CN105521797B - Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method - Google Patents
Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method Download PDFInfo
- Publication number
- CN105521797B CN105521797B CN201410510738.2A CN201410510738A CN105521797B CN 105521797 B CN105521797 B CN 105521797B CN 201410510738 A CN201410510738 A CN 201410510738A CN 105521797 B CN105521797 B CN 105521797B
- Authority
- CN
- China
- Prior art keywords
- active constituent
- metal
- preparation
- metal active
- catalyst
- 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
Landscapes
- Catalysts (AREA)
Abstract
A kind of load type double-metal component catalyst and its preparation method and application and aromatic hydrogenation saturation process, this method include：1) with the solution impregnating carrier of the compound containing the first metal active constituent and the compound of the second metal active constituent；2) by the carrier reduction activation after dipping；3) product after reduction activation is impregnated in reduction or inert atmosphere with the solution of the compound containing the second metal active constituent, wherein, in step 1) compound of the compound of the first metal active constituent and the second metal active constituent using the weight ratio of elemental metal as 10 600：1, the compound of the second metal active constituent is in step 1) and step 3) using the weight ratio of elemental metal as 0.01 0.8:1.Present invention also offers the load type double-metal component catalyst as made from the above method.Compared with the catalyst of identical bullion content prepared by prior art, there is considerably higher arene saturating activity using aromatic hydrocarbon saturation catalyst made from the method for the present invention.
Description
Technical field
The present invention relates to a kind of preparation method of load type double-metal component catalyst and aromatic hydrocarbons obtained by this method
The application and aromatic saturated hydrogenation method of saturation catalyst and the catalyst in aromatic hydrocarbons saturated reaction.
Background technology
With the development of World Economics, the demand of intermediate oil (including kerosene, diesel oil and oil used in fuel) is increasingly
Increase.This demand can not possibly be met by depending merely on straight-run diesel oil；This just needs to call in secondary processing diesel oil, as catalytic cracking diesel oil,
Coker gas oil.And containing substantial amounts of sulphur, nitrogen and aromatic hydrocarbons in secondary processing diesel oil, sulphur and nitrogen can be urged with traditional sulfide at present
Agent is removed, and technological difficulties are Porous deproteinized bones.High arene content brings many problems in diesel oil, as aromatic hydrocarbons carries in diesel oil
Height can not only reduce oil quality and Cetane number, and can increase the particle emission in diesel combustion waste gas.Industrial cut
Aromatic hydrocarbons saturation in oily (especially diesel oil) can use traditional sulphided state Co-Mo, Ni-Mo or Ni-W catalyst, either
The noble metal catalysts such as Pt, Pd.(such as aromatics quality content when less demanding to arene content<25 weight %), using non-expensive
Catalytic hydrogenation and single hop deep hydrogenation technique can reach requirement；The advantages of technique is not to be poisoned by pending raw material
The influence of thing, shortcoming are that hydrogenation activity is not high, it is necessary to harsh reaction condition.When there is higher requirement to aromatic content of diesel oil
(such as aromatics quality content<15 weight % or 10 weight %), then need to use noble metal hydrogenation catalyst and two-stage process flow,
I.e. first paragraph reactor carries out hydrodesulfurization, denitrification reaction, and second segment reactor carries out Porous deproteinized bone reaction；The advantages of technique is
Can with deep removal aromatic hydrocarbons and reaction condition it is more gentle, shortcoming is that second segment catalyst is very quick to the sulfide in raw material
Sense, it is desirable to which S contents drop to ppm levels in one section of refined rear product.
Eighties of last century, because noble metal is expensive and easy poisoning and deactivation, therefore unless there are particular/special requirement, if desired for most
High distillate liquid yield, maximum jet fuel selectivity and excellent product quality, general less use.After 2000,
With the development increasingly improved with Hydrofining Technology of environmental protection requirement, the one-stage hydrogenation desulfurization of diesel oil can reach sulphur and contain
Amount is horizontal less than 50ppm, and this causes the use of noble metal to be no longer limited because of poisoning.
GB2234518A discloses a kind of method with the coal that navigated containing two rings, the big proportion of polycyclic aromatic hydrocarbon raw material production.Feedstock oil
Enter first paragraph reactor after being mixed with hydrogen and carry out hydrodesulfurization, denitrification reaction, second segment reactor uses your fluorine-containing gold
Metal catalyst Porous deproteinized bone；And in order to protect two anti-noble metal catalysts, separator is set by H between one is anti-and two is on the contrary2S and NH3Point
From removing.
US5391291A discloses a kind of zeolite-loaded Pt-Pd aromatic ring hydrogenation catalysts, bullion content 0.05-
3wt.% (Pt:Pd mol ratios are 0.1-1), and the crystal formation of carrier Y molecular sieve is defined.First paragraph reactor uses
The Hydrobon catalyst of Co, Mo, Ni, W composition, reaction temperature are 225-375 DEG C；Second segment reactor uses described Pt-
Pd aromatic ring hydrogenation catalysts, reaction temperature are 225-375 DEG C.
