CN104148063B - A kind of reforming catalyst of active center stable dispersion and preparation method thereof - Google Patents
A kind of reforming catalyst of active center stable dispersion and preparation method thereof Download PDFInfo
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Abstract
Reforming catalyst of a kind of active center stable dispersion and preparation method thereof, belongs to reforming catalyst technical field.The multilevel hierarchy that this catalyst is aluminium oxide and brucite is constructed, utilizes hydrotalcite precursor topology transition process la m to surface metal atoms this feature of finite field effect, improves the dispersion stabilization of Pt.Advantage is that the dispersion stabilization of promoter metal and Pt is high；Catalyst reusability is good.It addition, the present invention is multilevel hierarchy, it is simple to commercial Application.
Description
Technical field
The invention belongs to reforming catalyst technical field, in particular, provide a kind of active center stable dispersion reforming catalyst and
Its preparation method.
Background technology
Catalytic reforming is exactly to carry out hydrocarbon molecules resetting under the effect of catalyst forming new molecular structure, is important oil
One of refining process, can be transformed into high octane gasoline component by Petroleum.Catalytic reforming process be unable to do without the catalysis of catalyst
Effect, the high performance catalyst target that everybody pursues always.
High performance catalyst refers to have high activity, high selectivity and the catalyst of high stability.For reforming catalyst,
Catalyst needs regeneration, the most originally realizes generally by oxychlorination, partly in order to the carbon deposit of burn off catalyst surface, separately
On the one hand it is then the redispersion realizing metal active centres, thus recovers the catalysis activity of catalyst.As can be seen here, metal active
The dispersion stabilization at center is also one of key factor affecting catalyst stability.The dispersion improving metal active centres is steady
Qualitative be conducive to extending the regeneration period, improve production efficiency.
Reforming catalyst is the bifunctional catalyst with metal function and acid function.Acid function is mainly chloride alchlor
Thering is provided, metal function is then mainly provided by the 8th race's metal platinum, and other metal, as stannum, rhenium or gallium etc. are as auxiliary agent, mainly
It is that platinum component is modified, changes the character of metal active centres, and then improve the catalytic performance of catalyst.
Catalyst active center's difficulty dispersion prepared by tradition infusion process, and in using, active center is the most easily assembled, and causes mistake
Live.At present, do substantial amounts of research improving in terms of metal active centres dispersion stabilization, mainly have following several approach:
(1) promoter metal, mainly Sn, Ge etc. are added；(2) modify carrier, use CeO2Or TiO2Repair Deng metal-oxide
Decorations carrier improves the active force between carrier and active metal；(3) method improving preparation, prepares by the method for gel-sol
Catalyst metals active center is the most stable；(4) available duct confinement, metallic particles enters in the duct of zeolite molecular sieve,
These ducts can suppress the further gathering of metallic particles；(5) Al of porous is covered on the surface of catalyst2O3Shell, play every
Effect from catalyst metals active center.But, while improving stability, bring again new problem, such as sol-gel
Method, cover porous shell etc. and be unfavorable for the exposure in active center, thus decrease active sites, reduce activity.Therefore, as
What is effectively improved the dispersion stabilization in active center is a difficult problem urgently to be resolved hurrily.
In recent years, brucite is widely applied to catalytic field with the construction features of its uniqueness, utilizes catalysis prepared by brucite
Agent metal active centres good dispersion, and stability have also been obtained large increase.Brucite is that a kind of bimetallic is combined hydroxide
Thing, a kind of novel multi-functional layered material, its chemical stability is good, has stronger heat resistanceheat resistant performance.Hydrotalcite precursor
In topology transition process, the rough surface that can be formed after the de--OH of laminate.Utilize the migration of rough surface limiting surface atom and gather
Collection.
Summary of the invention
Present invention aim at reforming catalyst that a kind of active center stable dispersion is provided and preparation method thereof, solve catalyst gold
The problem belonging to active center poor stability.
