CN105521797A - Supported double-metal-component catalyst, preparation method and application thereof, and aromatic hydrocarbon saturation hydrogenation method - Google Patents
Supported double-metal-component catalyst, preparation method and application thereof, and aromatic hydrocarbon saturation hydrogenation method Download PDFInfo
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Abstract
The invention relates to a supported double-metal-component catalyst, a preparation method and an application thereof, and an aromatic hydrocarbon hydrogenation saturation method. The method comprises the following steps: (1) a carrier is impregnated with a solution containing a compound of a first metal active component and a compound of a second metal active component; (2) the impregnated carrier is subjected to reductive activation; and (3) the reductive activation product is impregnated with a solution containing a compound of the second metal active component under a reductive or inert atmosphere. Calculated according to metal elements, the weight ratio of the compound of the first metal active component to the compound of the second metal active component in the step (1) is 10-600:1; and the weight ratio of the compound of the second metal active component in the step (1) to the compound of the second metal active component in the step (3) is 0.01-0.8:1. The invention also provides the supported double-metal-component catalyst. Compared with catalysts with same noble metal contents prepared with prior arts, the aromatic hydrocarbon saturation catalyst prepared with the method provided by the invention has substantially higher aromatic hydrocarbon saturation activity.
Description
Technical field
The present invention relates to application in aromatic saturation reaction of a kind of preparation method of load type double-metal component catalyst and aromatic hydrocarbon saturation catalyst obtained by this method and this catalyst and aromatic saturated hydrogenation method.
Background technology
Along with the development of World Economics, the demand of intermediate oil (comprising kerosene, diesel oil and oil used in fuel) is increasing day by day.Depend merely on straight-run diesel oil and can not meet this demand; This just needs to call in secondary processing diesel oil, as catalytic cracking diesel oil, coker gas oil.And containing a large amount of sulphur, nitrogen and aromatic hydrocarbons in secondary processing diesel oil, current sulphur and nitrogen can remove with traditional sulfide catalyst, and technological difficulties are Porous deproteinized bone.Arene content high in diesel oil brings many problems, and the raising as aromatic hydrocarbons in diesel oil not only can reduce oil quality and Cetane number, and can increase the particle emission in diesel combustion waste gas.Aromatic saturation in industry distillate (especially diesel oil) can use traditional sulphided state Co-Mo, Ni-Mo or Ni-W catalyst, or the noble metal catalyst such as Pt, Pd.When less demanding to arene content (as aromatics quality content <25 % by weight), non-noble metal hydrogenation catalyst and single hop deep hydrogenation technique is adopted to reach requirement; The advantage of this technique is that shortcoming is that hydrogenation activity is not high not by the impact of pending raw material toxicity, needs harsh reaction condition.When there being higher requirement to aromatic content of diesel oil (as aromatics quality content <15 % by weight or 10 % by weight), then need to adopt noble metal hydrogenation catalyst and two-stage process flow process, namely first paragraph reactor carries out hydrodesulfurization, denitrification reaction, and second segment reactor carries out Porous deproteinized bone reaction; The advantage of this technique is can deep removal aromatic hydrocarbons and reaction condition is comparatively gentle, and shortcoming is that second segment catalyst is very responsive to the sulfide in raw material, require one section refining after in product S content drop to ppm level.
Eighties of last century, due to the expensive and easy poisoning and deactivation of noble metal, therefore unless there are particular/special requirement, as needed the product quality of the highest distillate liquid yield, maximum jet fuel selectivity and excellence, general less use.After 2000, along with the development of raising and the Hydrofining Technology day by day of environmental protection requirement, the one-stage hydrogenation desulfurization of diesel oil can reach sulfur content lower than 50ppm level, and this makes the use of noble metal no longer because of poisoning and limited.
GB2234518A discloses a kind of with the method for producing large proportion boat coal containing two rings, polycyclic aromatic hydrocarbon raw material.Enter first paragraph reactor after feedstock oil mixes with hydrogen and carry out hydrodesulfurization, denitrification reaction, second segment reactor adopts fluorine-containing noble metal catalyst Porous deproteinized bone; And in order to protect two anti-noble metal catalysts, otherwise one anti-and two establish separator by H
2s and NH
3be separated removing.