CN1245204A discloses a kind of preparation method of platiniferous and palladium load type double-metal component catalyst, including by
A kind of a kind of solution dissolved with platinum or palladium compound in solvent contacts with a kind of carrier, then another by being dissolved with second of solvent
A kind of solution of palladium or platinum compounds contacts with the carrier, dries and is calcined, it is characterised in that only through overdrying after contacting for the first time
Dry, the platinum or palladium compound and palladium or platinum compounds are to react, reaction product indissoluble or molten insoluble in described second
Agent.Face hydrogen process available for high-sulfur feed with catalyst prepared by this method, there is higher hydrogenation activity and sulfur resistance.
CN101518740B discloses a kind of platinum-cobalt dual-metal catalyst with room-temperature benzene hydrogenation activity and its preparation side
Method, the preparation method for the platinum-cobalt dual-metal catalyst that the invention provides comprise the following steps：Absorbent charcoal carrier is added to solution A
In, water bath method, drying, obtain catalyst precarsor；The solution A is the aqueous solution containing cobalt salt and platinum salt.The invention obtains
Catalyst there is very high metal specific surface area, can at ambient temperature efficient catalytic aromatic hydrogenation react.
But the arene saturating activity of catalyst for preparing of method disclosed above be still greatly improved and improve it is remaining
Ground.
The content of the invention
It is an object of the invention to provide a kind of load type double-metal component catalyst with higher aromatic hydrocarbons saturation performance
And preparation method and application and aromatic hydrogenation saturation process.
The invention provides a kind of preparation method of load type double-metal component catalyst, this method comprises the steps：
1) impregnated with the solution of the compound containing the first metal active constituent and the compound of the second metal active constituent
Carrier；
2) the carrier reduction activation after the dipping for obtaining step 1)；
3) by the product after step 2) reduction activation in reduction or inert atmosphere with containing the second metal active constituent
The solution dipping of compound,
Wherein, in step 1) compound of the compound of the first metal active constituent and the second metal active constituent with metal
The weight ratio of element meter is 10-600：1, the compound of the second metal active constituent is in step 1) and step 3) with elemental metal
Weight ratio be 0.01-0.8:1, first metal active constituent is cobalt and/or nickel, and second metal active constituent is expensive
Metal.
Present invention also offers the load type double-metal component catalyst as made from the above method.
Present invention also offers application of the above-mentioned load type double-metal component catalyst in aromatic hydrocarbons saturated reaction.
Present invention also offers a kind of aromatic hydrogenation saturation process, this method is included under aromatic hydrogenation catalytic condition,
In the presence of hydrocatalyst for saturating arylhydrocarbon, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, the aromatic hydrocarbons saturation catalysis
Agent is above-mentioned aromatic hydrocarbon saturation catalyst.
Compared with the catalyst of identical bullion content prepared by prior art, using aromatic hydrocarbons made from the method for the present invention
Saturation catalyst has considerably higher arene saturating activity.Specifically, using the hexane solution containing 10 weight % toluene as original
Material, compare the arene saturating activity of catalyst.As a result find, (Pt-Co is catalyzed catalyst R1 prepared according to the methods of the invention
Agent) it is 71% to the conversion ratio of toluene, hence it is evident that better than the catalyst D1 according to made from CN101289365B (to the conversion ratio of toluene
For 54%)；Catalyst R2 (Pt-Pd-Co catalyst) prepared according to the methods of the invention is 76% to the conversion ratio of toluene, hence it is evident that
Better than the catalyst D2 according to made from CN201110139331.X (conversion ratio to toluene is 61%).
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
Present invention also offers the preparation method of load type double-metal component catalyst, this method comprises the steps：
1) impregnated with the solution of the compound containing the first metal active constituent and the compound of the second metal active constituent
Carrier；
2) the carrier reduction activation after the dipping for obtaining step 1)；
3) by the product after step 2) reduction activation in reduction or inert atmosphere with containing the second metal active constituent
The solution dipping of compound,
Wherein, in step 1) compound of the compound of the first metal active constituent and the second metal active constituent with metal
The weight ratio of element meter is 10-600：1, the compound of the second metal active constituent is in step 1) and step 3) with elemental metal
Weight ratio be 0.01-0.8:1, preferably 0.1-0.5：1；
First metal active constituent is cobalt and/or nickel, and the second metal active constituent is noble metal.
According to the present invention, the compound of first metal active constituent can be the various solubilityizatioies of cobalt and/or nickel
Compound, preferably water soluble salt, more preferably nitrate and/or chloride and/or acetate and its various hydrates.
