CN109833896A - A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst - Google Patents
A kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of high dispersive noble metal slurry bed hydrogenation catalyst.It is catalyst carrier that the hydrogenation catalyst, which is mainly by the compound that molecular sieve and silica form, using Pt race noble metal as active component.The preparation method is mainly on molding porous silica micron ball, in the method for growth in situ, the controllable molecular sieve layer of a layer thickness is synthesized in its outer layer, form molecular sieve-silica complex carrier, finally Pt race noble metal precursor body is carried on shaping carrier, final catalyst is obtained after roasting.(aperture is adjustable, and scale is in 2~50nm, and specific surface area is in 200~450m with the structure not only with mesoporous characteristic for the catalyst obtained using the method2Between/g, Kong Rong is between 0.5~1.5ml/g), while also with the micro/meso porous characteristic of molecular sieve, and noble metal dispersion degree is high, is a kind of hydrogenation catalyst of function admirable.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a kind of high dispersive noble metal slurry bed hydrogenation catalyst
Preparation method.
Technical background
In catalytic reaction engineering, the structure of catalyst, composition, granular size and can be to urging to the dispersion degree of active component
The Activity and stabill of agent impacts.Wherein, how the pore structure of improved carrier, especially improved carrier is to improve activity
The dispersion degree of component is one of the main means for improving catalyst activity.The pore structure parameter of catalyst and its carrier include than
Surface area, aperture and hole appearance etc., can directly affect the mass transfer of each substance in the activity and reaction system of catalyst, and then determine
The service performance of catalyst.While adjusting catalyst and its carrier pore structure, control material granule pattern, size,
The macroparameters such as uniformity coefficient enable to the material granule of preparation to be expanded in application range field.
Currently, noble metal catalyst mostly uses infusion process, ion-exchange, chemical deposition precipitation method system in industry
Standby, main thinking is how further noble-metal-supported is carried out on molding carrier.However it uses above-mentioned
Conventional preparation method inevitably exists due to collision, the friction between catalyst and leads to catalyst surface active group
Divide the loss of noble metal that subsequent reactions efficiency is caused to decline.For general fluidized bed or even slurry bed process catalyst and
Speech, how to consolidate active component is to improve the key factor of catalyst activity, stability.
In general, molecular sieve (based on micro porous molecular sieve) is with it with excellent duct characteristic, biggish specific surface
Long-pending and Kong Rong not only itself has certain catalytic activity, also can use the quantity of its duct characteristic and surface hydroxyl, controls
The degree of scatter and size of the noble metal granule of load thereon, to improve the activity of catalyst.
Silica holds adjustable property than table, hole due to having, and has played important function in catalysis and separation field.
According to the definition of International Association for Pure and Applied Chemistry (IUPAC), aperture is known as micropore less than 2nm's；Aperture 2 to 50nm it
Between referred to as mesoporous (or mesoporous)；Aperture is known as macropore greater than 50 nanometers.Since duct is important to being diffused with for substance
Influence, therefore prepare selectivity of the silica for catalytic process of special pore size distribution, the separative efficiency of separating-purifying have ten
Divide important meaning.
In catalytic reaction process, to make catalyst give full play to efficiency, it should just make the particle of catalyst in the reactor
Situations such as shape, size, is in optimum state, could promote catalyst efficiency to greatest extent.For silica, as urging
When agent or catalyst carrier, common shape has bar shaped, cylindricality, Raschig ring, honeycomb, spherical shape etc..When spherical silica conduct
When fixed bed catalyst or catalyst carrier, due to contacting with each other between particle with point, bed resistance can be both reduced, simultaneously
Substantially increase mass transfer and catalytic effect；When the volume of reactor is certain, when institute's catalyst filling is as much as possible, spherical shape is
(when general spheric granules filling reactor, the spacial volume of particle can reach 70%, and diameter and height for optimum shape
Equal cylindrical particle is spent, only reaches 63~68%).When as fluid catalyst or catalyst carrier in use, tiny
Spheric granules be conducive to the diffusion of substance, improve catalytic, be also convenient for conducting heat, be conducive to control reaction temperature, can
Make reaction temperature close within the temperature range of optimum, while spheric granules wear-resisting property is also preferable.
The method for preparing spheric catalyst at present has spray drying process, spherical whole grain method, micro emulsion method, rotational forming method etc..