The reforming catalyst of the present invention is for including promoter metal and the bimetallic catalyst of active metal, and solid carrier particle surface is raw
Long brucite, uses brucite as catalyst carrier, it is possible to use formed in hydrotalcite precursor topology transition process is coarse
Surface limits promoter metal atom and the migration of active metal atom and gathering.The active center of catalyst prepared by this method is divided
Dissipate stability high.The preferred spherical Al of solid carrier in the present invention2O3Granule, the M of composition brucite laminate2+For Zn2+、Mg2+、
Ni2+、Cu2+、Mn2+、Ti2+, preferably Zn2+、Mg2+, most preferably Mg2+, Y3+At least include Al3+, such as Al3+、Fe3+,
Preferably Al3+.Metal promoter is In3+、Fe3+、Ga3+、Cr3+、Sn2+、Sn4+、Zr4+, preferably Ga3+、Zr4+、Sn2+、
Sn4+, most preferably Sn4+.The preferred H of platinum precursor2PtCl6、[Pt(NH3)4](NO3)2、Pt(acac)2、Na2PtCl6·6H2O, optimum
Select Na2PtCl6·6H2O。
The preparation method of the reforming catalyst of the present invention is as follows:
(1) at spherical Al2O3Particle surface growth in situ binary brucite MY-LDH/Al2O3
Preferably: by M2+Soluble in water with carbamide, M2+: the mol ratio of carbamide=(1 3): (2 4)；To equipped with solid spherical Al2O3
The reactor of granule carries out evacuation process and is subsequently adding above-mentioned mixed solution, crystallization, washing, is dried；
(2) preparation of catalyst precarsor
To equipped with MY-LDH/Al in step (1)2O3Container carry out evacuation process, inject stannum precursor (such as SnCl4·5H2O)
Solution, controls Sn actual negative carrying capacity in catalyst and, within 0.10 0.40wt.%, stands, be dried；By above-mentioned preparation
Sn4+/MY-LDH/Al2O3Precursor is placed in container and carries out evacuation process, is then injected into platinum precursor (such as Na2PtCl6·6H2O)
Solution, controls Pt actual negative carrying capacity in catalyst and, within 0.10 0.40wt.%, stands, be dried；
In step (2), Pt and Sn ratio excursion is within 1:1 2:1, and the load capacity of preferably Pt is 0.30wt.%,
The load capacity of Sn is 0.30wt.%.
(3) preparation of catalyst
Catalyst precarsor prepared by step (2) roasting 4-8h in the air of 350-900 DEG C of scope (preferably 400-600 DEG C)
(flow velocity 50-100mL/min/g), at the H of 350-900 DEG C of scope (preferably 400-600 DEG C)2Reduction 4-8h (flow velocity 50-
100mL/min/g), heating rate is 0-10 DEG C/min.
The catalyst repetitive cycling of the present invention is applied to normal heptane conversion reaction.
The remarkable advantage brucite of the present invention has confinement effect in topology transition process to the atom of lamina surface, and then improves
The stability of Pt and Sn；Active center stable dispersion, reusability is good.It addition, the present invention is aluminium oxide and brucite is constructed
Multilevel hierarchy, it is simple to commercial Application.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following example.
Embodiment 1
Step A:Mg (NO3)2·6H2O and carbamide are with Mg2+: the ratio of carbamide=3:2 is dissolved in deionized water, to equipped with one
Quantitative Al2O3Reactor carry out evacuation process be subsequently adding above-mentioned mixed solution, 85 DEG C of crystallization 5h.Filtering and washing, uses
Deionized water is washed till neutrality, is dried.
Step B: to equipped with the MgAl-LDH/Al of synthesis in step (A)2O3Container carry out evacuation process, inject SnCl4
Solution (0.036g SnCl4·5H2O is dissolved in water), stand, be dried.Sn by above-mentioned preparation4+/MgAl-LDH/Al2O3Precursor
It is placed in container and carries out evacuation process, be then injected into 3.745mL Na2PtCl6Solution (0.046M), stands, and is dried.
Step C: roasting 4h (flow velocity 80mL/min/g) in preferably 600 DEG C air of catalyst precarsor prepared by step (B), excellent
Select the H of 400 DEG C2Reduction 4h (flow velocity 60mL/min/g), heating rate is 10 DEG C/min.
I.e. prepare PtSn/MgAl-LDO/Al2O3Catalyst, the actual negative carrying capacity of Pt is 0.29%, the actual negative carrying capacity of Sn
It is 0.29%.