It is excellent in the solution of the compound containing the first metal active constituent and the compound of the second metal active constituent
Choosing using the first metal active constituent count the first metal active constituent compound concentration as 500-2000 g/l, it is further excellent
Elect 800-1500 g/l as.
According to the present invention, the compound of second metal active constituent can be the various soluble chemical combination of noble metal
Thing, the noble metal can be at least one of Pt, Pd, Ru, Ir, preferably at least one of Pt, Pd, Ir.
It is preferred that the compound of second metal active constituent is Pd (NH3)4(NO3)2、Pd(NH3)4Cl2、Pt(NH3)4
(NO3)2、Pt(NH3)4Cl2、RuCl3、IrCl3And its one or more in various hydrates.
According to the present invention, in step 1), the presence of the second metal active constituent is used to promote the reduction reaction in step 2)
Progress and step 3) in the second metal active constituent load, therefore dosage is relative to total use of the second metal active constituent
It is smaller for amount, under preferable case, the compound of the first metal active constituent and the change of the second metal active constituent in step 1)
Compound is using the weight ratio of elemental metal as 50-200：1, more preferably 100-200：1.
It can be 10-90 DEG C that the condition of step 1) dipping, which includes temperature, and preferably 15-40 DEG C, the time can be that 1-10 is small
When, preferably 3-6 hours.Can also supersaturated infusion process using incipient impregnation.
Step 2) reduction activation preferably in pure hydrogen atmosphere or the gaseous mixture atmosphere of hydrogen and inert gas, as hydrogen with
Carried out in the gaseous mixture atmosphere of nitrogen and/or argon gas, it is 200-500 DEG C that the condition of the reduction activation, which includes temperature, is preferably
300-500 DEG C, more preferably 350-450 DEG C, time are 1-12 hours, preferably 1-5 hours, more preferably 2-4 hours.It is described
The pressure of reduction can be that normal pressure can also be pressurization, specifically, the pressure of hydrogen can be 0.1-4MPa, preferably 0.1-
2MPa.Pressure in the present invention refers to absolute pressure.
The compound of second metal active constituent in the solution of compound containing the second metal active constituent in step 3)
Concentration in terms of the second metal active constituent be preferably 0.2-100 g/l, preferably 1-50 g/l.
Preferred steps 1) solvent for use is water, step 2) solvent for use is water, ethanol, propyl alcohol, ethylene glycol, hexane, hexamethylene
At least one of alkane.
It can be 10-90 DEG C that the condition of step 3) dipping, which includes temperature, and preferably 15-40 DEG C, the time can be 0.1-10
Hour, preferably 0.5-2 hours.Can also supersaturated infusion process using incipient impregnation.
Under preferable case, the step 1) uses incipient impregnation, and maceration extract volume used is calculated by carrier water absorption rate, step
It is rapid 3) used in maceration extract volume be 1-3 times of step 1) maceration extract volume.
According to the present invention, the above method preferably also include the carrier after the dipping that obtains step 1) first dry successively or
Further roasting, then carries out the reduction activation again.
Dry temperature can be 80-150 DEG C.
The temperature of roasting can be 220-600 DEG C, and the time can be 1-6 hours.
According to the present invention, the above method preferably also includes the product after step 2) reduction activation in hydrogen and/or inertia
Atmosphere, the dipping of step 3) is carried out after the temperature as needed for being cooled to room temperature or step 3) in nitrogen and/or argon gas again.Complete step
3) after, O can also be further passed through2/N2Volume ratio is 0.05-1.0% gaseous mixture 0.5-4 hours, to be passivated metal therein
Active component, obtain the catalyst that directly can be preserved in atmosphere.
According to the present invention, the above method preferably also includes the product after being impregnated to step 3) and is dried.In order to prevent urging
Metal active constituent in agent is oxidized, the drying preferably under vacuum inert gas or reducibility gas protection
Lower progress, the mode that the gas drying of atmosphere is preferably impregnated using step 3) are dried to impregnating obtained product.
The dosage of carrier is preferably so that on the basis of the total amount of aromatic hydrocarbon saturation catalyst, the content of the carrier can be
70-94 weight %, preferably 75-90 weight %, the content for the first metal active constituent being supported on carrier can be 5-30
Weight %, preferably 10-25 weight %, the content of second metal active constituent is 0.05-2 weight, and preferably 0.1-1 is heavy
Measure %.
According to the present invention, the carrier can be the various carriers commonly used in aromatic hydrocarbon saturation catalyst, such as aluminum oxide, oxidation
One or more in silicon, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, activated carbon, it is especially excellent
Select γ-Al2O3Or SiO2-Al2O3Carrier.
