less.
CN101591564A discloses a kind of method of diesel oil distillates in direct coal liquefied oil hydrofinishing, predominantly raw material with
Enter in first reactor after hydrogen mixing, is first connect with the non-noble metal hydrogenation catalyst for refining loaded in the first reactor
It touches, then is contacted with non-noble metal hydrogenation modifying catalyst；The reaction effluent of first reactor removes impurity gas by separating dehydrogenated
Enter second reactor after body, is contacted with the noble metal hydrogenation catalyst loaded in the second reactor, second reactor
Reaction effluent passes through isolated diesel product；Wherein, the first reactor process conditions are：280-400 DEG C of temperature, hydrogen
Divide 4.0-12.0MPa, hydrogen to oil volume ratio 300Nm3/m3, liquid hourly space velocity (LHSV) 0.5-2.5h-1；The second reactor process conditions
For：220-400 DEG C of temperature, hydrogen partial pressure 4.0-12.0MPa, hydrogen to oil volume ratio 300Nm3/m3, liquid hourly space velocity (LHSV) 0.5-2.5h-1；It is described
Non-noble metal hydrogenation catalyst for refining is made of non-acidic support and active component, and the active component is VIII in the periodic table of elements
The oxide of the oxide of race's metal and/or VI B races metal；The carrier is molecular sieve, zeolite, heat-resistant inorganic oxide, work
It is one or more in property charcoal, carbon fiber, clay.The invention adds hydrogen by using two-stage method, and liquefied coal coil diesel oil can be made to evaporate
Sub-prime measures improvement, and arene content reduces, and Cetane number improves, and operating condition mitigates, equipment investment and operating cost
It reduces, used catalyst is conventional catalyst.
201110197778.2 disclose a kind of preparation method of the catalyst carrier of the big mesoporous with perforation, this method
Including：Solid fiber silk is added in catalyst carrier preparation or forming process, solid fiber silk is made to be dispersed in catalyst carrier
In, then solid fiber silk is removed to get to the catalyst carrier of the big mesoporous with perforation through being molded, roasting.The invention is also
It provides and the carrier is further supported to the method that active component prepares catalyst, additionally provide the method preparation according to the invention
Obtained carrier and catalyst.Using the method for the invention, the addition of solid fiber silk significantly improves duct in carrier
Penetrate through performance.The penetrated macropore that filament generates provides the quick diffusion admittance of reaction molecular, to reduce catalysis reaction
The resistance to mass tranfer of process.This method is suitable for preparing various catalyst of the reaction speed by interior diffusion control, such as petroleum cuts
(especially mink cell focus fraction) hydrogenation catalyst.
Above-mentioned patent improves the performance of catalyst either by the compound of catalyst carrier or by expanding agent, and
Certain effect is achieved, but does not obtain the catalyst and load with medium and small duct through hole suitable for diesel oil hydrogenation
Body.
Invention content
It is existing to overcome the main purpose of the present invention is to provide a kind of diesel oil hydrogenation catalyst carrier and preparation method thereof
The defect that the duct connectivity of medium and small duct catalyst carrier is poor in technology, crush strength is low.
In order to achieve the above object, the present invention provides a kind of diesel oil hydrogenation catalyst carriers, are with the catalyst carrier
Benchmark, the catalyst carrier include the solid fiber silk and 5wt%~20wt% modified additives of 5wt%~20wt%, surplus
Element for aluminium oxide, the modified additive is nonmetalloid or group ivb metallic element, and the modified additive is with oxide
Meter.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein the solid fiber silk average length is preferably 0.1 milli
Rice~1 millimeter, diameter is preferably 0.1 micron~30 microns.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein the solid fiber silk is preferably natural fiber, synthesis
Or mixtures thereof fiber.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein the natural fiber is preferably woody fiber, draft fibre
Dimension, seed wool fibre or silk.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein the synthetic fibers are preferably polyacrylonitrile fibre, gather
Dimethyl terephthalate (DMT) fiber, polyolefine fiber, polyurethane fiber, Fypro or vinylon.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein the element of the modified additive be preferably titanium, zirconium, boron,
Carbon, silicon, phosphorus, selenium or tellurium.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein it is preferred that the diesel oil hydrogenation catalyst carrier is also
Including adhesive, on the basis of the catalyst carrier, described adhesive weight content is preferably 0~30wt%.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein it is preferred that the diesel oil hydrogenation catalyst carrier is also
Including extrusion aid.