Comparative example 1
Step A: accurately weigh 0.036g SnCl4·5H2O, dissolves with deionized water, to equipped with a certain amount of Al2O3's
Container carries out evacuation process, injects above-mentioned SnCl4Solution, places a period of time, is dried overnight.
Step B: the container of the sample obtained equipped with step (A) is carried out evacuation process, injects 3.745mL Na2PtCl6
Solution, places a period of time, is dried overnight.
Step C: roasting 4h (flow velocity 80mL/min/g) in preferably 600 DEG C air of catalyst precarsor prepared by step (B), excellent
Select the H of 400 DEG C2Reduction 4h (flow velocity 60mL/min/g), heating rate is 10 DEG C/min.
I.e. prepare PtSn/Al2O3Catalyst, the actual negative carrying capacity of Pt is 0.29%, and the actual negative carrying capacity of Sn is 0.28%.
With the PtSn/MgAl-LDO/Al obtained by embodiment 12O3PtSn/Al obtained by catalyst and comparative example 12O3Catalyst
Carry out redox cycle process.Roasting 7h and the H at 400 DEG C in 600 DEG C of air2Reduction 7h is that an oxidoreduction is followed
Ring.To fresh catalyst and once, secondary oxidation reduction circulation after catalyst carry out dispersion test, result is listed in table 1.
From the point of view of the result of Pt dispersion, PtSn/MgAl-LDO/Al2O3In catalyst, the dispersion stabilization of Pt will be apparently higher than
PtSn/Al2O3Catalyst.
Table 1PtSn/MgAl-LDO/Al2O3Catalyst and PtSn/Al2O3The dispersion of catalyst Pt
With the PtSn/MgAl-LDO/Al obtained by embodiment 12O3PtSn/Al obtained by catalyst and comparative example 12O3Catalyst
The conversion reaction of catalysis normal heptane, reaction temperature is 400 DEG C, and reaction pressure is 0.50MPa, and hydrogen-oil ratio is 7.0, and air speed is
3.0h-1, catalyst amount is 0.50g.Regenerating after reaction 8h, reproducer is 600 DEG C of air roasting 7h and 400 DEG C
Hydrogen reducing 7h.
Shown by the result reacted, PtSn/MgAl-LDO/Al2O3Fresh catalyst and PtSn/Al2O3The positive heptan of fresh catalyst
Alkane initial conversion is close, all reaches 65%, and after twice regeneration, PtSn/MgAl-LDO/Al2O3The activity of catalyst
Substantially fresh catalyst level can be returned to selectivity, and PtSn/Al2O3The activity and selectivity of catalyst is but urged not as fresh
Agent, illustrates PtSn/MgAl-LDO/Al2O3The reusability of catalyst is better than PtSn/Al2O3Catalyst.Additionally, with newly
Fresh catalyst is compared, the PtSn/MgAl-LDO/Al after regeneration2O3The initial activity (65%) of catalyst does not becomes, and C1 selectivity is also
It is not changed in, the PtSn/Al after regeneration2O3The C1 selectivity of catalyst adds about 1%, this is because PtSn/Al2O3Catalysis
There is Severe aggregation, PtSn/MgAl-LDO/Al in the Pt in agent2O3In catalyst there is not Severe aggregation in Pt,
PtSn/MgAl-LDO/Al2O3In catalyst, the dispersion stabilization of Pt is better than PtSn/Al2O3Catalyst, during this is with embodiment 2
Result shown in table 1 is consistent.
Embodiment 2
Step A:Mg (NO3)2·6H2O and carbamide are with Mg2+: the ratio of carbamide=3:2 is dissolved in deionized water, to equipped with one
Quantitative Al2O3Reactor carry out evacuation process be subsequently adding above-mentioned mixed solution, 85 DEG C of crystallization 5h.Filtering and washing, uses
Deionized water is washed till neutrality, is dried.
Step B: to equipped with the MgAl-LDH/Al of synthesis in step (A)2O3Container carry out evacuation process, inject SnCl4
Solution (0.018g SnCl4·5H2O is dissolved in water), stand, be dried.Sn by above-mentioned preparation4+/MgAl-LDH/Al2O3Precursor
It is placed in container and carries out evacuation process, be then injected into 3.745mL Na2PtCl6Solution (0.046M), stands, and is dried.