Present invention also offers the load type double-metal component catalyst as made from the above method.Prepared with prior art
The catalyst of identical bullion content is compared, and is had using load type double-metal component catalyst made from the method for the present invention bright
Aobvious higher arene saturating activity, traces it to its cause, it may be possible to because step 1) be prepared for it is bimetallic containing the first metal and the
Bimetallic catalyst, in this bimetallic system, the reduction degree of the first metal can be greatly improved in the second a small amount of metal, have
Beneficial to the high degree of dispersion of follow-up a large amount of noble metals.
Present invention also offers application of the above-mentioned load type double-metal component catalyst in aromatic hydrocarbons saturated reaction.
Present invention also offers a kind of aromatic hydrogenation saturation process, this method is included under aromatic hydrogenation catalytic condition,
In the presence of hydrocatalyst for saturating arylhydrocarbon, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, the aromatic hydrocarbons saturation catalysis
Agent is above-mentioned load type double-metal component catalyst.
The present invention catalyst can be used for the various raw materials containing aromatic hydrocarbons aromatic hydrogenation saturated reaction (preferably sulfur content is small
In 50ppm), the particularly deepness hydrogenation dearomatization process containing aroamtic hydrocarbon raw material such as clean fuel oil, white oil, lubricating oil and base oil.
The catalyst of the present invention can be also used for benzene hydrogenation saturation preparing cyclohexane.
Catalytic condition is referred to prior art progress, such as temperature is 80-280 DEG C preferably 120-240 DEG C, pressure
Power is 0.2-8MPa preferred 0.5-4MPa, hydrogen to oil volume ratio 100-10000：1 preferred 300-1500：1, mass space velocity 0.1-
100 hours-1。
Following embodiment facilitates a better understanding of the present invention, but does not limit the present invention.It is described in following embodiments
Percentage composition, it is weight/mass percentage composition unless otherwise instructed.
Embodiment 1
The embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh 19.75 grams of Co (NO3)2·6H2O and 0.079 gram of Pt (NH3)4(NO3)2, solvent is made with deionized water, by etc.
Solution needed for volume impregnation method is made into 28.5 milliliters of maceration extracts.Maceration extract is decanted into 36 grams of γ-Al2O3Carrier (Chang Ling catalyst
Factory's product, granularity 20-40 mesh are same as below) on, standing is stirred evenly after 4 hours, through 120 DEG C of drying, is calcined 4 hours at 350 DEG C,
350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure are 0.1 MPa.Room temperature is down to after reduction, and 42.8 are added under logical hydrogen atmosphere
Milliliter is dissolved with 0.159 gram of Pt (NH3)4(NO3)2The aqueous solution, stand 1 hour, then dried up with hydrogen.Then through O2/N2Volume
Than being passivated 0.5 hour for 0.5% gaseous mixture, it is standby to be stored in drier.Obtained catalyst is designated as R1, and its composition is shown in Table 1.
Comparative example 1
The comparative example is used to illustrate comparative catalyst and preparation method thereof.
Catalyst D1 is prepared according to the CN101289365B methods provided.
Weigh 19.75 grams of Co (NO3)2·6H2O and 0.238 gram of Pt (NH3)4(NO3)2It is dissolved in 100 ml deionized waters,
Add 36 grams of γ-Al2O3Carrier, electromagnetic agitation are evaporated after 2 hours in 95 DEG C of water-baths, and through 120 DEG C of drying, 4 are calcined at 500 DEG C
Hour, 450 DEG C of hydrogen reducings 1 hour, Hydrogen Vapor Pressure is 0.1 MPa.Room temperature is down to after reduction, through O2/N2Volume ratio is 0.5%
Gaseous mixture be passivated 0.5 hour, it is standby to be stored in drier.Obtained catalyst is designated as D1, and its composition is shown in Table 1.
Embodiment 2
The embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh 29.63 grams of Co (NO3)2·6H2O and 0.079 gram of Pt (NH3)4(NO3)2, solvent is made with deionized water, by etc.
Solution needed for volume impregnation method is made into 28.5 milliliters of maceration extracts.Maceration extract is decanted into 36 grams of SiO2-Al2O3Carrier (reference
It is prepared by CN201110139331.X embodiment 2), standing is stirred evenly after 4 hours, through 120 DEG C of drying, is calcined 3 hours at 400 DEG C,
400 DEG C of hydrogen reducings 3 hours, Hydrogen Vapor Pressure are 0.1 MPa.Room temperature is down to after reduction, and 42.8 are added under logical nitrogen atmosphere
Milliliter is dissolved with 0.159 gram of Pt (NH3)4(NO3)2With 0.368 gram of Pd (NH3)4(NO3)2The aqueous solution, stand 1 hour, then use nitrogen
Air-blowing is done.Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 1 hour, and it is standby to be stored in drier.Obtained catalyst note
For R2, its composition is shown in Table 1.