Diesel oil hydrogenation catalyst carrier of the present invention, wherein the crushing strength of the catalyst carrier is preferably greater than
155N/CM, inner surface of the carrier accessibility improve 5% or more, and specific surface area is preferably 310m2/ g~370m2/ g, hole hold preferred
For 0.45ml/g~0.65ml/g, wherein aperture accounts for the 76%~86% of total pore volume in the pore size distribution of 5nm~12nm.
In order to achieve the above object, the present invention also provides a kind of preparation method of diesel oil hydrogenation catalyst carrier, the systems
Preparation Method is to mix aluminium oxide, modified additive, solid fiber silk, and the medium and small with penetrating through of modification is obtained through overmolding, roasting
The diesel oil hydrogenation catalyst carrier in duct, on the basis of the catalyst carrier, which includes 5wt%~20wt%'s
The aluminium oxide of solid fiber silk, 5wt%~20wt% modified additives and surplus, wherein the element of the modified additive is non-
Metallic element or group ivb metallic element, the modified additive is in terms of oxide.
Beneficial effects of the present invention：
The present invention develops a kind of diesel oil hydrogenation catalyst carrier, the carrier use Group IVB element and nonmetalloid for
The crushing strength of carrier, acidity, support chemistry property is adjusted in modified additive, by appropriate modification, can adjust
Support acidity and surface chemical property improve since the shortcomings that support strength that a large amount of solid fiber silk ribbons come becomes smaller is added, make
Carrier after adjusting disclosure satisfy that industrial production needs；
In addition, modified additive can also improve state of the solid fiber silk in carrier forming process, strong acid is avoided to help crowded
The influence to solid fiber silk such as agent successfully builds medium and small duct perforation diesel oil hydrogenation catalyst carrier；
Finally, the present invention improves the surface nature of carrier while realizing that medium and small duct penetrates through in carrier, in carrier
Surface accessibility improves 5% or more, improves the activated centre utilization rate of the catalyst based on the carrier, is conducive to improve bavin
The Hydrogenation of oil hydrogenation catalysts.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The diesel oil hydrogenation catalyst carrier of the present invention includes following component：Aluminium oxide, modified additive, solid fiber silk and
Extrusion aid.The content of each component is as follows in carrier：On the basis of the weight percent of carrier, solid fiber silk is relative to carrier
Total weight content is 5wt%~20wt%, preferably 7wt%~18wt%, further preferably 10wt%~15wt%；Modification helps
Agent is 5wt%~20wt%, preferably 7wt%~18wt%, further preferably 10wt% relative to the total weight content of carrier
~15wt%；Extrusion aid is 0~30wt%, preferably 0~20wt% relative to the content of carrier.
The diesel oil hydrogenation catalyst carrier of the present invention is main constituents with aluminium oxide, modified additive, solid fiber silk,
Wherein aluminium oxide is main carriers component, and thermal stability is good, pore-size distribution is suitable for diesel oil hydrogenation catalyst, modified additive conduct
The crushing strength of carrier, the conditioning agent of acidity, support chemistry property, by appropriate modification, can adjust support acidity and
Surface chemical property improves since the shortcomings that support strength that a large amount of solid fiber silk ribbons come becomes smaller is added, makes the load after adjusting
Body disclosure satisfy that industrial production needs, while modified additive can also improve shape of the solid fiber silk in carrier forming process
State avoids the influence to solid fiber silk such as strong acid extrusion aid, middle aperture of the solid fiber silk as structure perforation in carrier
Road can increase the specific surface area and diffusion of carrier.