Patent CN 1660489A is that catalyst for synthesizing copper based methanol is prepared using spray drying process, and this method has input and output material temperature high
The shortcomings that.Peptizing agent and molding will be typically added in the method that prior art spherical shape whole grain prepares spheric catalyst in material
Auxiliary agent.Peptizing agent generally is nitric acid, citric acid, acetic acid or tartaric acid etc..Shaping assistant is generally sesbania powder or polyethylene glycol
Deng.Adhesive, the rheological characteristic of the cylindrical bars squeezed out by cylinder orifice plate are bad, cause shaping efficiency not high.CN101497044B
Disclose a kind of teeth spherical heavy oil hydrotreating catalyst and preparation method thereof.The preparation method of alumina support precursor
It is: peptizing agent, expanding agent and shaping assistant is added in aluminium hydroxide, after mixing, deionized water and nitric acid is added, mixing is equal
It is even, magma shape plastic is made；The peptizing agent is nitric acid, citric acid, acetic acid or tartaric acid or aforementioned any two or more
Mixture.Stronger interaction will certainly occur for strong acid and aluminium oxide in this way, will cause Kong Rong and specific surface loss is serious, make
The Kong Rong and specific surface area of final catalyst are reduced.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of preparation sides of high dispersive noble metal slurry bed hydrogenation catalyst
Method, the active component dispersion degree of the catalyst is high, catalyst aperture is adjustable, wearability is high, active spy high, stability is good
Point, and this method is simple and easy, high-efficient, large-scale production easy to accomplish.
In order to solve the above technical problems, a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst, feature
It is to follow the steps below:
A) silicon oxide powder of certain partial size is added in certain density silica solution first, acid, dispersion is then added
Agent, additive, organic amine form slurry after being sufficiently mixed；
B) mixed slurry in step (a) is injected in high temperature oil column by the certain fluidic generator in aperture and is shaped to aoxidize
Silicon ball presoma；
C) by the above-mentioned presoma in step (b) in oil column after aging, washed, dry, roasting obtains a micron oxygen
SiClx ball；
D) silicon source, the silicon source (or phosphorus source) of molecular sieve needed for preparing are mixed and stirred for uniformly with corresponding template, system
For at precursor sol, the leaching of above-mentioned micron silicon oxide ball is placed in colloidal sol, makes colloidal sol uniform fold in silica micron ball table
Face；The micron ball is filled into kettle later, at a certain temperature, makes target molecule sieve on silicon oxide ball surface by hydrothermal method
Growth in situ；
E) after carrier molding, noble metal precursor body is carried on carrier, catalyst adult is obtained after roasting.
Fluidic generator nozzle bore employed in step (2) is 0.1~1.0mm, the speed of jet stream is preferably 0.1~
10m/s；
Ageing time in step (3) is 3~r for 24 hours；
Molecular sieve in step (4), can be one of silicate, alumino-silicate, aluminophosphates of crystalline state or a few
The mixture of kind；
The synthetic method of molecular sieve in step (4) mainly uses Vacuum-assisted method；
The synthesis temperature of molecular sieve in step (4), between 100 DEG C to 300 DEG C；
Synthesis of molecular sieve in step (4), template used can be the monomer of organic amine, alcohols, ammonium salt, be also possible to
The mixture of several templates of certain in above-mentioned three；
Synthesis of molecular sieve in step (4), silicon source used can be aluminium oxide, aluminium hydroxide, meta-aluminate, isopropanol
One of aluminium, boehmite；Silicon source used can be silica solution, tetraethyl orthosilicate (TEOS), waterglass, silicic acid
One of sodium, fumed silica；Phosphorus source used, can be one of phosphoric acid and phosphorous acid；
Noble metal precursor body in step (5) can be ruthenium, rhodium, palladium, osmium, iridium, inorganic (organic) hydrochlorate of platinum or nothing
The couplings that machine (organic) hydrochlorate and ligand are formed；
The mode of carrier-supported precious metal is infusion process, ion-exchange, the chemical deposition precipitation method, gas phase in step (5)
One of sedimentation；
Catalyst maturing temperature in step (5) is between 230 DEG C to 1000 DEG C.
One kind prepared by the present invention is micron-sized, growth in situ molecular sieve spherical silica, and carried noble metal activity
The catalyst of component, using the ratio table for measuring sample on NOVA2200e type specific surface-pore-size distribution instrument of Quanta company, the U.S.
Area, pore size and pore size distribution.The spherical silica particle aperture of preparation is 2~50nm, and specific surface area is 200~450m2/ g,
0.5~1.5ml/g of Kong Rongwei.Catalyst individual particle diameter is 30~100 μm.
One kind prepared by the present invention is micron-sized, growth in situ molecular sieve spherical silica, and carried noble metal activity
The catalyst of component measures catalysis using the JEM-2100 type 200kV high resolution transmission electron microscopy of Jeol Ltd.
The size of active component particles contained by agent.
One kind prepared by the present invention is micron-sized, growth in situ molecular sieve spherical silica, and carried noble metal activity
The catalyst of component has the advantage that active component has higher dispersion degree under the action of molecular sieve and more concentrates
Size distribution；Simultaneous oxidation silicon shell has the meso-hole structure of suitable specific surface area and Kong Rong, so that the catalyst possesses
Higher activity, selectivity and stability.Such catalyst is suitable for the slurry reactor that anthraquinone hydrogenation prepares hydrogen peroxide process
In device, the process of similarly suitable other slurry bed system liquid-phase hydrogenatins and gas phase FCC technique.
Detailed description of the invention
Fig. 1 is the TEM photo of catalyst prepared by embodiment 1,
Fig. 2 is 1 catalyst hydrogenation Evaluation results of embodiment；
Fig. 3 is the TEM photo of catalyst prepared by embodiment 2,
Fig. 4 is 2 catalyst hydrogenation Evaluation results of embodiment；
Fig. 5 is the TEM photo of catalyst prepared by embodiment 3,
Fig. 6 is 3 catalyst hydrogenation Evaluation results of embodiment；
Fig. 7 is the TEM photo of catalyst prepared by embodiment 4,
Fig. 8 is 4 catalyst hydrogenation Evaluation results of embodiment；
Fig. 9 is the TEM photo of catalyst prepared by embodiment 5,
Figure 10 is 5 catalyst hydrogenation Evaluation results of embodiment；
Figure 11 is the TEM photo of catalyst prepared by embodiment 6,
Figure 12 is 6 catalyst hydrogenation Evaluation results of embodiment.
Specific embodiment
A kind of preparation of high dispersive noble metal slurry bed hydrogenation catalyst is described in further detail with embodiment below,
But the range that this should not be interpreted as to the claims of the present invention is only limitted to following embodiments.Unless otherwise noted, in this hair
All numbers occurred in bright specification and claims, such as dry, maturing temperature, operating condition, the quality hundred of composition
Point than etc. numerical value be not construed as absolute exact value, which is that those of ordinary skill in the art is understood
, in the permitted error range of well-known technique.
The performance evaluation of catalyst, which is then reacted by the anthraquinone hydrogenation in slurry bed system perfectly mixed reactor, to be carried out, experimental evaluation
The working solution used uses anthraquinone for working material, and solvent is the mixture of heavy aromatics and diisobutyl carbinol (DIBC).
The slurry bed system perfectly mixed reactor volume is 300ml, built-in stirring blade and gas distributor.Taking volume is about 5ml
Catalyst be placed in inside reactor.Evaluation uses continuous feeding and discharging mode, and total liquid measure is 150ml, charging rate 5ml/
Min, hydrogen flowing quantity 100ml/min.
Embodiment 1
(1-1) weighs SiO2Powder 50g, and mixed with the silica solution of concentrated hydrochloric acid 10mL and 100g 30%wt, obtain slurry
Main body, then 5g hexamethylenetetramine is added in slurry, stirring dissolves it sufficiently；
(1-2) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (1-1) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of oil temperature of transformer oil and form, after standing aging 4 hours, molding spherical oxygen is isolated from oil
SiClx, it is 12 hours dry in 100 DEG C；
Obtained product is roasted 12 hours at 700 DEG C and obtains spherical silica carrier by (1-3)；
15g analysis pure phosphoric acid and 10g boehmite are mixed to form gel by (1-4), and are diluted in 100g deionized water
In, and 10g di-n-propylamine is added, hydro-thermal 36 hours at 170 DEG C；
(1-5) by after products therefrom centrifuge washing, prior to 120 DEG C at it is 6 hours dry, roasted 12 hours at 700 DEG C,
Obtain the silicon oxide ball carrier of A-31 type molecular sieve growth in situ；
Pd (the NO that 11.5mL concentration is 5mg/mL by (1-6)3)2Solution is carried on above-mentioned original in a manner of incipient impregnation
On the carrier ball of position growth molecular sieve, after 120 DEG C of water removals in drying 6 hours, 500 DEG C are to obtain final catalyst after roasting 3 hours.
TEM photo is shown in that Fig. 1, catalyst hydrogenation Evaluation results are shown in Fig. 2.
Embodiment 2
(2-1) weighs SiO2Powder 21g, and mixed with the silica solution of concentrated hydrochloric acid 15mL and 200g 30%wt, obtain slurry
Main body, then 10g hexamethylenetetramine is added in slurry, stirring dissolves it sufficiently；
(2-2) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (2-1) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of oil temperature of transformer oil and form, after standing aging 4 hours, molding spherical oxygen is isolated from oil
SiClx, it is 12 hours dry in 100 DEG C；
Obtained product is roasted 12 hours at 700 DEG C and obtains spherical silica carrier by (2-3)；
15g analysis pure phosphoric acid and 20g boehmite are mixed to form gel by (2-4), and are diluted in 100g deionized water
In, and 10g triethylamine is added, hydro-thermal 36 hours at 170 DEG C；
(2-5) by after products therefrom centrifuge washing, prior to 120 DEG C at it is 6 hours dry, roasted 12 hours at 700 DEG C,
Obtain the silicon oxide ball carrier of A-5 type molecular sieve growth in situ；
Pd (the NO that 11.5mL concentration is 5mg/mL by (2-6)3)2Solution is carried on above-mentioned original in a manner of incipient impregnation
On the carrier ball of position growth molecular sieve, after 120 DEG C of water removals in drying 6 hours, 500 DEG C are to obtain final catalyst after roasting 3 hours.
TEM photo is shown in that Fig. 3, catalyst hydrogenation Evaluation results are shown in Fig. 4.
Embodiment 3
(3-1) weighs SiO2Powder 42g, and after being mixed with concentrated hydrochloric acid 15mL with the silica solution of 126g 30%wt, it is starched
Expect main body, then 15g ammonium citrate is added in slurry, stirring dissolves it sufficiently；
(3-2) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (3-1) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of oil temperature of transformer oil and form, after standing aging 4 hours, molding spherical oxygen is isolated from oil
SiClx, it is 12 hours dry in 100 DEG C；
Obtained product is roasted 12 hours at 700 DEG C and obtains spherical silica carrier by (3-3)；
15g analysis pure phosphoric acid and 20g aluminium hydroxide are mixed to form gel by (3-4), and are diluted in 100g deionized water,
And 10g tetraethyl ammonium hydroxide is added, hydro-thermal 24 hours at 200 DEG C；
(3-5) by after products therefrom centrifuge washing, prior to 120 DEG C at it is 6 hours dry, roasted 12 hours at 700 DEG C,
Obtain the silicon oxide ball carrier of A-5 molecular sieve growth in situ；
The PdCl that 11.5mL concentration is 5mg/mL by (3-6)2Solution is carried on above-mentioned original position in a manner of incipient impregnation
On the carrier ball for growing molecular sieve, after 120 DEG C of water removals in drying 6 hours, 550 DEG C are to obtain final catalyst after roasting 3 hours.
TEM photo is shown in that Fig. 5, catalyst hydrogenation Evaluation results are shown in Fig. 6.
Embodiment 4
(4-1) weighs SiO2Powder 21g, and after being mixed with the silica solution of concentrated hydrochloric acid 15mL and 126g 30%wt, it is starched
Expect main body, then 21g urea is added in slurry, stirring dissolves it sufficiently；
(4-2) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (4-1) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of oil temperature of transformer oil and form, after standing aging 4 hours, molding spherical oxygen is isolated from oil
SiClx, it is 12 hours dry in 100 DEG C；
Obtained product is roasted 12 hours at 700 DEG C and obtains spherical silica carrier by (4-3)；
15g analysis pure phosphoric acid and 17g are intended sodium metaaluminate and are mixed to form gel by (4-4), and are diluted in 100g deionized water
In, and 10g dihexylamine is added, hydro-thermal 18 hours at 170 DEG C；
(4-5) by after products therefrom centrifuge washing, prior to 120 DEG C at it is 6 hours dry, roasted 12 hours at 700 DEG C,
Obtain the silicon oxide ball carrier of A-34 type molecular sieve growth in situ；
The PdCl that 11.5mL concentration is 13mg/mL by (4-6)2Solution is carried on above-mentioned original position in a manner of incipient impregnation
On the carrier ball for growing molecular sieve, after 120 DEG C of water removals in drying 6 hours, 550 DEG C are to obtain final catalyst after roasting 5 hours.
TEM photo is shown in that Fig. 7, catalyst hydrogenation Evaluation results are shown in Fig. 8.
Embodiment 5
(5-1) weighs SiO2Powder 21g, and after being mixed with concentrated hydrochloric acid 15mL with the silica solution of 126g 30%wt, it is starched
Expect main body, then 15g ammonium citrate is added in slurry, stirring dissolves it sufficiently；
(5-2) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (5-1) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of oil temperature of transformer oil and form, after standing aging 4 hours, molding spherical oxygen is isolated from oil
SiClx, it is 12 hours dry in 100 DEG C；
Obtained product is roasted 12 hours at 700 DEG C and obtains spherical silica carrier by (5-3)；
15g silica solution and 10g boehmite are mixed to form gel by (5-4), and are diluted in 100g deionized water, are added
Enter 20g tetrapropylammonium hydroxide, hydro-thermal 24 hours at 180 DEG C；
(5-5) by after products therefrom centrifuge washing, prior to 120 DEG C at it is 6 hours dry, roasted 12 hours at 700 DEG C,
Obtain the silicon oxide ball carrier of type ZSM 5 molecular sieve growth in situ；
Pd (the NO that 11.5mL concentration is 20mg/mL by (5-6)3)2Solution is carried on above-mentioned original in a manner of incipient impregnation
On the carrier ball of position growth molecular sieve, after 120 DEG C of water removals in drying 6 hours, 500 DEG C are to obtain final catalyst after roasting 3 hours.
TEM photo is shown in that Fig. 9, catalyst hydrogenation Evaluation results are shown in Figure 10.
Embodiment 6
(6-1) weighs SiO2Powder 21g, and after being mixed with concentrated hydrochloric acid 15mL with the silica solution of 126g 30%wt, it is starched
Expect main body, then 15g hexamethylenetetramine is added in slurry, stirring dissolves it sufficiently；
(6-2) chooses the nozzle that internal diameter is 0.25mm and installs to fluidic generator, and the slurry that (6-1) is obtained is with 0.1m/s
Speed be injected into 95 DEG C of oil temperature of transformer oil and form, after standing aging 4 hours, molding spherical oxygen is isolated from oil
SiClx, it is 12 hours dry in 100 DEG C；
Obtained product is roasted 12 hours at 700 DEG C and obtains spherical silica carrier by (6-3)；
(6-4) by 15gHS-30 silica solution, 15g analysis pure phosphoric acid and 10g boehmite are mixed to form gel, and dilute
In 100g deionized water, 20g triethylamine, hydro-thermal 24 hours at 180 DEG C are added；
(6-5) by after products therefrom centrifuge washing, prior to 120 DEG C at it is 6 hours dry, roasted 12 hours at 700 DEG C,
Obtain the silicon oxide ball carrier of S-34 type molecular sieve growth in situ；
Pd (the NO that 11.5mL concentration is 20mg/mL by (6-6)3)2Solution is carried on above-mentioned original in a manner of incipient impregnation
On the carrier ball of position growth molecular sieve, after 120 DEG C of water removals in drying 6 hours, 500 DEG C are to obtain final catalyst after roasting 3 hours.
TEM photo is shown in that Figure 11, catalyst hydrogenation Evaluation results are shown in Figure 12.
Claims (19)
1. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst, it is characterised in that the catalyst is that kernel is oxygen
SiClx micron ball, shell are the carrier of molecular sieve, and the hydrogenation catalyst of supporting Pt race noble metal active component, the catalyst
Preparation method follows the steps below:
(1) silicon oxide powder of certain partial size is added in certain density silica solution first, then be added acid, dispersing agent,
Additive, organic amine form slurry after being sufficiently mixed；
(2) mixed slurry in step (1) is injected in high temperature oil column by the certain fluidic generator in aperture and is shaped to silica
Ball presoma；
(3) by the above-mentioned presoma in step (2) in oil column after aging, washed, dry, roasting obtains a micron silica
Ball；
(4) silicon source, the silicon source (or phosphorus source) of molecular sieve needed for preparing are mixed and stirred for uniformly, being prepared into corresponding template
The leaching of above-mentioned micron silicon oxide ball is placed in colloidal sol, makes colloidal sol uniform fold in silica micron ball surface by precursor sol；It
The micron ball is filled into kettle afterwards, at a certain temperature, makes target molecule sieve in silicon oxide ball surface in situ by hydrothermal method
Growth；
(5) after carrier molding, Pt race noble metal precursor body is carried on carrier, the catalysis of Precious metal oxidation state is obtained after roasting
Agent.
2. according to a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst described in claim 1, it is characterised in that:
The particle scale for the silicon oxide powder selected in step (1) is 2~15 μm.
3. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: mass ratio of the solid powder being added in step (1) in whole slurry is 10~50%；Silica solution used is accounted for entire
The mass ratio of slurry is 10~60%；The dispersing agent additional amount is 0.1~5% of solid masses in slurry system；Institute
State 5~20% that organic amine is solid masses in slurry system；The additive is 0.1 of mass fraction of solids in slurry system
~5%.
4. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: the silica solution in step (1), contained SiO2Mass fraction be 20~40%, particle scale be 2~50nm.
5. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: acid is hydrochloric acid, nitric acid, phosphoric acid, other inorganic acids, salicylic acid, acetic acid, ethanedioic acid, citric acid in step (1) or other are organic
The one or more of acid.
6. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: organic amine described in step (1) is mainly ethylenediamine, ethanol amine, triethylene diamine, diethylenetriamines, hexa-methylene four
One or more of amine or urea.
7. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: additive described in step (1) be one of wollastonite, kaolin, silicon carbide fibre, glass fibre, talcum powder or
It is a variety of.
8. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: dispersing agent described in step (1) is methanol, ethyl alcohol, one of monohydric alcohols such as isopropanol or a variety of.
9. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: fluidic generator nozzle bore employed in step (2) is 0.1~1.0mm, and the speed of jet stream is preferably 0.1~10m/
s。
10. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: it is pumping fluid, transformer oil, paraffin oil, solvent naphtha, vegetable oil, mineral oil that oil is formed in oil column described in step (2)
It is one or more in C10~C13 mixing linear paraffin, and oil column temperature is 80~150 DEG C.
11. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: ageing time in step (3) be 3~r for 24 hours.
12. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In molecular sieve in step (4), it can be one of silicate, alumino-silicate, aluminophosphates of crystalline state or certain be several mixed
Close object.
13. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: the synthetic method of molecular sieve in step (4) mainly uses Vacuum-assisted method.
14. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: the synthesis temperature of molecular sieve in step (4), between 100 DEG C to 300 DEG C.
15. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: synthesis of molecular sieve in step (4), template used can be the monomer of organic amine, alcohols, ammonium salt, be also possible to above-mentioned
The mixture of several templates of certain in three.
16. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In synthesis of molecular sieve in step (4), silicon source used can be aluminium oxide, aluminium hydroxide, meta-aluminate, aluminium isopropoxide, intend it is thin
One of diaspore；Silicon source used can be silica solution, tetraethyl orthosilicate, waterglass, sodium metasilicate, gas phase titanium dioxide
One of silicon；Phosphorus source used, can be one of phosphoric acid and phosphorous acid.
17. according to a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst described in claim 1, feature exists
In the noble metal precursor body in step (5), can be ruthenium, rhodium, palladium, osmium, iridium, platinum inorganic (organic) hydrochlorate or inorganic (have
Machine) couplings that are formed of hydrochlorate and ligand.
18. a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst according to claim 1, feature exist
In: the mode of carrier-supported precious metal is one of infusion process, ion-exchange, the chemical deposition precipitation method, vapour deposition process.
19. according to a kind of preparation method of high dispersive noble metal slurry bed hydrogenation catalyst described in claim 1, feature exists
In: the catalyst maturing temperature in step (5) is between 230 DEG C to 1000 DEG C.
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| CN112973726A (en) * | 2019-12-13 | 2021-06-18 | 山西潞安矿业(集团)有限责任公司 | Palladium-cobalt alloy catalyst and preparation method and application thereof |
| CN115283007A (en) * | 2022-08-25 | 2022-11-04 | 中山大学 | Preparation of platinum metal nanocluster HA molecular sieve and application of platinum metal nanocluster HA molecular sieve in synthesis of 1,2,3, 4-tetrahydroquinoline |
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