US5391291A discloses a kind of zeolite-loaded Pt-Pd aromatic ring hydrogenation catalyst, and bullion content is 0.05-3wt.% (Pt:Pd mol ratio is 0.1-1), and limits the crystal formation of carrier Y molecular sieve.First paragraph reactor adopts the Hydrobon catalyst of Co, Mo, Ni, W composition, and reaction temperature is 225-375 DEG C; Pt-Pd aromatic ring hydrogenation catalyst described in second segment reactor adopts, reaction temperature is 225-375 DEG C.
CN1245204A discloses the preparation method of a kind of platiniferous and palladium load type double-metal component catalyst, comprise and will be dissolved with the solution of a kind of platinum or palladium compound and a kind of carrier contact in the first solvent, solution and this carrier contact of another kind of palladium or platinum compounds will be dissolved with again in the second solvent, dry also roasting, it is characterized in that, only through super-dry after first time contact, described platinum or palladium compound and palladium or platinum compounds react, product indissoluble or be insoluble to described the second solvent.What can be used for high-sulfur feed with catalyst prepared by the method faces hydrogen process, has higher hydrogenation activity and sulfur resistance.
CN101518740B discloses a kind of platinum-cobalt dual-metal catalyst with room-temperature benzene hydrogenation activity and preparation method thereof, the preparation method of the platinum-cobalt dual-metal catalyst that this invention provides comprises the steps: absorbent charcoal carrier to join in solution A, water bath method, dries, obtains catalyst precarsor; Described solution A is the aqueous solution containing cobalt salt and platinum salt.The catalyst that this invention obtains has very high metal specific area, can efficient catalytic aromatic hydrogenation reaction at ambient temperature.
But the arene saturating activity of catalyst prepared by above-mentioned disclosed method still has the leeway improved very greatly.
Summary of the invention
The object of the present invention is to provide a kind of have load type double-metal component catalyst of higher aromatic saturation performance and preparation method thereof and application and aromatic hydrogenation saturation process.
The invention provides a kind of preparation method of load type double-metal component catalyst, the method comprises the steps:
1) with the solution impregnating carrier containing the compound of the first metal active constituent and the compound of the second metal active constituent;
2) by step 1) carrier reduction activation after the dipping that obtains;
3) by step 2) product after reduction activation in reduction or inert atmosphere by the solution impregnation of the compound containing the second metal active constituent,
Wherein, step 1) in the compound of the compound of the first metal active constituent and the second metal active constituent with the weight ratio of elemental metal for 10-600:1, the compound of the second metal active constituent is in step 1) and step 3) with the weight ratio of elemental metal for 0.01-0.8:1, described first metal active constituent is cobalt and/or nickel, and described second metal active constituent is noble metal.
Present invention also offers the load type double-metal component catalyst obtained by said method.
Present invention also offers the application of above-mentioned load type double-metal component catalyst in aromatic saturation reaction.
Present invention also offers a kind of aromatic hydrogenation saturation process, under the method is included in aromatic hydrogenation catalytic condition, under hydrocatalyst for saturating arylhydrocarbon exists, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, described aromatic hydrocarbon saturation catalyst is above-mentioned aromatic hydrocarbon saturation catalyst.
Compared with the catalyst of the identical bullion content prepared with prior art, the aromatic hydrocarbon saturation catalyst adopting method of the present invention to obtain has obviously higher arene saturating activity.Particularly, with the hexane solution containing 10 % by weight toluene for raw material, the arene saturating activity of catalyst is compared.Found that, catalyst R1 (Pt-Co catalyst) conversion ratio to toluene prepared according to the methods of the invention is 71%, is obviously better than according to the obtained catalyst D1 of CN101289365B (be 54% to the conversion ratio of toluene); Catalyst R2 (Pt-Pd-Co catalyst) conversion ratio to toluene prepared according to the methods of the invention is 76%, is obviously better than according to the obtained catalyst D2 of CN201110139331.X (be 61% to the conversion ratio of toluene).
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Present invention also offers the preparation method of load type double-metal component catalyst, the method comprises the steps:
1) with the solution impregnating carrier containing the compound of the first metal active constituent and the compound of the second metal active constituent;
2) by step 1) carrier reduction activation after the dipping that obtains;
3) by step 2) product after reduction activation in reduction or inert atmosphere by the solution impregnation of the compound containing the second metal active constituent,
Wherein, step 1) in the compound of the compound of the first metal active constituent and the second metal active constituent with the weight ratio of elemental metal for 10-600:1, the compound of the second metal active constituent is in step 1) and step 3) with the weight ratio of elemental metal for 0.01-0.8:1, be preferably 0.1-0.5:1;
Described 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 described first metal active constituent can be the various soluble compounds of cobalt and/or nickel, is preferably water soluble salt, more preferably nitrate and/or chloride and/or acetate and various hydrate thereof.