Comparative example 2
Illustrate comparative catalyst and preparation method thereof.
Catalyst D2 is prepared according to the CN201110139331.X methods provided.
Weigh 0.238 gram of Pt (NH3)4(NO3)2With 0.368 gram of Pd (NH3)4(NO3)2Dissolving is formulated as soaking in deionized water
Stain liquid, by 36 grams of SiO2-Al2O3Carrier (prepared by the embodiment 2 with reference to CN201110139331.X) is completely immersed in maceration extract,
Dipping filters after 6 hours, through 120 DEG C of drying, is calcined 4 hours at 500 DEG C, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure 0.1
MPa, the catalyst after reduction is designated as D2, and its composition is shown in Table 1.
Embodiment 3
The embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh 19.75 grams of Ni (NO3)2·6H2O and 0.061 gram of Pd (NH3)4(NO3)2, solvent is made with deionized water, by etc.
Solution needed for volume impregnation method is made into 28.5 milliliters of maceration extracts.Maceration extract is decanted into 36 grams of SiO2Carrier (Qingdao Haiyang chemical industry
Factory), standing is stirred evenly after 4 hours, through 120 DEG C of drying, is calcined 2 hours at 350 DEG C, 350 DEG C of hydrogen reducings 2 hours, Hydrogen Vapor Pressure
For 0.1 MPa.Room temperature is down to after reduction, and adds 42.8 milliliters under logical hydrogen atmosphere and is dissolved with 0.306 gram of Pd (NH3)4
(NO3)2The aqueous solution, stand 1 hour, then dried up with hydrogen.Then through O2/N2The gaseous mixture passivation 3 that volume ratio is 0.1% is small
When, it is standby to be stored in drier.Obtained catalyst is designated as R3, and its composition is shown in Table 1.
Embodiment 4
The embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh 29.63 grams of Co (NO3)2·6H2O and 0.084 gram of RuCl3, solvent is made with deionized water, by incipient impregnation
Solution needed for method is made into 28.5 milliliters of maceration extracts.Maceration extract is decanted into 36 grams of γ-Al2O3On carrier, standing is stirred evenly after 4 hours,
Through 120 DEG C of drying, it is calcined 5 hours at 300 DEG C, 300 DEG C of hydrogen reducings 5 hours, Hydrogen Vapor Pressure is 0.1 MPa.It is down to after reduction
Room temperature, and add 57.0 milliliters under logical hydrogen atmosphere and be dissolved with 0.17 gram of RuCl3Ethanol solution, stand 3 hours, then use hydrogen
Air-blowing is done.Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 1 hour, and it is standby to be stored in drier.Obtained catalyst note
For R4, its composition is shown in Table 1.
Embodiment 5
The embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh 43.46 grams of Co (NO3)2·6H2O and 0.196 gram of IrCl3, make solvent with deionized water and be made into 41.8 milliliters of leachings
Stain liquid.Maceration extract is decanted into 36 grams of γ-Al2O3On carrier, standing is stirred evenly after 4 hours, and through 120 DEG C of drying, 1 is calcined at 500 DEG C
Hour, 500 DEG C of hydrogen reducings 1 hour, Hydrogen Vapor Pressure is 0.1 MPa.Room temperature is down to after reduction, and is added under logical hydrogen atmosphere
57.0 milliliters are dissolved with 0.786 gram of IrCl3Ethanol solution, stand 2 hours, then dried up with hydrogen.Then through O2/N2Volume ratio
It is passivated 1 hour for 0.5% gaseous mixture, it is standby is stored in drier.Obtained catalyst is designated as R5, and its composition is shown in Table 1.
Embodiment 6
The embodiment is used to illustrate catalyst provided by the invention and preparation method thereof.
Weigh 15.80 grams of Co (NO3)2·6H2O and 0.032 gram of Pt (NH3)4(NO3)2, solvent is made with deionized water, by etc.
Solution needed for volume impregnation method is made into 28.5 milliliters of maceration extracts.Maceration extract is decanted into 36 grams of γ-Al2O3On carrier, standing is stirred evenly
After 4 hours, through 120 DEG C of drying, it is calcined 2 hours at 350 DEG C, 350 DEG C of hydrogen reducings 2 hours, Hydrogen Vapor Pressure is 0.1 MPa.Also
Room temperature is down to after original, and adds 42.8 milliliters under logical hydrogen atmosphere and is dissolved with 0.032 gram of Pt (NH3)4(NO3)2Ethanol it is molten
Liquid, 1 hour is stood, then dried up with hydrogen.Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 1 hour, is stored in drier
It is standby.Obtained catalyst is designated as R6, and its composition is shown in Table 1.
Embodiment 7~12
These embodiments are used to illustrate arene saturating activity of the catalyst provided by the invention to model compound toluene.