Step C: roasting 4h (flow velocity 80mL/min/g) in preferably 600 DEG C air of catalyst precarsor prepared by step (B), excellent
Select the H of 400 DEG C2Reduction 4h (flow velocity 60mL/min/g), heating rate is 10 DEG C/min.
I.e. prepare PtSn/MgAl-LDO/Al2O3Catalyst, the actual negative carrying capacity of Pt is 0.29%, the actual negative carrying capacity of Sn
It is 0.16%.
Embodiment 3
Step A:Mg (NO3)2·6H2O and carbamide are with Mg2+: the ratio of carbamide=3:2 is dissolved in deionized water, to equipped with one
Quantitative Al2O3Reactor carry out evacuation process be subsequently adding above-mentioned mixed solution, 85 DEG C of crystallization 5h.Filtering and washing, uses
Deionized water is washed till neutrality, is dried.
Step B: to equipped with the MgAl-LDH/Al of synthesis in step (A)2O3Container carry out evacuation process, inject SnCl4
Solution (0.047g SnCl4·5H2O is dissolved in water), stand, be dried.Sn by above-mentioned preparation4+/MgAl-LDH/Al2O3Precursor
It is placed in container and carries out evacuation process, be then injected into 3.745mL Na2PtCl6Solution (0.046M), stands, and is dried.
Step C: roasting 4h (flow velocity 80mL/min/g) in preferably 600 DEG C air of catalyst precarsor prepared by step (B), excellent
Select the H of 400 DEG C2Reduction 4h (flow velocity 60mL/min/g), heating rate is 10 DEG C/min.
I.e. prepare PtSn/MgAl-LDO/Al2O3Catalyst, the actual negative carrying capacity of Pt is 0.29%, the actual negative carrying capacity of Sn
It is 0.39%.
Catalyst obtained by embodiment 2 and embodiment 3 is for being catalyzed the reforming reaction of normal heptane, reusability and embodiment
The reusability of the catalyst of 1 gained is consistent.
Claims (7)
1. the preparation method of the reforming catalyst of an active center stable dispersion, it is characterised in that comprise the following steps:
(1) at spherical Al2O3Particle surface growth in situ binary brucite MY-LDH/Al2O3；
(2) preparation of catalyst precarsor
To equipped with MY-LDH/Al in step (1)2O3Container carry out evacuation process, inject stannum precursor solution,
Control Sn actual negative carrying capacity in catalyst, within 0.10 0.40wt.%, to stand, be dried；By above-mentioned system
Standby Sn4+/MY-LDH/Al2O3Precursor is placed in container and carries out evacuation process, is then injected into platinum precursor molten
Liquid, controls Pt actual negative carrying capacity in catalyst and, within 0.10 0.40wt.%, stands, be dried；
(3) preparation of catalyst
Catalyst precarsor roasting 4-8h in the air of 350-900 DEG C of scope prepared by step (2),
The H of 350-900 DEG C of scope2Middle reduction 4-8h, heating rate is 0-10 DEG C/min.
2. according to the method for claim 1, it is characterised in that step (1) is by M2+Soluble in water with carbamide, M2+: urine
Mol ratio=(1 3) of element: (2 4)；To equipped with solid spherical Al2O3The reactor of granule carries out evacuation
Process is subsequently adding above-mentioned mixed solution, crystallization, washing, is dried.
3. according to the method for claim 1, it is characterised in that Pt and Sn mass ratio excursion in step (2)
Within 1:1 2:1.
4. according to the method for claim 1, it is characterised in that in step (3), catalyst precarsor is at 400-600 DEG C
Roasting 4-8h in air, at the H of 400-600 DEG C2Middle reduction 4-8h.
5. according to the method for claim 1, it is characterised in that step (3) air velocity 50-100mL/min/g,
Hydrogen flow rate 50-100mL/min/g.
6. according to the method for claim 1, it is characterised in that stannum precursor is SnCl2·2H2O or SnCl4·5H2O；Platinum
Precursor is H2PtCl6、[Pt(NH3)4](NO3)2、Pt(acac)2Or Na2PtCl6·6H2O。
7. the application of any one of claim 1-6 method gained catalyst, repetitive cycling is applied to normal heptane conversion reaction.
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