There is no particular restriction to used aluminium oxide by the present invention, alumina precursor commonly used in the art, such as work
Industry boehmite has the pore-size distribution suitable for diesel oil hydrogenation catalyst.
The catalyst of the present invention can be used common inorganic oxide as the adhesive component of catalyst when prepared by carrier,
Such as clay, the weight content of adhesive component in the final catalyst are 0~30%.Diesel oil hydrogenation catalyst carrier of the present invention
Adhesive component can not also be added when preparation, but be directly added into Ludox, kneading extruded moulding.
The present invention is in the preparation process of catalyst carrier, and extrusion aid can be used in when extrusion, and common extrusion aid can be
One or more of sesbania powder, citric acid, acetic acid, tartaric acid, oxalic acid, cellulose, starch, high molecular surfactant, it is excellent
Choosing is sesbania powder, citric acid, acetic acid and high molecular surfactant.
The shape of the catalyst carrier of the present invention can be sheet, spherical shape, cylindrical bars or irregular strip (clover, four leaves
Grass), preferably cylindrical bars and irregular strip (clover, bunge bedstraw herb).The diameter of catalyst can be the slice of 0.5mm~2.5mm
Or>The thick item of 2.5mm, the preferably slice of 1.0mm~1.8mm.
The crushing strength of the diesel oil hydrogenation catalyst carrier of the present invention is more than 155N/CM, specific surface area 310m2/ g~
370m2/ g, Kong Rongwei 0.45ml/g~0.65ml/g, wherein aperture the pore size distribution of 5nm~12nm account for total pore volume 76%~
86%.
Diesel oil hydrogenation catalyst carrier of the present invention, solid fiber silk be natural fiber, synthetic fibers or they
Mixture；Preferred natural fiber includes plant fiber and animal origin, such as woody fiber, Herbaceous Fiber, seed hair fibre
Dimension and silk etc.；Synthetic fibers refer to artificial synthesized various organic polymer fibers, such as：Polyacrylonitrile fibre gathers to benzene
Dicarboxylic acid dimethyl ester fiber, polyolefine fiber, polyurethane fiber, Fypro or vinylon etc.；More preferably
, the solid fiber silk average length is 0.1 millimeter~1 millimeter, 0.1 micron~30 microns of filament diameter.Modified additive
For group ivb element and nonmetalloid, preferred modified additive element is：Titanium, zirconium, boron, carbon, silicon, phosphorus, selenium and tellurium.
Catalyst carrier preparation method of the present invention is, by aluminium oxide, modified additive, solid fiber silk, binder
And extrusion aid, it is mixed in a certain ratio uniformly, is obtained with certain specific surface area and duct after extruded moulding, drying, roasting
The carrier material of structure.
Sulfide in document report diesel oil is broadly divided into four classes in addition to a small amount of thiophene derivant：1. alkyl benzo thiophene
Pheno；2. dibenzothiophenes and alkyl substituents are not in 4 or 6 methyldibenzothiophenes；3. only there are one alkyl at 4 or
6 methyldibenzothiophenes；4. having alkyl-substituted methyldibenzothiophene in 4 and 6.Above-mentioned four classes sulfide accounts for
The ratio of total sulfur content respectively may be about 39%, 20%, 26%, 15% in diesel oil, and the hydrogenation phase of all kinds of sulfide is to reaction rate
Constant ra-tio is respectively 36,8,3,1.Even if under the reaction condition of high temperature or low-speed, the 4th group of sulfur species are still difficult to remove,
And the reaction rate constant of thiophene derivant is its 100 times.Therefore, during diesel oil hydrofining, effectively removing 4 and 6
There is alkyl-substituted methyldibenzothiophene in position, is the key that production sulfur content is less than 10 μ g/g ultra-low-sulphur diesels.4,6- bis-
Methyldibenzothiophene is the representative species in the 4th class sulfur species.Studies have shown that it is difficult to the major influence factors of hydrodesulfurization
It is due to its space steric effect, secondly because the duct being not penetrated in catalyst affects the biography of medium in the catalyst
Matter, and then the hydrodesulfurization efficiency of catalyst is affected, in catalyst catalyst activity will be influenced if there is dead hole, blind hole
The dispersion of metal component prevents the Hydrogenation of catalyst from playing completely.