Evaluate catalyst R1, R2, R3, R4, R5 and R6 respectively as steps described below.
Activity rating is continuously being carried out on flowing fixed-bed micro-devices to catalyst, feedstock oil is containing 10 weight % toluene
Hexane solution, loaded catalyst is 0.2 gram, and reaction condition is：Pressure is 1.0 MPas, and feedstock oil input is 0.2 milli
Liter/min, hydrogen to oil volume ratio 1000, temperature is 140 DEG C, and reaction samples after 3 hours and carries out online gas chromatographic analysis.Reaction
Before beginning, first 200 DEG C, 1.0 MPas, the ml/min of flow velocity 200 nitrogen atmosphere reductase 12 hour.Reaction result is listed in table
2。
Comparative example 3~4
These comparative examples are used for the arene saturating activity for illustrating comparative catalyst.
Comparative catalyst D1 and D2 are evaluated respectively according to method and condition same as Example 7.Reaction result is listed in table
2。
The catalyst of table 1 (preparation) parameter
Arene saturating activity evaluation result of the catalyst of table 2 to model compound toluene
| Embodiment is numbered | Catalyst is numbered | Toluene conversion (%) |
| Embodiment 7 | R1 | 71 |
| Comparative example 3 | D1 | 54 |
| Embodiment 8 | R2 | 76 |
| Comparative example 4 | D2 | 61 |
| Embodiment 9 | R3 | 68 |
| Embodiment 10 | R4 | 66 |
| Embodiment 11 | R5 | 70 |
| Embodiment 12 | R6 | 67 |
Embodiment 13~18
These embodiments illustrate arene saturating activity during catalyst treatment oil product provided by the invention.
Evaluate catalyst R1, R2, R3, R4, R5 and R6 respectively as steps described below.
On 30 milliliters of hydrogenation plants, using the catalytic cracking diesel oil after deep hydrodesulfurizationof as reaction raw materials, (total aromatic hydrocarbons contains
Measure 17.5 weight %), carry out the arene saturating activity evaluation of oil product.20 milliliters of loaded catalyst, and be diluted to quartz sand
30 milliliters, granularity is all 20~40 mesh.Reaction start before, first 220 DEG C, 4.0 MPas, the ml/min of flow velocity 200 hydrogen
Atmosphere reduces 4 hours.Then, in the case where temperature, pressure are constant, by liquid volume air speed 1 hour-1, hydrogen to oil volume ratio 800
Under conditions of activity rating is carried out to catalyst, stable reaction samples after 24 hours, is contained with chromatograph-mass spectrometer coupling analysis aromatic hydrocarbons
Amount.Evaluation result is shown in Table 3.Total aromatic hydrocarbons saturation factor in table is provided by total arene content change of oil product before and after catalytic reaction.
Comparative example 5~6
The comparative example is used to illustrate arene saturating activity when comparative catalyst handles oil product.
Comparative catalyst D1 and D2 are evaluated respectively according to the identical method of embodiment 13 and condition.Reaction result is listed in table
3。
The catalyst treatment oil product evaluation result of table 3
| Embodiment is numbered | Catalyst is numbered | Total aromatic hydrocarbons saturation factor (%) |
| Embodiment 13 | R1 | 77.1 |
| Comparative example 5 | D1 | 58.2 |
| Embodiment 14 | R2 | 88.3 |
| Comparative example 6 | D2 | 64.0 |
| Embodiment 15 | R3 | 71.1 |
| Embodiment 16 | R4 | 70.3 |
| Embodiment 17 | R5 | 73.5 |
| Embodiment 18 | R6 | 69.8 |
Using the inventive method it can be seen from embodiment 7 and comparative example 3 and the result of embodiment 13 and comparative example 5
The catalyst R1 of preparation is substantially better than the catalyst D1 of co-impregnation preparation, and the conversion ratio of toluene brings up to 71% from 54%, oil
Total aromatic hydrocarbons saturation factor of product brings up to 77.1% from 58.2%.
Using the inventive method it can be seen from embodiment 8 and comparative example 4 and the result of embodiment 14 and comparative example 6
The Pt-Pd-Co catalyst R2 of preparation is better than Pt-Pd catalyst D2 prepared by traditional co-impregnation, and the conversion ratio of toluene is from 61%
76% is brought up to, total aromatic hydrocarbons saturation factor of oil product brings up to 88.3% from 64.0%.
