CN106466600A - A kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the application of the catalyst prepared by the method and this catalyst - Google Patents
A kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the application of the catalyst prepared by the method and this catalyst Download PDFInfo
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Abstract
The invention discloses the application of a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and the catalyst prepared by the method and this catalyst, the preparation method of this hydrocatalyst for saturating arylhydrocarbon includes：A, silica alumina carrier ammonium salt solution is impregnated and is dried, obtain impregnated carrier；Wherein, the ratio of described ammonium salt and described silica alumina carrier is 0.01 0.2 moles/100 grams；B, by step a gained impregnated carrier load hydrogenation active metals component, obtain hydrocatalyst for saturating arylhydrocarbon.Using the hydrocatalyst for saturating arylhydrocarbon prepared by this hydrocatalyst for saturating arylhydrocarbon preparation method, when carrying out aromatic hydrogenation saturated reaction, there is higher hydrogenation activity.
Description
Technical field
The present invention relates to a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and by prepared by the method urging
Agent and the application of this catalyst.
Background technology
Aromatic hydrogenation saturation is carried out under relatively low reaction temperature using metal catalyst, is to realize such as
The aromatic hydrogenation saturation material depth such as clean fuel oil, white oil and top-grade lubricating oil base oil takes off one kind of virtue
Effective means.
Because metal mold hydrocatalyst for saturating arylhydrocarbon is to sulfur sensitive, therefore prior art is removed and is needed to adopt sulfur
The hydrogenation catalyst changing state carries out outside refining desulfurization to raw material, and more pay attention to day by day is urged to highly active metal mold
The exploitation of agent, and main in terms of hydrogenation active component, bearer type and method for preparing catalyst etc. pair
Catalyst is studied.
A kind of important way improving catalyst hydrogenation performance is exactly to optimize carrier pore structure, makes active metal
It is distributed on effectively interval and surface, adjust carrier surface property, to improve activity gold further simultaneously
Belong to utilization rate, make active metal all change into effective active center as far as possible.Chinese patent CN
102205241 disclose a kind of aromatic hydrocarbon hydrogenation catalyst using special alumina support, prepare this oxidation
The boehmite crystal characteristic of alumina supporter is different from conventional boehmite.Chinese patent application CN
201110139331 provide the virtue that a kind of aluminium oxide-silicon oxide using the preparation of special aluminium oxide is carrier
Hydrocarbon hydrogenation catalyst, by adjusting support, improves catalyst hydrogenation activity.
Content of the invention
It is an object of the invention to provide a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon and by the method
The catalyst of preparation and the application of this catalyst, made using this hydrocatalyst for saturating arylhydrocarbon preparation method
Standby hydrocatalyst for saturating arylhydrocarbon, when carrying out aromatic hydrogenation saturated reaction, has higher hydrogenation and lives
Property.
To achieve these goals, the present invention provides a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon,
The method includes：A, silicaalumina carrier ammonium salt solution is impregnated and is dried, obtain dipping and carry
Body；Wherein, the ratio of described ammonium salt and described silicaalumina carrier is 0.01-0.2 mole/100
Gram；B, by step a gained impregnated carrier load hydrogenation active metals component, obtain aromatic hydrogenation
Saturation catalyst.
Preferably, the method according to the invention, the ratio of described ammonium salt and described silicaalumina carrier
Example is 0.02-0.05 mole/100 grams.
Preferably, the method according to the invention, the content of aluminium oxide in described silicaalumina carrier
For 60-99 mass %, the content of silicon oxide is 1-40 mass %.
Preferably, the method according to the invention, the preparation method of described silicaalumina carrier includes：
Mixture containing boehmite and silicon-containing compound is carried out successively molding and roasting.
Preferably, the method according to the invention, described silicon-containing compound is selected from esters of silicon acis, silanol, silicon
Ether, silicone, silicone oil, silica gel, Ludox, silicic acid, waterglass, amorphous silica-alumina and zeolite molecular sieve
In at least one.
Preferably, the method according to the invention, described silicon-containing compound is selected from silica gel, Ludox, silicon
At least one in acid and waterglass.
Preferably, the method according to the invention, the condition of described roasting is：Sintering temperature is 400-900 DEG C,
Roasting time is 1-12 hour.
Preferably, the method according to the invention, ammonium salt described in step a be selected from ammonium nitrate, ammonium chloride,
At least one in ammonium carbonate and ammonium hydrogen carbonate.
Preferably, the method according to the invention, described in step a, dry condition is：Baking temperature is
60-120 DEG C, drying time is 2-8 hour.
Preferably, the method according to the invention, hydrogenation active metals component described in step b pass through dipping
Load in described impregnated carrier.
Preferably, the method according to the invention, described hydrogenation active metals group be divided into selected from cobalt, nickel, ruthenium,
At least one in rhodium, palladium and platinum；Gross mass in terms of metal simple-substance and with hydrocatalyst for saturating arylhydrocarbon
On the basis of, in described hydrocatalyst for saturating arylhydrocarbon, the content of hydrogenation active metals component is 0.1-5 matter
Amount %.
Preferably, the method according to the invention, described hydrogenation active metals component contains platinum and palladium；With matter
Gauge on the basis of the gross mass of platinum in hydrocatalyst for saturating arylhydrocarbon and palladium, the mass fraction of described palladium
For 30 mass % to less than 100 mass %.
The present invention also provides the virtue prepared by the preparation method according to hydrocatalyst for saturating arylhydrocarbon of the present invention
Hydrocarbon hydrocatalyst for saturating.
The present invention further provides a kind of hydrocatalyst for saturating arylhydrocarbon of the present invention is in aromatic hydrogenation saturation
Application in reaction, this application includes：Will be former with aromatic hydrogenation saturation for described hydrocatalyst for saturating arylhydrocarbon
Material contacts and aromatic hydrogenation saturated reaction occurs.
Preferably, application according to the present invention, this application also includes：Described aromatic hydrogenation saturation is catalyzed
Agent is contacted with aromatic hydrogenation saturation raw material after hydrogen reducing again and aromatic hydrogenation saturated reaction occurs；Described
The temperature of reduction is 300-550 DEG C, and the time of reduction is 2-10 hour, and Hydrogen Vapor Pressure is 0.01-2.0 million
Handkerchief.
Preferably, application according to the present invention, described aromatic hydrogenation saturation raw material be selected from clean fuel oil,
At least one in white oil and lube base oil.
Preferably, application according to the present invention, the condition of described aromatic hydrogenation saturated reaction is：Reaction temperature
Spend for 200-380 DEG C, hydrogen dividing potential drop is 0.5-15 MPa, liquid volume air speed is 0.1-5 hour-1, hydrogen oil
Volume ratio is 100-3000.
Compared with prior art, the preparation method step of the hydrocatalyst for saturating arylhydrocarbon of the present invention is simple,
And compared with the catalyst providing with prior art, hydrocatalyst for saturating arylhydrocarbon provided by the present invention exists
During for aromatic hydrogenation saturated reaction, there is higher Hydrogenation.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that this place is retouched
The specific embodiment stated is merely to illustrate and explains the present invention, is not limited to the present invention.
The present invention provides a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon, and the method includes：A, general
Silicaalumina carrier ammonium salt solution impregnates and is dried, and obtains impregnated carrier；Wherein, described ammonium
The ratio of salt and described silicaalumina carrier is 0.01-0.2 mole/100 grams, preferably 0.02-0.05
Mole/100 grams；B, by step a gained impregnated carrier load hydrogenation active metals component, obtain
Hydrocatalyst for saturating arylhydrocarbon.
The method according to the invention, described silicaalumina carrier can adopt those skilled in the art
Known silicaalumina carrier, aluminium oxide and silicon oxide in described silicaalumina carrier
Content can for arbitrarily than it is preferable that in described silicaalumina carrier the content of aluminium oxide permissible
For 60-99 mass %, preferably 68-92 mass %, the content of silicon oxide can be 1-40 mass %,
It is preferably 8-32 mass %.It is further preferred that the preparation method of described silicaalumina carrier is permissible
Including：Mixture containing boehmite and silicon-containing compound is carried out successively molding and roasting；Described
Boehmite can adopt boehmite well-known to those skilled in the art or boehmite, that is,
Boehmite or Pseudo-Boehmite；Described silicon-containing compound can for organic silicon-containing compound and/
Or inorganic silicon-containing compound, it is selected from esters of silicon acis, silanol, silicon ether, silicone, silicone oil, silica gel (water
Close silicon dioxide), Ludox, silicic acid, waterglass, in amorphous silica-alumina and zeolite molecular sieve at least
One kind, inorganic silicon-containing compound therein can be in silica gel, Ludox, silicic acid and waterglass
At least one；Described silicaalumina carrier optionally can be made into the article shaped being arbitrarily easy to operate,
As spherical, tabletting and bar shaped etc., the method for described molding can be in tabletting, spin and extrusion
At least one；Described roasting can be carried out using conventional condition, and for example, sintering temperature can be
400-900 DEG C, preferably 500-750 DEG C, roasting time can be 1-12 hour, preferably 2-8 hour.
Method according to the invention it is possible to described boehmite be contained with described using any prior art
Silicon compound be mixed with described in the mixture containing boehmite and silicon-containing compound.Wherein,
Described mixing can be that described boehmite and described silicon-containing compound are placed in simple accumulation at one,
Can also be using any one prior art, for example, it is possible to directly will intend in blender, grinder
Boehmite is mixed by way of stirring with silicon-containing compound, can be under conditions of enough to pulp
Boehmite, silicon-containing compound and water are mixed, filters afterwards, dry or moist method is carried out
Mixing.When being mixed using any one prior art, those skilled in the art optionally can be to institute
State the uniformity that should reach of mixing to be controlled, this present invention is not particularly limited.
In one preferred embodiment, the preparation method of described silicaalumina carrier includes：
(1), under conditions of enough to pulp, boehmite, silicon-containing compound and water are mixed, afterwards
Filter, dry or moist, obtain the described mixture containing boehmite and silicon-containing compound；
(2), by mixture extrusion molding on banded extruder of step (1) gained；
(3), step (2) gained extrusion molding thing is dried and roasting.
Wherein, for ensureing being smoothed out of extruded moulding, include to described mixture in step (2)
Middle introduce appropriate water, peptizer (as selected from one or more of nitric acid, acetic acid and citric acid),
Extrusion aid (can be such as one of sesbania powder, cellulose, starch, polyvinyl alcohol and PVOH or several
Kind) and the step that mixes.Described drying is conventional method, such as using baking oven, mesh-belt kiln, converter and stream
Change bed to be dried, when being dried using heating means, preferred baking temperature is 100-200 DEG C,
Drying time 1-12 hour, further preferred baking temperature be 120-150 DEG C, drying time be 2-8 little
When.The method of described roasting and condition are the adopted conventional method of catalyst carrier preparation and condition, such as
Roasting is carried out using mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter, the condition of described roasting is preferably,
Roasting 1-12 hour at a temperature of 400-900 DEG C, roasting further preferably at a temperature of 500-750 DEG C
2-8 hour.
Silicaalumina carrier that is provided by the present invention or being adopted can have following materialization
Matter：Pore volume is 0.5-1.1 ml/g, and specific surface is 100-500 meters squared per gram, can several bore dias be 5-20
Nanometer, the pore volume of bore dia 4-10 nanometer is more than the 70% of total pore volume.Further preferably, described
The pore volume of silicaalumina carrier be 0.55-0.90 ml/g, specific surface be 150-350 square metre/
Gram, can several bore dias be 6-15 nanometer, the pore volume of bore dia 4-10 nanometer is more than the 75% of total pore volume.
The method according to the invention, ammonium salt described in step a can adopt inorganic ammonium salt, for example, can be
At least one in ammonium nitrate, ammonium chloride, ammonium carbonate and ammonium hydrogen carbonate.
The method according to the invention, the dipping described in step a can using those skilled in the art institute often
The dipping method that rule use, such as saturation infusion process or excessive infusion process.Wherein it should be noted that adopting
During with saturation impregnation silicaalumina carrier, the silica-alumina after dipping can be carried
Body is directly dried, and need not carry out filtration step；On the contrary, according to excessive impregnation oxygen
During SiClx-alumina support, need the silicon oxide-oxygen after time of infusion (such as 1-8 hour)
After change alumina supporter is filtered, then it is dried step；During using excessive infusion process, the method for the present invention
Preferably ammonium salt concentration is 0.1-1.0 mol/L.
The method according to the invention, drying described in step a can be under the conventional drying condition in this area
Carry out, for example, baking temperature can be 60-120 DEG C, and drying time can be 2-8 hour.
The method according to the invention, the method for load hydrogenation active metals component can adopt art technology
Method known to personnel, for example, hydrogenation active metals component described in step b can be by dipping (leaching
Bubble or spray) load in described impregnated carrier, can be dried afterwards and calcination stepses, here institute
State drying condition to be preferably：Temperature 100-200 DEG C, the time is 2-12 hour；Described roasting condition is preferred
For：Temperature 300-600 DEG C, the time is 2-10 hour.Wherein, described hydrogenation active metals component also may be used
With the hydrogenation active metals component conventional using this area, can be for example selected from cobalt, nickel, ruthenium, rhodium,
At least one in palladium and platinum；Counted with metal simple-substance and with the gross mass of hydrocatalyst for saturating arylhydrocarbon as base
Standard, in described hydrocatalyst for saturating arylhydrocarbon, the content of hydrogenation active metals component can be 0.1-5 matter
Amount %, preferably 0.2 mass %-1 mass %.The method of the present invention preferably, described hydrogenation activity
Metal component can contain platinum and palladium；In mass and total with platinum in hydrocatalyst for saturating arylhydrocarbon and palladium
On the basis of quality, the mass fraction of described palladium can be for 30 mass % to less than 100 mass %, preferably
50-80 mass %.Described dipping (can be selected from it using the compound containing hydrogenation active component
One or more of soluble compound) carry out, for example, it may be these hydrogenation active component
Nitrate, acetate, carbonate, one or more of chloride and soluble complexes；Work as institute
When the hydrogenation active component stated is platinum and palladium, described COMPOUNDS EXAMPLE can include PtCl4、Pt(NO3)2、
H2PtCl6、Pt(NH3)4Cl2、Pt(NH3)2(NO2)2With Pt (NH3)4(NO3)2And PdCl2、Pd(NO3)2、
H2PdCl4、Pd(NH3)4Cl2With Pd (NH3)4(NO3)2Deng.
The present invention also provides the virtue prepared by the preparation method according to hydrocatalyst for saturating arylhydrocarbon of the present invention
Hydrocarbon hydrocatalyst for saturating.
The present invention further provides a kind of hydrocatalyst for saturating arylhydrocarbon of the present invention is in aromatic hydrogenation saturation
Application in reaction, this application includes：Will be former with aromatic hydrogenation saturation for described hydrocatalyst for saturating arylhydrocarbon
Material contacts and aromatic hydrogenation saturated reaction occurs.
Application according to the present invention, this application can also include：By described hydrocatalyst for saturating arylhydrocarbon warp
Contact with aromatic hydrogenation saturation raw material again after hydrogen reducing and aromatic hydrogenation saturated reaction occurs；Described reduction
Temperature be 300-550 DEG C, time of reduction is 2-10 hour, and Hydrogen Vapor Pressure is 0.01-2.0 MPa.
Application according to the present invention, described aromatic hydrogenation saturation raw material can be former using this area routine
Material, for example, can be at least one in clean fuel oil, white oil and lube base oil.Described
The condition of aromatic hydrogenation saturated reaction can also be the conventional reaction condition in this area, for example, reaction temperature
Can be 200-380 DEG C, hydrogen dividing potential drop can be 0.5-15 MPa, and liquid volume air speed can be 0.1-5
Hour-1, hydrogen to oil volume ratio can be 100-3000.
The present invention will be further illustrated by embodiment below, but the present invention will not therefore be taken office
What limits.The instrument that the embodiment of the present invention is adopted if no special instructions, is those skilled in the art institute
Conventional use of instrument；The reagent being used, if no special instructions, is chemically pure reagent.
The embodiment of the present invention adopts hydrogenation active metals group in RIPP 132-90 determination of test method catalyst
The content divided；Content using silicon oxide and aluminium oxide in RIPP 134-90 determination of test method carrier；
Method using National Standard of the People's Republic of China GB/T 11081-2005 measures the ultraviolet light absorption of white oil
Degree.RIPP test method of the present invention is selected from《Petrochemical Engineering Analysis method (RIPP test method)》,
Yang Cui surely waits and compiles, Science Press, and 1990.
Boehmite P1-1 adopts following method preparations：
In one 2 liters of retort cocurrent add 1000 milliliters of concentration be 48 grams of aluminium oxidies/liter trichlorine
Change aluminum solutions and 300 milliliters contain 200 grams of aluminium oxidies/liter, causticity coefficient be that 1.58, Sorbitol content is
1.82 g/l of sodium aluminate solution carries out precipitation, and reaction temperature is 80 DEG C, adjusts reaction stream
It is 4.0 that amount makes neutralization pH value, reaction time 15 minutes；In gained serosity, addition concentration is
The weak ammonia of 5 weight % adjusts serosity pH to 10.0, and is warming up to 80 DEG C, aging 3 hours, then
Filtered with vacuum filter, to be filtered complete after, filter cake supplements and adds 20 liters of deionized waters (temperature
80 DEG C of degree) rinse filter cake about 30 minutes.The filter cake washing qualified is added in 1.5 liters of deionized waters and stirs
Mix serosity, serosity is dried with being pumped into spray dryer, control spray dryer outlet temperature to exist
100-110 DEG C of scope, about 2 minutes dry materials time, obtains hydrated alumina P1-1 after being dried.
Boehmite P1-2 adopts following method preparations：
By containing 210 grams of aluminium oxidies/liter, causticity coefficient be 1.62 high concentration NaAlO2Solution and deionization
Water is configured to Al2O3Concentration is 40 g/l of 5 liters of solution, is subsequently adding 16.3 grams of sodium gluconate and obtains
To the NaAlO containing sodium gluconate2Solution, is then transferred in the plastic reactor of cumulative volume 8L, instead
Kettle ratio of height to diameter is answered to be 8, lower bands CO2Gas distributor.Solution temperature is controlled to be 25 ± 5 DEG C, from reaction
Device bottom is passed through the CO of concentration 90 volume %2Gas carries out plastic reaction, and gelling temperature controls in 20-
40 DEG C, adjust CO2Gas flow is 15 ± 2 liters/min, makes reaction end pH value in 4-6 minute
Reach 8.0-8.5, that is, stop ventilation, terminate plastic reaction.Gained serosity is heated to 70 DEG C always
Change 4 hours, then filtered with vacuum filter, to be filtered complete after, on filter cake supplement addition 20
Rise deionized water (temperature 70 C) and rinse filter cake about 30 minutes.The filter cake washing qualified is added to 1.5 liters
Stir into serosity in deionized water, serosity is dried with being pumped into spray dryer, obtain aqua oxidation
Aluminum P1-2.
Embodiment 1
Catalyst that the present invention provides and preparation method thereof is described.
By 400 grams of boehmite P1-1 (butt 70%) and Ludox (containing SiO230 weight %,
Beijing flying dragon horse company) 295 grams, after 11 grams of mixing of sesbania powder, then with 8.2 milliliters of nitric acid (concentration
65-68%, analyzes pure, Shantou Xi Long chemical plant) and 90 milliliters of mixing of water, afterwards this mixture is existed
Continue kneading on double screw banded extruder, obtain compositionss ZH-1 of the present invention.ZH-1 is a kind of plastic
Body, measures the composition of ZH-1, in terms of oxide and with oxygen in described compositionss using x-ray fluorescence method
On the basis of the total amount of SiClx and aluminium oxide, silica content is 24 weight %, and alumina content is 76 weights
Amount %.
Double screw banded extruder continues all aforementioned ZH-1 are extruded into the butterfly bar of 1.3 millimeters of ф, wet bar
After 120 DEG C of dryings 4 hours, in 600 DEG C of roastings 3 hours, obtain silicaalumina carrier SA-1.
Take 2.0 grams of ammonium chloride (analysis is pure), be dissolved in 120 milliliters of water, by the 100 grams of leachings of SA-1 carrier
Stain enters in above-mentioned ammonium chloride solution, and dipping filtered after 4 hours, through 100 DEG C of dryings 4 hours, is obtained and contains
Ammonium impregnated carrier NSA-1.
By nitric acid four ammonia platinum [Pt (NH3)4(NO3)2] 893 milligrams and nitric acid four ammonia palladium [Pd (NH3)4(NO3)2]
2941 milligrams in deionized water dissolving be formulated as impregnation liquid, 103 grams of carrier NSA-1 are completely immersed in
In impregnation liquid, dipping filtered after 3 hours, dried through 120 DEG C, in 450 DEG C of roastings 4 hours, 450 DEG C
Hydrogen reducing 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as C1, and it organizes prejudice
Table 1.Tenor in catalyst is analyzed with x-ray fluorescence method.
Embodiment 2
Catalyst that the present invention provides and preparation method thereof is described.
Boehmite P1-2 (butt 71%) and amorphous silica-alumina (Siral by 114 grams of laboratory synthesis
40, containing SiO240 weight %, German Condea Products) 304 grams, 11 grams of mixing of sesbania powder,
Again by this mixture and 7 milliliters of nitric acid (concentration 65-68% analyzes pure, Shantou Xi Long chemical plant),
246 milliliters of water mixing, after kneading is uniform on double screw banded extruder afterwards, obtain combination of the present invention
Thing ZH-2.ZH-2 is a kind of plastic, measures the composition of ZH-2 using x-ray fluorescence method, with oxygen
Compound meter on the basis of the total amount of silicon oxide and aluminium oxide in described compositionss, silica content is
30%, alumina content is 70%.
Aforementioned ZH-2 is extruded into by the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar is through 120 DEG C
After being dried 4 hours, in 600 DEG C of roastings 3 hours, obtain silicaalumina carrier SA-2.
Take 2.0 grams of ammonium hydrogen carbonate (analysis pure), be dissolved in 120 milliliters of water, by 100 grams of SA-2 carrier
It is impregnated in above-mentioned solution, dipping filtered after 3 hours, through 60 DEG C of dryings 8 hours, be obtained containing ammonium dipping
Carrier NSA-2.
By dichloro four ammonia platinum [Pt (NH3)4Cl2] 862 milligrams and nitric acid four ammonia palladium [Pd (NH3)4(NO3)2]840
Dissolving is formulated as impregnation liquid to milligram in deionized water, and 105 grams of carrier NSA-2 are completely immersed in dipping
In liquid, dipping filtered after 6 hours, dried through 120 DEG C, in 500 DEG C of roastings 4 hours, 350 DEG C of hydrogen
Reduction 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as C2, and its composition is shown in Table 1.
Tenor in catalyst is analyzed with x-ray fluorescence method.
Embodiment 3
Catalyst that the present invention provides and preparation method thereof is described.
Boehmite P1-2 (butt 71%) and amorphous silica-alumina (Siral by 285 grams of laboratory synthesis
40, containing SiO240 weight %, German Condea Products) 152 grams, 9 grams of mixing of sesbania powder,
Again by this mixture and 9 milliliters of nitric acid (concentration 65-68% analyzes pure, Shantou Xi Long chemical plant),
275 milliliters of water mixing, after kneading is uniform on double screw banded extruder afterwards, obtain combination of the present invention
Thing ZH-3.ZH-3 is a kind of plastic, measures the composition of ZH-3 using x-ray fluorescence method, with oxygen
Compound meter on the basis of the total amount of silicon oxide and aluminium oxide in described compositionss, silica content is
15%, alumina content is 85%.
Aforementioned ZH-3 is extruded into by the butterfly bar of 1.3 millimeters of ф on double screw banded extruder, wet bar is through 120 DEG C
After being dried 4 hours, in 600 DEG C of roastings 3 hours, obtain silicaalumina carrier SA-3.
Take 12 grams of ammonium nitrate (analysis is pure), be dissolved in 150 milliliters of water, by the 100 grams of leachings of SA-3 carrier
Stain enters in above-mentioned solution, and dipping filtered after 3 hours, through 60 DEG C of dryings 8 hours, containing ammonium dipping is obtained and carries
Body NSA-3.
431 milligrams of ruthenic chloride and 840 milligrams of nitric acid four ammonia palladium are dissolved in deionized water and is formulated as impregnating
Liquid, 105 grams of carrier NSA-3 are completely immersed in impregnation liquid, and dipping filtered after 6 hours, through 120 DEG C
Dry, in 500 DEG C of roastings 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa,
Catalyst after reduction is designated as C3, and its composition is shown in Table 1.Tenor in catalyst is glimmering with X-ray
Light method is analyzed.
Comparative example 1
Comparative catalyst and preparation method thereof is described.
By nitric acid four ammonia platinum [Pt (NH3)4(NO3)2] 893 milligrams and nitric acid four ammonia palladium
[Pd(NH3)4(NO3)2] 2941 milligrams in deionized water dissolving be formulated as impregnation liquid, by 100 grams of carriers
SA-1 is completely immersed in impregnation liquid, and dipping filtered after 3 hours, dries through 120 DEG C, in 450 DEG C of roastings
4 hours, 450 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as
DC1, its composition is shown in Table 1.Tenor in catalyst is analyzed with x-ray fluorescence method.
Comparative example 2
Comparative catalyst and preparation method thereof is described.
By dichloro four ammonia platinum [Pt (NH3)4Cl2] 862 milligrams and nitric acid four ammonia palladium [Pd (NH3)4(NO3)2]840
Dissolving is formulated as impregnation liquid to milligram in deionized water, and 105 grams of carrier S A-2 are completely immersed in impregnation liquid
In, dipping filtered after 6 hours, dried through 120 DEG C, in 500 DEG C of roastings 4 hours, 350 DEG C of hydrogen were also
Former 4 hours, Hydrogen Vapor Pressure was 0.1 MPa, and the catalyst after reduction is designated as DC2, and its composition is shown in Table 1.
Tenor in catalyst is analyzed with x-ray fluorescence method.
Comparative example 3
Comparative catalyst and preparation method thereof is described.
431 milligrams of ruthenic chloride and 840 milligrams of nitric acid four ammonia palladium are dissolved in deionized water and is formulated as impregnating
Liquid, 105 grams of carrier S A-3 are completely immersed in impregnation liquid, and dipping filtered after 6 hours, through 120 DEG C
Dry, in 500 DEG C of roastings 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa,
Catalyst after reduction is designated as DC3, and its composition is shown in Table 1.Tenor in catalyst is glimmering with X-ray
Light method is analyzed.
Embodiment 4
This example demonstrates that the application of the catalyst of present invention offer.
Evaluating catalyst is carried out using a kind of high viscosity naphthenic base white oil raw material, its property is shown in Table 2.Reaction
100 milliliters of hydrogenation reaction devices are carried out, catalyst is C1, its particle diameter is 0.30～0.45 milli
Rice.Process conditions and reaction result are shown in Table 3.
Embodiment 5
This example demonstrates that the application of the catalyst of present invention offer.
Evaluating catalyst is carried out using a kind of high viscosity naphthenic base white oil raw material, its property is shown in Table 2.Reaction
100 milliliters of hydrogenation reaction devices are carried out, catalyst is C2, its particle diameter is 0.30～0.45 milli
Rice.Process conditions and reaction result are shown in Table 3.
Embodiment 6
Identical with embodiment 4 condition, except that catalyst is C3.Reaction result is shown in Table 3.
Comparative example 4
Identical with embodiment 4 condition, except that catalyst is DC1.Reaction result is shown in Table 3.
Comparative example 5
Identical with embodiment 5 condition, except that catalyst is DC2.Reaction result is shown in Table 3.
Comparative example 6
Identical with embodiment 6 condition, except that catalyst is DC3.Reaction result is shown in Table 3.
The result of table 3 shows, by using the catalyst prepared by the inventive method with using prior art institute
When the catalyst of preparation is applied to white oil hydrogenation reaction, carried out using the catalyst prepared by the inventive method
The ultraviolet absorptivity of reaction products obtained therefrom is lower, illustrates that the catalyst prepared by the inventive method has higher
Activity.
Table 1
Table 2
Table 3
Claims (17)
1. a kind of preparation method of hydrocatalyst for saturating arylhydrocarbon, the method includes：
A, silicaalumina carrier ammonium salt solution is impregnated and is dried, obtain impregnated carrier；Wherein,
The ratio of described ammonium salt and described silicaalumina carrier is 0.01-0.2 mole/100 grams；
B, by step a gained impregnated carrier load hydrogenation active metals component, obtain aromatic hydrogenation
Saturation catalyst.
2. method according to claim 1, wherein, described ammonium salt and described silica-alumina
The ratio of carrier is 0.02-0.05 mole/100 grams.
3. method according to claim 1, wherein, aoxidizes in described silicaalumina carrier
The content of aluminum is 60-99 mass %, and the content of silicon oxide is 1-40 mass %.
4. method according to claim 1, wherein, the preparation of described silicaalumina carrier
Method includes：Mixture containing boehmite and silicon-containing compound is carried out successively molding and roasting.
5. method according to claim 4, wherein, described silicon-containing compound be selected from esters of silicon acis,
Silanol, silicon ether, silicone, silicone oil, silica gel, Ludox, silicic acid, waterglass, amorphous silica-alumina and boiling
At least one in stone molecular sieve.
6. method according to claim 4, wherein, described silicon-containing compound be selected from silica gel,
At least one in Ludox, silicic acid and waterglass.
7. method according to claim 4, wherein, the condition of described roasting is：Sintering temperature
For 400-900 DEG C, roasting time is 1-12 hour.
8. method according to claim 1, wherein, ammonium salt described in step a is selected from nitric acid
At least one in ammonium, ammonium chloride, ammonium carbonate and ammonium hydrogen carbonate.
9. method according to claim 1, wherein, the condition being dried described in step a is：
Baking temperature is 60-120 DEG C, and drying time is 2-8 hour.
10. method according to claim 1, wherein, hydrogenation active metals group described in step b
Divide by dip loading in described impregnated carrier.
11. methods according to claim 1, wherein, described hydrogenation active metals group is divided into and being selected from
At least one in cobalt, nickel, ruthenium, rhodium, palladium and platinum；Urge in terms of metal simple-substance and with aromatic hydrogenation saturation
On the basis of the gross mass of agent, the content of hydrogenation active metals component in described hydrocatalyst for saturating arylhydrocarbon
For 0.1-5 mass %.
12. methods according to claim 11, wherein, described hydrogenation active metals component contains
Platinum and palladium；In mass and on the basis of the gross mass of platinum in hydrocatalyst for saturating arylhydrocarbon and palladium, described
The mass fraction of palladium is 30 mass % to less than 100 mass %.
The preparation of 13. hydrocatalyst for saturating arylhydrocarbon according to claim 1-12 any one
Hydrocatalyst for saturating arylhydrocarbon prepared by method.
Hydrocatalyst for saturating arylhydrocarbon described in 14. claim 13 is in aromatic hydrogenation saturated reaction
Application, this application includes：Described hydrocatalyst for saturating arylhydrocarbon is contacted simultaneously with aromatic hydrogenation saturation raw material
There is aromatic hydrogenation saturated reaction.
15. applications according to claim 14, this application also includes：Described aromatic hydrogenation saturation is urged
Agent is contacted with aromatic hydrogenation saturation raw material after hydrogen reducing again and aromatic hydrogenation saturated reaction occurs；Institute
The temperature stating reduction is 300-550 DEG C, and the time of reduction is 2-10 hour, and Hydrogen Vapor Pressure is 0.01-2.0
MPa.
16. applications according to claim 14, wherein, described aromatic hydrogenation saturation raw material is selected from clear
At least one in clean fuel oil, white oil and lube base oil.
17. applications according to claim 14, wherein, the condition of described aromatic hydrogenation saturated reaction is：
Reaction temperature is 200-380 DEG C, and hydrogen dividing potential drop is 0.5-15 MPa, and liquid volume air speed is 0.1-5 hour-1,
Hydrogen to oil volume ratio is 100-3000.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109603902A (en) * | 2018-12-29 | 2019-04-12 | 青岛汇益明催化新材料科技有限公司 | The combination catalyst of boat coal and low freezing point diesel fuel is produced with coal tar refining distillate |
| CN111068728A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071604A (en) * | 1984-11-19 | 1993-05-05 | 切夫尔昂研究公司 | The manufacturing of noble metal-zeolite catalysts |
| CN1510112A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Metal aromatic hydrosaturation catalyst |
| CN101254471A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN101254472A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN102309963A (en) * | 2010-06-03 | 2012-01-11 | 中国石油化工股份有限公司 | Aromatic hydrocarbon hydrogenation saturated catalyst and applications thereof |
| CN102688770A (en) * | 2012-04-28 | 2012-09-26 | 中国科学院青岛生物能源与过程研究所 | Aromatics hydrogenation catalyst and preparation method and application of aromatics hydrogenation catalyst |
| CN103041804A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN104826647A (en) * | 2014-02-08 | 2015-08-12 | 中国石油化工股份有限公司 | Preparation method for hydrogenation dearomatization catalyst |
-
2015
- 2015-08-14 CN CN201510502349.XA patent/CN106466600B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1071604A (en) * | 1984-11-19 | 1993-05-05 | 切夫尔昂研究公司 | The manufacturing of noble metal-zeolite catalysts |
| CN1510112A (en) * | 2002-12-24 | 2004-07-07 | 中国石油化工股份有限公司 | Metal aromatic hydrosaturation catalyst |
| CN101254471A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN101254472A (en) * | 2008-04-17 | 2008-09-03 | 中国石油天然气集团公司 | Modified molecular screen base precious metal diesel oil deepness hydrogenation dearomatization catalyst and method of preparing the same |
| CN102309963A (en) * | 2010-06-03 | 2012-01-11 | 中国石油化工股份有限公司 | Aromatic hydrocarbon hydrogenation saturated catalyst and applications thereof |
| CN103041804A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method thereof and aromatic hydrogenation catalytic method |
| CN102688770A (en) * | 2012-04-28 | 2012-09-26 | 中国科学院青岛生物能源与过程研究所 | Aromatics hydrogenation catalyst and preparation method and application of aromatics hydrogenation catalyst |
| CN104826647A (en) * | 2014-02-08 | 2015-08-12 | 中国石油化工股份有限公司 | Preparation method for hydrogenation dearomatization catalyst |
Non-Patent Citations (2)
| Title |
|---|
| J.斯科特: "《沸石制备技术及其在石油化工中的应用》", 31 August 1986 * |
| 吕春绪: "《硝酰阳离子理论》", 30 September 2006 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111068728A (en) * | 2018-10-18 | 2020-04-28 | 中国石油化工股份有限公司 | Aromatic hydrogenation catalyst, preparation method and application thereof |
| CN109603902A (en) * | 2018-12-29 | 2019-04-12 | 青岛汇益明催化新材料科技有限公司 | The combination catalyst of boat coal and low freezing point diesel fuel is produced with coal tar refining distillate |
| CN109603902B (en) * | 2018-12-29 | 2022-10-21 | 青岛汇益明催化新材料科技有限公司 | Combined catalyst for producing aviation kerosene and low-freezing-point diesel oil by using coal tar refined distillate oil |
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