Describedly contain in the solution of the compound of the first metal active constituent and the compound of the second metal active constituent, preferably in the concentration of the compound of the first metal active constituent first metal active constituent for 500-2000 grams per liter, more preferably 800-1500 grams per liter.
According to the present invention, the compound of described second metal active constituent can be the various soluble compounds of noble metal, and described noble metal can be at least one in Pt, Pd, Ru, Ir, is preferably at least one in Pt, Pd, Ir.
Preferably the compound of described second metal active constituent is Pd (NH
3)
4(NO
3)
2, Pd (NH
3)
4cl
2, Pt (NH
3)
4(NO
3)
2, Pt (NH
3)
4cl
2, RuCl
3, IrCl
3and one or more in various hydrate.
According to the present invention, step 1) in, the existence of the second metal active constituent is for promoting step 2) in the carrying out of reduction reaction and step 3) in the load of the second metal active constituent, therefore consumption relative to the second metal active constituent total consumption less, under preferable case, step 1) in the compound of the compound of the first metal active constituent and the second metal active constituent with the weight ratio of elemental metal for 50-200:1, be more preferably 100-200:1.
Step 1) to comprise temperature can be 10-90 DEG C for the condition of flooding, be preferably 15-40 DEG C, the time can be 1-10 hour, preferably 3-6 hour.Can adopt incipient impregnation also can supersaturation infusion process.
Step 2) reduction activation is preferably in the gaseous mixture atmosphere of pure hydrogen atmosphere or hydrogen and inert gas, as carried out in the gaseous mixture atmosphere of hydrogen and nitrogen and/or argon gas, it is 200-500 DEG C that the condition of described reduction activation comprises temperature, be preferably 300-500 DEG C, be more preferably 350-450 DEG C, time is 1-12 hour, is preferably 1-5 hour, is more preferably 2-4 hour.The pressure of described reduction can be normal pressure can be also pressurization, and concrete, the pressure of hydrogen can be 0.1-4MPa, is preferably 0.1-2MPa.Pressure in the present invention refers to absolute pressure.
Step 3) in containing the second metal active constituent compound solution in the second metal active constituent compound concentration in the second metal active constituent be preferably 0.2-100 grams per liter, preferred 1-50 grams per liter.
Preferred steps 1) solvent for use is water, step 2) solvent for use is at least one in water, ethanol, propyl alcohol, ethylene glycol, hexane, cyclohexane.
Step 3) to comprise temperature can be 10-90 DEG C for the condition of flooding, be preferably 15-40 DEG C, the time can be 0.1-10 hour, preferably 0.5-2 hour.Can adopt incipient impregnation also can supersaturation infusion process.
Under preferable case, described step 1) adopt incipient impregnation, maceration extract volume used press carrier water absorption rate and is calculated, step 3) maceration extract volume used is step 1) 1-3 times of maceration extract volume.
According to the present invention, said method preferably also comprises step 1) carrier first dry or roasting further successively after the dipping that obtains, and then carry out described reduction activation.
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 hour.
According to the present invention, said method preferably also comprises step 2) product after reduction activation at hydrogen and/or inert atmosphere, as being cooled to room temperature or step 3 in nitrogen and/or argon gas) temperature required after carry out step 3 again) dipping.Completing steps 3) after, O can also be passed into further
2/ N
2volume ratio is the gaseous mixture 0.5-4 hour of 0.05-1.0%, with passivation metal active constituent wherein, obtains the catalyst that can directly preserve in atmosphere.
According to the present invention, said method preferably also comprises step 3) dipping after product carry out drying.In order to prevent the metal active constituent in catalyst oxidized; described drying is preferably carried out under vacuum or under inert gas or reducibility gas protection, preferably uses step 3) mode that the gas of dipping atmosphere dries up carries out drying to flooding the product obtained.
The consumption of carrier preferably makes with the total amount of aromatic hydrocarbon saturation catalyst as benchmark, the content of described carrier can be 70-94 % by weight, be preferably 75-90 % by weight, the content of first metal active constituent of load on carrier can be 5-30 % by weight, be preferably 10-25 % by weight, the content of described second metal active constituent is 0.05-2 weight, is preferably 0.1-1 % by weight.
According to the present invention, described carrier can be various carriers conventional in aromatic hydrocarbon saturation catalyst, as one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide, clay, molecular sieve, active carbon, particularly preferably γ-Al
2o
3or SiO
2-Al
2o
3carrier.
Present invention also offers the load type double-metal component catalyst obtained by said method.Compared with the catalyst of the identical bullion content prepared with prior art, the load type double-metal component catalyst adopting method of the present invention to obtain has obviously higher arene saturating activity, trace it to its cause, may be because step 1) prepare containing the first metal and bimetallic bimetallic catalyst, in this bimetallic system, the second a small amount of metal can increase substantially the reduction degree of the first metal, is conducive to the high degree of dispersion of follow-up a large amount of noble metal.
Present invention also offers the application of above-mentioned load type double-metal component catalyst in aromatic saturation reaction.
Present invention also offers a kind of aromatic hydrogenation saturation process, under the method is included in aromatic hydrogenation catalytic condition, under hydrocatalyst for saturating arylhydrocarbon exists, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, described aromatic hydrocarbon saturation catalyst is above-mentioned load type double-metal component catalyst.
Catalyst of the present invention can be used for aromatic hydrogenation saturated reaction (preferred sulfur content is less than 50ppm), particularly clean fuel oil of the various raw material containing aromatic hydrocarbons, white oil, lubricating oil and the basic wet goods deepness hydrogenation dearomatization process containing aroamtic hydrocarbon raw material.Catalyst of the present invention can also be used for the saturated preparing cyclohexane of benzene hydrogenation.
Catalytic condition can be carried out with reference to prior art, and such as temperature is 80-280 DEG C of preferred 120-240 DEG C, and pressure is the preferred 0.5-4MPa of 0.2-8MPa, and hydrogen to oil volume ratio is the preferred 300-1500:1 of 100-10000:1, and mass space velocity is 0.1-100 hour
-1.
Following embodiment is convenient to understand the present invention better, but does not limit the present invention.In following embodiment, described percentage composition, if no special instructions, is mass percentage.
Embodiment 1
This embodiment is for illustration of Catalysts and its preparation method provided by the invention.
Take 19.75 grams of Co (NO
3)
26H
2o and 0.079 gram of Pt (NH
3)
4(NO
3)
2, make solvent by deionized water, be made into 28.5 milliliters of maceration extracts by solution needed for equi-volume impregnating.Maceration extract is decanted into 36 grams of γ-Al
2o
3on carrier (Chang Ling catalyst plant product, granularity 20-40 order, identical below), after stirring evenly standing 4 hours, through 120 DEG C of oven dry, 350 DEG C of roastings 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa.Be down to room temperature after reduction, and under logical hydrogen atmosphere, add 42.8 milliliters be dissolved with 0.159 gram of Pt (NH
3)
4(NO
3)
2the aqueous solution, leave standstill 1 hour, then to dry up with hydrogen.Then through O
2/ N
2volume ratio is the gaseous mixture passivation 0.5 hour of 0.5%, is stored in drier for subsequent use.The catalyst obtained is designated as R1, and its composition is in table 1.
Comparative example 1
This comparative example is for illustration of comparative catalyst and preparation method thereof.
The method Kaolinite Preparation of Catalyst D1 provided according to CN101289365B.
Take 19.75 grams of Co (NO
3)
26H
2o and 0.238 gram of Pt (NH
3)
4(NO
3)
2be dissolved in 100 ml deionized water, add 36 grams of γ-Al
2o
3carrier, electromagnetic agitation is after 2 hours, evaporate to dryness in 95 DEG C of water-baths, and through 120 DEG C of oven dry, 500 DEG C of roastings 4 hours, 450 DEG C of hydrogen reducings 1 hour, Hydrogen Vapor Pressure is 0.1 MPa.Room temperature is down to, through O after reduction
2/ N
2volume ratio is the gaseous mixture passivation 0.5 hour of 0.5%, is stored in drier for subsequent use.The catalyst obtained is designated as D1, and its composition is in table 1.
Embodiment 2
This embodiment is for illustration of Catalysts and its preparation method provided by the invention.
Take 29.63 grams of Co (NO
3)
26H
2o and 0.079 gram of Pt (NH
3)
4(NO
3)
2, make solvent by deionized water, be made into 28.5 milliliters of maceration extracts by solution needed for equi-volume impregnating.Maceration extract is decanted into 36 grams of SiO
2-Al
2o
3carrier (preparing with reference to the embodiment 2 of CN201110139331.X), after stirring evenly standing 4 hours, through 120 DEG C of oven dry, 400 DEG C of roastings 3 hours, 400 DEG C of hydrogen reducings 3 hours, Hydrogen Vapor Pressure is 0.1 MPa.Be down to room temperature after reduction, and under logical nitrogen atmosphere, add 42.8 milliliters be dissolved with 0.159 gram of Pt (NH
3)
4(NO
3)
2with 0.368 gram of Pd (NH
3)
4(NO
3)
2the aqueous solution, leave standstill 1 hour, then to dry up with nitrogen.Then through O
2/ N
2volume ratio is the gaseous mixture passivation 1 hour of 0.5%, is stored in drier for subsequent use.The catalyst obtained is designated as R2, and its composition is in table 1.
Comparative example 2
Comparative catalyst and preparation method thereof is described.
The method Kaolinite Preparation of Catalyst D2 provided according to CN201110139331.X.
Take 0.238 gram of Pt (NH
3)
4(NO
3)
2with 0.368 gram of Pd (NH
3)
4(NO
3)
2dissolve in deionized water and be formulated as maceration extract, by 36 grams of SiO
2-Al
2o
3carrier (prepared by the embodiment 2 with reference to CN201110139331.X) immerses in maceration extract completely, flood after 6 hours and filter, through 120 DEG C of oven dry, 500 DEG C of roastings 4 hours, 350 DEG C of hydrogen reducings 4 hours, Hydrogen Vapor Pressure is 0.1 MPa, and the catalyst after reduction is designated as D2, and its composition is in table 1.
Embodiment 3
This embodiment is for illustration of Catalysts and its preparation method provided by the invention.
Take 19.75 grams of Ni (NO
3)
26H
2o and 0.061 gram of Pd (NH
3)
4(NO
3)
2, make solvent by deionized water, be made into 28.5 milliliters of maceration extracts by solution needed for equi-volume impregnating.Maceration extract is decanted into 36 grams of SiO
2carrier (Haiyang Chemical Plant, Qingdao), after stirring evenly standing 4 hours, through 120 DEG C of oven dry, 350 DEG C of roastings 2 hours, 350 DEG C of hydrogen reducings 2 hours, Hydrogen Vapor Pressure is 0.1 MPa.Be down to room temperature after reduction, and under logical hydrogen atmosphere, add 42.8 milliliters be dissolved with 0.306 gram of Pd (NH
3)
4(NO
3)
2the aqueous solution, leave standstill 1 hour, then to dry up with hydrogen.Then through O
2/ N
2volume ratio is the gaseous mixture passivation 3 hours of 0.1%, is stored in drier for subsequent use.The catalyst obtained is designated as R3, and its composition is in table 1.
Embodiment 4
This embodiment is for illustration of Catalysts and its preparation method provided by the invention.
Take 29.63 grams of Co (NO
3)
26H
2o and 0.084 gram RuCl
3, make solvent by deionized water, be made into 28.5 milliliters of maceration extracts by solution needed for equi-volume impregnating.Maceration extract is decanted into 36 grams of γ-Al
2o
3on carrier, after stirring evenly standing 4 hours, through 120 DEG C of oven dry, 300 DEG C of roastings 5 hours, 300 DEG C of hydrogen reducings 5 hours, Hydrogen Vapor Pressure is 0.1 MPa.Be down to room temperature after reduction, and under logical hydrogen atmosphere, add 57.0 milliliters be dissolved with 0.17 gram of RuCl
3ethanolic solution, leave standstill 3 hours, then to dry up with hydrogen.Then through O
2/ N
2volume ratio is the gaseous mixture passivation 1 hour of 0.5%, is stored in drier for subsequent use.The catalyst obtained is designated as R4, and its composition is in table 1.
Embodiment 5
This embodiment is for illustration of Catalysts and its preparation method provided by the invention.
Take 43.46 grams of Co (NO
3)
26H
2o and 0.196 gram IrCl
3, make solvent by deionized water and be made into 41.8 milliliters of maceration extracts.Maceration extract is decanted into 36 grams of γ-Al
2o
3on carrier, after stirring evenly standing 4 hours, through 120 DEG C of oven dry, 500 DEG C of roastings 1 hour, 500 DEG C of hydrogen reducings 1 hour, Hydrogen Vapor Pressure is 0.1 MPa.Be down to room temperature after reduction, and under logical hydrogen atmosphere, add 57.0 milliliters be dissolved with 0.786 gram of IrCl
3ethanolic solution, leave standstill 2 hours, then to dry up with hydrogen.Then through O
2/ N
2volume ratio is the gaseous mixture passivation 1 hour of 0.5%, is stored in drier for subsequent use.The catalyst obtained is designated as R5, and its composition is in table 1.
Embodiment 6
This embodiment is for illustration of Catalysts and its preparation method provided by the invention.
Take 15.80 grams of Co (NO
3)
26H
2o and 0.032 gram of Pt (NH
3)
4(NO
3)
2, make solvent by deionized water, be made into 28.5 milliliters of maceration extracts by solution needed for equi-volume impregnating.Maceration extract is decanted into 36 grams of γ-Al
2o
3on carrier, after stirring evenly standing 4 hours, through 120 DEG C of oven dry, 350 DEG C of roastings 2 hours, 350 DEG C of hydrogen reducings 2 hours, Hydrogen Vapor Pressure is 0.1 MPa.Be down to room temperature after reduction, and under logical hydrogen atmosphere, add 42.8 milliliters be dissolved with 0.032 gram of Pt (NH
3)
4(NO
3)
2ethanolic solution, leave standstill 1 hour, then to dry up with hydrogen.Then through O
2/ N
2volume ratio is the gaseous mixture passivation 1 hour of 0.5%, is stored in drier for subsequent use.The catalyst obtained is designated as R6, and its composition is in table 1.
Embodiment 7 ~ 12
These embodiments are for illustration of the arene saturating activity of catalyst provided by the invention to model compound toluene.
According to following step evaluate catalysts R1, R2, R3, R4, R5 and R6 respectively.
Continuous-flow fixed-bed micro-devices carries out activity rating to catalyst, feedstock oil is the hexane solution containing 10 % by weight toluene, loaded catalyst is 0.2 gram, reaction condition is: pressure is 1.0 MPas, feedstock oil input is 0.2 ml/min, hydrogen to oil volume ratio is 1000, and temperature is 140 DEG C, reacts sampling after 3 hours and carries out online gas chromatographic analysis.Before reaction starts, first 200 DEG C, 1.0 MPa, flow velocity 200 ml/min nitrogen atmosphere reductase 12 hour.Reaction result lists in table 2.
Comparative example 3 ~ 4
These comparative examples are for illustration of the arene saturating activity of comparative catalyst.
Comparative catalyst D1 and D2 is evaluated respectively according to the method identical with embodiment 7 and condition.Reaction result lists in table 2.
Table 1 catalyst (preparation) parameter
Table 2 catalyst is to the arene saturating activity evaluation result of 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.
According to following step evaluate catalysts R1, R2, R3, R4, R5 and R6 respectively.
On 30 milliliters of hydrogenation plants, with the catalytic cracking diesel oil after deep hydrodesulfurizationof for reaction raw materials (total arene content 17.5 % by weight), carry out the arene saturating activity evaluation of oil product.Loaded catalyst 20 milliliters, and be diluted to 30 milliliters with quartz sand, granularity is all 20 ~ 40 orders.Before reaction starts, first 220 DEG C, 4.0 MPa, flow velocity 200 ml/min nitrogen atmosphere reduce 4 hours.Then, when temperature, pressure are constant, by liquid volume air speed 1 hour
-1, carry out activity rating to catalyst under the condition of hydrogen to oil volume ratio 800, stable reaction sampled after 24 hours, analyzed arene content by chromatograph-mass spectrometer coupling.Evaluation result is in table 3.Total aromatic saturation rate in table is provided by total arene content change of oil product before and after catalytic reaction.
Comparative example 5 ~ 6
Arene saturating activity when this comparative example processes oil product for illustration of comparative catalyst.
Comparative catalyst D1 and D2 is evaluated respectively according to the method identical with embodiment 13 and condition.Reaction result lists in table 3.
Table 3 catalyst treatment oil product evaluation result
| Embodiment is numbered | Catalyst is numbered | Total aromatic saturation rate (%) |
| 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 |
As can be seen from the result of embodiment 7 and comparative example 3 and embodiment 13 and comparative example 5, the catalyst R1 adopting the inventive method to prepare obviously is better than catalyst D1 prepared by co-impregnation, the conversion ratio of toluene brings up to 71% from 54%, and total aromatic saturation rate of oil product brings up to 77.1% from 58.2%.
As can be seen from the result of embodiment 8 and comparative example 4 and embodiment 14 and comparative example 6, the Pt-Pd-Co catalyst R2 adopting the inventive method to prepare is better than Pt-Pd catalyst D2 prepared by traditional co-impregnation, the conversion ratio of toluene brings up to 76% from 61%, and total aromatic saturation rate of oil product brings up to 88.3% from 64.0%.
These embodiment results illustrate, compared with the catalyst of identical bullion content prepared by catalyst provided by the present invention and prior art, have better arene saturating activity.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
Claims (14)
1. a preparation method for load type double-metal component catalyst, this preparation method comprises the steps:
1) with the solution impregnating carrier containing the compound of the first metal active constituent and the compound of the second metal active constituent;
2) by step 1) carrier reduction activation after the dipping that obtains;
3) by step 2) product after reduction activation in reduction or inert atmosphere by the solution impregnation of the compound containing the second metal active constituent,
Wherein, step 1) in the compound of the compound of the first metal active constituent and the second metal active constituent with the weight ratio of elemental metal for 10-600:1, the compound of the second metal active constituent is in step 1) and step 3) with the weight ratio of elemental metal for 0.01-0.8:1, described first metal active constituent is cobalt and/or nickel, and described second metal active constituent is noble metal.
2. preparation method according to claim 1, wherein, step 1) in the compound of the compound of the first metal active constituent and the second metal active constituent with the weight ratio of elemental metal for 50-200:1, the compound of the second metal active constituent is in step 1) and step 3) amount ratio be 0.1-0.5:1.
3. preparation method according to claim 1 and 2, wherein, the compound of described first metal active constituent is the nitrate of cobalt and/or nickel and/or chloride and/or acetate, and the compound of described second metal active constituent is containing one or more in the slaine of Pt, Pd, Ru, Ir.
4. according to the preparation method in claim 1-3 described in any one, wherein, step 1) to comprise temperature be 10-90 DEG C for the condition of flooding, be preferably 15-40 DEG C, the time is 1-10 hour, is preferably 2-6 hour.
5. according to the preparation method in claim 1-4 described in any one, wherein, step 2) reduction activation carries out in a hydrogen atmosphere, and it is 200-500 DEG C that the condition of described reduction activation comprises temperature, and the time is 1-12 hour.
6. preparation method according to claim 1, wherein, step 3) to comprise temperature be 10-90 DEG C for the condition of flooding, the time is 0.1-10 hour.
7. according to the preparation method in claim 1-6 described in any one, wherein, the method also comprises step 1) carrier after the dipping that obtains first carries out drying and roasting successively, and then carries out described reduction activation.
8. according to the preparation method in claim 1-7 described in any one, wherein, the method also comprises step 2) product after reduction activation is cooled to room temperature or step 3 under hydrogen or inert atmosphere) temperature required after carry out step 3 again) described in dipping.
9. according to the preparation method in claim 1-8 described in any one, wherein, the method also comprises to step 3) solid that obtains passes into O
2/ N
2volume ratio is the gaseous mixture 0.5-4 hour of 0.05-1.0%, with passivation metal active constituent wherein, obtains the catalyst that can directly preserve in atmosphere.
10. preparation method according to claim 1, wherein, the consumption of carrier makes with the total amount of aromatic hydrocarbon saturation catalyst as benchmark, the content of described carrier is 70-94 % by weight, the content of first metal active constituent of load on carrier is 5-30 % by weight, and the content of described second metal active constituent is 0.05-2 % by weight.
11. preparation methods according to claim 1 or 10, wherein, described carrier is one or more in aluminium oxide, silica, titanium oxide, magnesia, zirconia, thorium oxide, beryllium oxide, clay, molecular sieve, active carbon.
The 12. load type double-metal component catalysts obtained by the method in claim 1-11 described in any one.
The application of 13. load type double-metal component catalysts according to claim 12 in aromatic saturation reaction.
14. 1 kinds of aromatic hydrogenation saturation process, under the method is included in aromatic hydrogenation catalytic condition, under hydrocatalyst for saturating arylhydrocarbon exists, by the raw material containing aromatic hydrocarbons and hydrogen haptoreaction, wherein, described aromatic hydrocarbon saturation catalyst is load type double-metal component catalyst according to claim 12.
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