These embodiment results explanation, the identical bullion content that catalyst provided by the present invention is prepared with prior art
Catalyst compare, there is more preferable arene saturating activity.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
Claims (15)
1. a kind of preparation method of load type double-metal component catalyst, the preparation method comprise the steps：
1) with the solution impregnating carrier of the compound containing the first metal active constituent and the compound of the second metal active constituent；
2) the carrier reduction activation after the dipping for obtaining step 1)；
3) by the product after step 2) reduction activation in reduction or inert atmosphere with the chemical combination containing the second metal active constituent
The solution dipping of thing,
Wherein, in step 1) compound of the compound of the first metal active constituent and the second metal active constituent with metallic element
The weight ratio of meter is 10-600：1, the compound of the second metal active constituent is in step 1) and step 3) with the weight of elemental metal
It is 0.01-0.8 to measure ratio:1, first metal active constituent is cobalt and/or nickel, and your gold second metal active constituent is
Category.
2. preparation method according to claim 1, wherein, the compound of the first metal active constituent and second in step 1)
The compound of metal active constituent is using the weight ratio of elemental metal as 50-200：1, the compound of the second metal active constituent exists
The amount ratio of step 1) and step 3) is 0.1-0.5:1.
3. preparation method according to claim 1, wherein, the compound of first metal active constituent for cobalt and/or
The nitrate and/or chloride and/or acetate of nickel, the compound of second metal active constituent is containing Pt, Pd, Ru, Ir
Metal salt in one or more.
4. according to the preparation method described in any one in claim 1-3, wherein, the condition of step 1) dipping is including temperature
10-90 DEG C, the time is 1-10 hours.
5. preparation method according to claim 4, wherein, it is 15-40 DEG C that the condition of step 1) dipping, which includes temperature, the time
For 2-6 hours.
6. according to the preparation method described in any one in claim 1-3, wherein, step 2) reduction activation is in a hydrogen atmosphere
Carry out, it is 200-500 DEG C that the condition of the reduction activation, which includes temperature, and the time is 1-12 hours.
7. preparation method according to claim 1, wherein, it is 10-90 DEG C that the condition of step 3) dipping, which includes temperature, the time
For 0.1-10 hours.
8. according to the preparation method described in any one in claim 1-3, wherein, this method also includes obtain step 1)
Carrier after dipping is first dried and is calcined successively, then carries out the reduction activation again.
9. according to the preparation method described in any one in claim 1-3, wherein, this method also includes reducing step 2) living
Product after change is cooled to the leaching carried out again after temperature needed for room temperature or step 3) described in step 3) under hydrogen or inert atmosphere
Stain.
10. according to the preparation method described in any one in claim 1-3, wherein, this method also includes obtaining to step 3)
Solid be passed through O2/N2Volume ratio is 0.05-1.0% gaseous mixture 0.5-4 hours, to be passivated metal active constituent therein, is obtained
To the catalyst that directly can be preserved in atmosphere.
11. preparation method according to claim 1, wherein, the dosage of carrier causes the total amount with aromatic hydrocarbon saturation catalyst
On the basis of, the content of the carrier is 70-94 weight %, and the content for the first metal active constituent being supported on carrier is 5-30
Weight %, the content of second metal active constituent is 0.05-2 weight %.
12. the preparation method according to claim 1 or 11, wherein, the carrier is aluminum oxide, silica, titanium oxide, oxygen
Change the one or more in magnesium, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, activated carbon.
13. the load type double-metal component catalyst as made from the method described in any one in claim 1-12.
14. application of the load type double-metal component catalyst in aromatic hydrocarbons saturated reaction described in claim 13.
15. a kind of aromatic hydrogenation saturation process, this method are included under aromatic hydrogenation catalytic condition, it is catalyzed in aromatic hydrogenation saturation
In the presence of agent, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, the aromatic hydrocarbon saturation catalyst is claim 13 institute
The load type double-metal component catalyst stated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410510738.2A CN105521797B (en) | 2014-09-28 | 2014-09-28 | Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410510738.2A CN105521797B (en) | 2014-09-28 | 2014-09-28 | Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105521797A CN105521797A (en) | 2016-04-27 |
| CN105521797B true CN105521797B (en) | 2018-02-23 |
Family
ID=55764519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410510738.2A Active CN105521797B (en) | 2014-09-28 | 2014-09-28 | Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105521797B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106693962B (en) * | 2017-01-21 | 2019-10-01 | 明光市天骄科技发展有限公司 | A kind of preparation method of double noble metal nano catalyst |