The present invention provides a kind of diesel oil hydrogenation catalyst carrier, diesel oil hydrogenation catalyst carrier provided by the invention, tool
Have by modified medium and small perforation duct, there is high mechanical strength, large pore volume, surface with the diesel oil hydrogenation catalyst of its preparation
Acid amount is moderate, when for diesel oil hydrogenation processing, with bed pressure drop is small, reaction temperature is low, the active high, aromatic hydrocarbons of hydrogenation desulfurization and denitrogenation
The features such as saturability is strong reduces the resistance to mass tranfer of medium, makes catalysis simultaneously because having the medium and small duct of perforation in carrier
Agent has that lengthy and jumbled ability is big, and the strong feature of anti-coking performance improves the dispersion of active metal component, has promoted steric hindrance
The removing of sulfide.
The following examples will be further described a kind of catalyst carrier provided by the invention, but not therefore
And limit the present invention.
Solid fiber silk used in embodiment is mainly plant fiber, animal origin silk and synthetic fibres, solid
Filament is to be obtained after special process is handled, and pass through break process, is sieved by 200 mesh, and selection screening is lower solid
Body filament.
Comparative example 1
100g boehmites (aluminium oxide butt 70wt%) are taken, 5g sesbania powders are added, are uniformly mixed, 7.5g nitric acid is added dropwise
(68wt%), 5g citric acids and 100g deionized waters composition mixed solution kneading, extrusion at 1.5mm trifolium-shaped, 120 DEG C
Dry 2h, 4h is then roasted at 550 DEG C, carrier D-1 is made.The physico-chemical property of carrier is shown in Table 1.
Comparative example 2
100g boehmites (aluminium oxide butt 70wt%) are taken, 2.8g cornstalk solid fibers silk, 5g sesbania powders is added,
It is uniformly mixed, the mixed solution kneading being made of 7.5g nitric acid (68wt%), 5g citric acids and 100g deionized waters, extrusion is added dropwise
At the trifolium-shaped of 1.5mm, then 120 DEG C of dry 4h roast 4h at 550 DEG C, carrier D-2 are made.The physico-chemical property of carrier is shown in
Table 1.
Comparative example 3
100g boehmites (aluminium oxide butt 70wt%) are taken, 10g needlebush solid fibers silk, 5g sesbania powders is added,
It is uniformly mixed, the mixed solution kneading being made of 7.5g nitric acid (68wt%), 5g citric acids and 100g deionized waters, extrusion is added dropwise
At the trifolium-shaped of 1.5mm, then 120 DEG C of dry 4h roast 4h at 550 DEG C, carrier D-3 are made.The physico-chemical property of carrier is shown in
Table 1.
Comparative example 4
100g boehmites (aluminium oxide butt 70wt%) are taken, 5g needlebush solid fibers silk, 5g sesbania powders is added, are mixed
Close uniform, be added dropwise the mixed solution kneading being made of 7.5g nitric acid (68wt%), 5g citric acids and 100g deionized waters, extrusion at
Then the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h roast 4h at 550 DEG C, carrier D-4 are made.The physico-chemical property of carrier is shown in Table
1。
Comparative example 5
100g boehmites (aluminium oxide butt 70wt%) are taken, 10g cornstalk solid fibers silk, 5g sesbania powders is added,
It is uniformly mixed, the mixed solution kneading being made of 7.5g nitric acid (68wt%), 5g citric acids and 100g deionized waters, extrusion is added dropwise
At the trifolium-shaped of 1.5mm, then 120 DEG C of dry 4h roast 4h at 550 DEG C, carrier D-5 are made.The physico-chemical property of carrier is shown in
Table 1.
Embodiment 1
100g boehmites (aluminium oxide butt 70wt%) are taken, 20g cornstalk solid fibers silk, 5g sesbania powders is added,
It is uniformly mixed, is added dropwise by 7.5g nitric acid (68wt%), 5g citric acids, modified additive 5.0g silica 5.0g metatitanic acids, 100g is gone
Then the mixed solution kneading of ionized water composition, extrusion roast 4h at the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h at 550 DEG C,
Carrier 1 is made.The physico-chemical property of carrier is shown in Table 1.
Embodiment 2
100g boehmites (aluminium oxide butt 70wt%) are taken, 10g cornstalk solid fibers silk, 5g sesbania powders is added,
It is uniformly mixed, is added dropwise by 7.5g nitric acid (68wt%), 5g citric acids, modified additive 12.5g silica and 100g deionized water groups
At mixed solution kneading, extrusion is at the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h, and 4h is then roasted at 550 DEG C, carrier is made
2.The physico-chemical property of carrier is shown in Table 1.
Embodiment 3
100g boehmites (aluminium oxide butt 70wt%) are taken, 10g polyethylene terephthalate fibers, modification is added
Auxiliary agent 12.5g metatitanic acids, 5g sesbania powders are uniformly mixed, and are added dropwise by 7.5g nitric acid (68wt%), 5g citric acids and 100g deionizations
Then the mixed solution kneading of water composition, extrusion roast 4h at 550 DEG C, are made at the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h
Carrier 3.The physico-chemical property of carrier is shown in Table 1.
Embodiment 4
100g boehmites (aluminium oxide butt 70wt%) are taken, 10g polyethylene terephthalate fibers, modification is added
Auxiliary agent 25g metatitanic acids, 5g sesbania powders are uniformly mixed, and are added dropwise by 7.5g nitric acid (68wt%), 5g citric acids and 100g deionized waters
Then the mixed solution kneading of composition, extrusion roast 4h at 550 DEG C, load are made at the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h
Body 4.The physico-chemical property of carrier is shown in Table 1.
Embodiment 5
100g boehmites (aluminium oxide butt 70wt%) are taken, 5g mulberry silk solid fibers silk, modified additive 5g is added
Zirconium oxide, 5g sesbania powders are uniformly mixed, what dropwise addition was made of 7.5g nitric acid (68wt%), 5g citric acids and 100g deionized waters
Then mixed solution kneading, extrusion roast 4h at 550 DEG C, carrier 5 are made at the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h.It carries
The physico-chemical property of body is shown in Table 1.
Embodiment 6
100g boehmites (aluminium oxide butt 70wt%) are taken, 10g mulberry silk solid fibers silk, modified additive 5g is added
Zirconium oxide, 5g sesbania powders are uniformly mixed, and are added dropwise by 7.5g nitric acid (68wt%), 5g citric acids, modified additive 12.5g Ludox
With the mixed solution kneading of 100g deionized waters composition, extrusion is at the trifolium-shaped of 1.5mm, 120 DEG C of dry 4h, then 550
DEG C roasting 4h, carrier 6 is made.The physico-chemical property of carrier is shown in Table 1.
1 carrier physico-chemical property of table
Remarks：Inner surface accessibility：The accessibility carrier specific surface area of reactant molecule accounts for the total specific surface area of carrier
Ratio.
Comparative example 2-5 is added to the specific surface area and Kong Rongyu of the carrier of solid fiber silk it can be seen from the data of table 1
Compared to increased, hole holds maximum and increases 108.6% comparative example 1, and specific surface area maximum increases 56.6%, and carrier
Crushing strength maximum reduces 138.6%, and inner surface accessibility maximum improves 7.5%, it can be seen that solid fiber silk
Being added contributes to the increase of carrier pore structure and specific surface area, but affects the crushing strength of carrier；
And study in find, when the additive amount of solid fiber silk be less than 5wt% when, the above contradiction be not it is very prominent, when
When additive amount is within the scope of 5~20wt%, need to solve the contradiction；
By introducing modified additive into carrier, modified additive is as the crushing strength of carrier, acidity, support chemistry property
Conditioning agent support acidity and surface chemical property can be adjusted by appropriate modification, improve since a large amount of solids are added
The shortcomings that support strength that filament is brought becomes smaller makes the carrier after adjusting disclosure satisfy that industrial production needs, while modification helps
Agent can also improve state of the solid fiber silk in carrier forming process, avoid extrusion aids such as strong acid etc. to solid fiber silk
Influence, make solid fiber silk as the medium and small duct of structure perforation in carrier, and specific surface area and the diffusion of carrier can be increased
Performance.Increase the carrier crushing strength maximum after modified additive and improve 150%, the crushing strength of carrier is made to meet industrial production
It is required that.(industrial crushing strength generally requires to be more than 150, and excessively high crushing strength not only influences the aperture of carrier
Distribution, while the water absorption rate of carrier can be also influenced, which is not the bigger the better, but meets demand of industrial production.)
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (10)
1. a kind of diesel oil hydrogenation catalyst carrier, which is characterized in that on the basis of the catalyst carrier, the catalyst carrier packet
The solid fiber silk and 5wt%~20wt% modified additives of 5wt%~20wt% are included, surplus is aluminium oxide, the modified additive
Element be nonmetalloid or group ivb metallic element, the modified additive is in terms of oxide.
2. diesel oil hydrogenation catalyst carrier according to claim 1, which is characterized in that the solid fiber silk average length
It is 0.1 millimeter~1 millimeter, a diameter of 0.1 micron~30 microns.
3. diesel oil hydrogenation catalyst carrier according to claim 1, which is characterized in that the solid fiber silk is natural fine
Or mixtures thereof dimension, synthetic fibers.
4. diesel oil hydrogenation catalyst carrier according to claim 3, which is characterized in that the natural fiber is woody fibre
Dimension, Herbaceous Fiber, seed wool fibre or silk.
5. diesel oil hydrogenation catalyst carrier according to claim 3, which is characterized in that the synthetic fibers are polyacrylonitrile
Fiber, polyethylene terephthalate fiber, polyolefine fiber, polyurethane fiber, Fypro or Pioloform, polyvinyl acetal are fine
Dimension.
6. diesel oil hydrogenation catalyst carrier according to claim 1, which is characterized in that the element of the modified additive is
Titanium, zirconium, boron, carbon, silicon, phosphorus, selenium or tellurium.
7. diesel oil hydrogenation catalyst carrier according to claim 1, which is characterized in that the diesel oil hydrogenation catalyst carrier
Further include adhesive, on the basis of the catalyst carrier, described adhesive weight content is 0~30wt%.
8. diesel oil hydrogenation catalyst carrier according to claim 1 or claim 7, which is characterized in that the diesel oil hydrogenation catalyst
Carrier further includes extrusion aid.
9. diesel oil hydrogenation catalyst carrier according to claim 1, which is characterized in that the crushing of the catalyst carrier is strong
Degree is more than 155N/CM, and inner surface of the carrier accessibility improves 5% or more, specific surface area 310m2/ g~370m2/ g, Kong Rongwei
0.45ml/g~0.65ml/g, wherein aperture account for the 76%~86% of total pore volume in the pore size distribution of 5nm~12nm.
10. the preparation method of claim 1 to 7 any one of them diesel oil hydrogenation catalyst carrier, which is characterized in that the preparation
Method obtains aperture during modified having penetrates through to mix aluminium oxide, modified additive, solid fiber silk, through overmolding, roasting
The diesel oil hydrogenation catalyst carrier in road, on the basis of the catalyst carrier, which includes consolidating for 5wt%~20wt%
The aluminium oxide of body filament, 5wt%~20wt% modified additives and surplus, wherein the element of the modified additive is non-gold
Belong to element or group ivb metallic element, the modified additive is in terms of oxide.
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| CN117467041A (en) * | 2023-12-26 | 2024-01-30 | 天津鲁华泓锦新材料科技有限公司 | Hydrogenated petroleum resin and preparation method thereof |
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