| CN108654611B (en) * | 2017-03-28 | 2020-09-22 | 中国石油化工股份有限公司 | Supported bimetallic catalyst, preparation method thereof and glycerin hydrogenolysis reaction method |
| CN108654612B (en) * | 2017-03-28 | 2020-09-18 | 中国石油化工股份有限公司 | Supported bimetallic catalyst, preparation method thereof and naphthenic hydrocarbon hydrogenolysis ring-opening method |
| CN108654635B (en) * | 2017-03-29 | 2020-08-18 | 中国石油化工股份有限公司 | Supported trimetal catalyst, preparation method thereof and method for catalyzing hydrogenolysis reaction of glycerol |
| CN109395729B (en) * | 2017-08-18 | 2021-10-01 | 中国石油化工股份有限公司 | Catalyst for preparing monocyclic aromatic hydrocarbon by selective hydrogenation of polycyclic aromatic hydrocarbon |
| CN109957424B (en) * | 2017-12-22 | 2020-10-27 | 中国石油化工股份有限公司 | Process method for converting catalytic cracking light cycle oil into jet fuel |
| CN109926067B (en) * | 2019-04-23 | 2022-08-12 | 中化泉州石化有限公司 | Platinum-palladium-cobalt ternary metal hydrogenation dearomatization catalyst and preparation method thereof |
| CN109967089A (en) * | 2019-04-23 | 2019-07-05 | 中化泉州石化有限公司 | A kind of platinum-palladium-cobalt ternary metal catalytic hydro-dearomatization catalyst and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
| CN101289365A (en) * | 2008-06-03 | 2008-10-22 | 北京大学 | Low-temperature catalytic benzene hydrogenation method and special catalyst thereof |
| CN101518740A (en) * | 2009-03-18 | 2009-09-02 | 北京大学 | Platinum-cobalt dual-metal catalyst with room-temperature benzene hydrogenation activity and preparation method thereof |
| 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 |
-
2014
- 2014-09-28 CN CN201410510738.2A patent/CN105521797B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1775361A (en) * | 2005-07-28 | 2006-05-24 | 大连理工大学 | Method for preparing nano noble metal hydrogenation catalyst by substitution method and its use |
| CN101289365A (en) * | 2008-06-03 | 2008-10-22 | 北京大学 | Low-temperature catalytic benzene hydrogenation method and special catalyst thereof |
| CN101518740A (en) * | 2009-03-18 | 2009-09-02 | 北京大学 | Platinum-cobalt dual-metal catalyst with room-temperature benzene hydrogenation activity and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105521797A (en) | 2016-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105521797B (en) | Load type double-metal component catalyst and preparation method and application and aromatic saturated hydrogenation method | |
| CN105521778B (en) | A kind of bimetallic catalyst of platiniferous and palladium and preparation method and application and aromatic saturation process | |
| CN109225254B (en) | PtNi/C bimetallic catalyst and preparation method thereof | |
| CN111054390B (en) | Catalyst for preparing methyl propionate by hydrogenating methyl acrylate and preparation and application thereof | |
| CN104096564A (en) | Fischer-Tropsch synthesis iron-based catalyst, preparation method and application thereof | |
| CN105903465A (en) | Load type hydrodeoxygenation catalyst and preparation method thereof | |
| CN109833883A (en) | A kind of high activity bimetallic load combustion catalyst and preparation method thereof | |
| CN108067244A (en) | A kind of spent catalyst recovery method | |
| CN106582668A (en) | Supported alloy type hydrogenation saturated catalyst and preparation method thereof | |
| CN106582707B (en) | Alloy-loaded aromatic saturation catalyst and preparation method thereof | |
| US20200188873A1 (en) | Nanometal oxide Adsorbents for Desulfurization of Hydrocarbon Fuels | |
| CN106552646A (en) | A kind of loaded catalyst and its preparation method and application and catalysis cycloalkane hydrogenolysis open-loop method | |
| CN104148083B (en) | A kind of preparation method of dual-functional hydrogenation catalyst for refining | |
| CN1916121B (en) | Method for preparing diene selective hydrotreating catalyst for gasoline | |
| CN106701158B (en) | The desulfuration processing method and desulfurization carbolic oil of carbolic oil | |
| CN1301154C (en) | Regenerable hydrogenation catalyst and method for producing the same | |
| CN105670690A (en) | Method for preparing solvent oil with low aromatics level by catalytic hydrogenation | |
| CN105505591A (en) | Method for hydrotreating of biomass pyrolysis oil | |
| CN102211029A (en) | Preparation method of hydrodesulfurization sulfide catalyst for diesel oil | |
| CN105732281A (en) | Front-depropanization front-hydrogenation method for C2 fraction | |
| RU2535990C1 (en) | METHOD OF OBTAINING CATALYST OF CARBONIC ACID METHANATION BASED ON BI-METAL NITRIDE Ni2Mo3N | |
| CN108654636A (en) | A kind of support type trimetallic catalyst and preparation method thereof and catalysis cycloalkane hydrogenolysis open-loop method | |
| CN109692699A (en) | Alloy with high activity type aromatic hydrocarbon hydrogenation catalyst and preparation method thereof | |
| CN109261145A (en) | A kind of preparation method and applications of the activated carbon supported noble metal catalyst of sulphur modification | |
| CN109603902A (en) | The combination catalyst of boat coal and low freezing point diesel fuel is produced with coal tar refining distillate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |