CN108745406A - A kind of method enhancing Silicalite-1 zeolite molecular sieve acidity and its application in paraffin dehydrogenation - Google Patents
A kind of method enhancing Silicalite-1 zeolite molecular sieve acidity and its application in paraffin dehydrogenation Download PDFInfo
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Abstract
The present invention provides a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity, includes the following steps：Silicalite-1 zeolite molecular sieves are placed in zinc salt solution and are impregnated；The Silicalite-1 zeolite molecular sieves drying of zinc salt solution will be impregnated, has obtained the solid content of load zinc salt；Solid content is roasted, the Silicalite-1 zeolite molecular sieves of loading ZnO are obtained.ZnO is carried on Silicalite-1 zeolite molecular sieves by the present invention, the acidity of Silicalite-1 zeolite molecular sieves, acid amount can be made to significantly increase, the acid centre of generation has unique catalytic performance, it can be used for being catalyzed propane or dehydrogenation of isobutane reaction, there are the remarkable advantages such as reactivity is high, olefine selective is good, cracking dry gas is few.
Description
Technical field
The invention belongs to technical field of zeolite, and in particular to a kind of that ZnO is carried on Silicalite-1 zeolites
The method for making Silicalite-1 zeolite molecular sieve acidity enhance on molecular sieve and its application in paraffin dehydrogenation.
Background technology
It is (complete that Flanigen in 1978 etc. has synthesized the Silicalite-1 zeolite molecular sieves with MFI topological structures for the first time
Silicone zeolite molecular sieve).Silicalite-1 molecular sieves are not since zeolitic frameworks contain aluminium atom, thus with hydrophobic, oleophylic
Characteristic.In addition, Silicalite-1 zeolite molecular sieves also have good thermal stability and acid resistance.Perfectly
Silicalite-1 zeolite molecular sieves are made up of oxygen-octahedron bridging oxygen link.But it is roasted in hydrothermal synthesis or high temperature
During burning etc., the silicon atom of four-coordination can fall off to generate defect silicon position in Silicalite-1 molecular sieve zeolites skeletons,
And then a large amount of silicone hydroxyl species are generated inside zeolite cavity.The presence of a large amount of silicone hydroxyl species, makes Silicalite-1 boil
Stone molecular sieve hydrophobicity is deteriorated, and generates certain faintly acid.It can with weakly acidic Silicalite-1 zeolite molecular sieves
Catalysis of pimelinketone oxime Beckmann, which is reset, generates caprolactam.Traditional Beckmann rearrangement reactions are usually using sulfuric acid or more
The problems such as polyphosphoric acid etc. is used as catalyst, and there are the environmental pollution of equipment burn into and poor selectivity of product.
Although being capable of catalysis of pimelinketone oxime progress Beckmann weights with weakly acidic Silicalite-1 zeolite molecular sieves
It arranges reaction and generates caprolactam, but since Silicalite-1 zeolite molecular sieves are also all relatively scarce in acid amount and acid strength etc.
It is weary, therefore it has significant limitation in the application of catalytic field.Differ widely with this situation, with Silicalite-1
Zeolite molecular sieve has the HZSM-5 zeolite molecular sieves of same MFI topological structures because skeleton is containing aluminium generation strong acid center, thus
It is used widely in the fields such as petroleum refining, petrochemical industry, Modern Coal-based Chemical, organic synthesis and fine chemistry industry.For example, highly acid
ZSM-5 zeolite molecular sieve being capable of catalyzed alkene isomery, alkylating aromatic hydrocarbon, toluene disproportionation, methanol to hydro carbons (MTG, MTO, MTA)
And the series reactions such as light-hydrocarbon aromatized.It can be seen that making Silicalite-1 zeolite molecular sieves using suitable method
Acidity increases, and perhaps can effectively expand its application in catalytic field.
It is well known that it is miscellaneous to be inserted into Silicalite-1 zeolitic frameworks Al, B, Ga, Ge, Ti etc. by means of hydrothermal synthesis
Atom (the heteroatom type zeolite for synthesizing Silicalite-1) is that Silicalite-1 zeolite molecular sieve acidity is made to significantly increase
Effective ways.Such as open source literature Applied Catalysis A:General 337 (2008) 58-65 passes through Density functional
It calculates and nuclear-magnetism characterization is studies have shown that the acid strength of the Silicalite-1 zeolites of Heteroatom doping is ranked sequentially as following：Al-
Silicalite-1>Fe-Silicalite-1>B-Silicalite-1>Ti-Silicalite-1.In addition, being synthesized by modulation
The methods of condition and soda acid post-processing, can also be effectively increased the acidity of Silicalite-1 zeolite molecular sieves.Such as open source literature
Microporous and Mesoporous Materials 182 (2013) 220-228 are by changing hydrothermal synthesis crystallization condition
And it is post-processed by ammonium hydroxide or ammonium chloride, effective modulation acidity of Silicalite-1 zeolites.After modulation
Silicalite-1 zeolite molecular sieves show isopropanol dehydration and Cumene cracking catalytic activity.But Silicalite-1
Heteroatom type zeolite hydrothermal synthesis difficulty it is big, hetero atom enters skeleton limited amount, and in catalyst processing middle skeleton
Hetero atom is also very easy to move out from skeleton.Change hydrothermal synthesizing condition and carries out soda acid post-processing for Silicalite-1
For increase that sour degree is very limited and difficulty or ease regulate and control.
Alkane (such as propane and iso-butane) anaerobic dehydrogenation catalyst is mainly Pt/Al at present2O3Or CrxO3/Al2O3It urges
Agent, they belong to metal or metal oxide oxidation catalyst dehydrogenation.Although UOP and Lummus companies are respectively by Pt/Al2O3
And CrxO3/Al2O3Catalyst industrialization, but above-mentioned two classes catalyst still has following notable defects：(1)Pt/Al2O3Catalysis
Pt element resources are rare and expensive in agent；(2)CrxO3/Al2O3Catalyst can generate Cr VI in use, and six
Valence chromium is toxic, and environment is unfriendly.Therefore, exploitation efficiently still merits attention with highly selective paraffin dehydrogenation catalyst.
Transiting metal oxidation zinc (ZnO) is carried on by post-modification approach on Silicalite-1 zeolite molecular sieves, it can
The acidity of Silicalite-1 zeolite molecular sieves is dramatically increased, and is applied in paraffin dehydrogenation, this technical method mesh
It is preceding there is not yet patent and document report.
Invention content
In order to solve the above technical problems, present invention offer is a kind of to be supported on Silicalite- by ZnO by post-modification approach
On 1 zeolite molecular sieve, to the method for making Silicalite-1 zeolite molecular sieve acidity dramatically increase.
The principles of science of this method is, when transition metal ZnO is carried on Silicalite-1 zeolite molecular sieves, dropping place
ZnO nano cluster in Silicalite-1 zeolite cavities can be with the hydroxyl nest of silicon shortcoming position in Silicalite-1 zeolite cavities
Strong interaction occurs to generate the Louis acid site (Lewis) of moderate strength and belong to the Blang Si Taide of weak acid rankAcid site, quantity are positively correlated with ZnO load capacity in a certain range, meanwhile, modified total silicon
Total acid amount and acid strength of Silicalite-1 zeolites significantly improves.The total silicon Silicalite-1 zeolite molecules of loading ZnO
Sieve catalyst is because acid with the appropriateness different from highly acid ZSM-5 zeolite, Louis (Lewis) acid of moderate strength of the present invention
Center and the Taides Bu LangsiAcid site shows urge excellent to paraffin dehydrogenation and alkene hydrocarbon isomerization respectively
Change activity.
Technical scheme is as follows：
A kind of method (Silicalite-1 zeolites of loading ZnO point of enhancing Silicalite-1 zeolite molecular sieve acidity
The preparation method of son sieve), include the following steps：
A. Silicalite-1 zeolite molecular sieves are placed in zinc salt solution and are impregnated, dip time is 0.2~100h, leaching
Stain temperature is 10~90 DEG C；
B. the Silicalite-1 zeolite molecular sieves for having impregnated zinc salt solution are dried, obtains the solid of load zinc salt
Object；
C. solid content is roasted, obtains the Silicalite-1 zeolite molecular sieves of loading ZnO, is denoted as ZnO/
Silicalite-1；
A concentration of 0.005~1.0mol/L of zinc salt, zinc salt solution and Silicalite-1 in the zinc salt solution
It is 1 that the liquid of zeolite molecular sieve, which consolidates volume ratio,:1~20:1, unit ml/g.
It is preferred that it is 3 that the liquid of zinc salt solution and Silicalite-1 zeolite molecular sieves, which consolidates volume ratio,:1~10:1 (ml/g),
With this condition, the load of zinc salt is not only contributed to, and is economized on resources, is effectively reduced cost and energy consumption.
It is preferred that the zinc salt is one or more of zinc nitrate, zinc chloride and zinc carbonate.
Dip time is 0.5~6h in preferred steps A, and dipping temperature is 30~80 DEG C, and impregnation pressure is normal pressure or negative pressure.
Dry condition is in preferred steps B：Drying temperature be 110 DEG C, drying time be 1~for 24 hours.Further, it does
The dry time is 6~12h.Further, the Silicalite-1 zeolite molecular sieve liters of zinc salt solution will have been impregnated when dry
Aqueous solution is evaporated by temperature to 90 DEG C, then the dry 12h at 110 DEG C.
In preferred steps C roasting condition be calcination temperature be 450~550 DEG C, roasting time be 1~for 24 hours.Further,
Calcination temperature is 500 DEG C, and roasting time is 3~6h.
The present invention also provides a kind of Silicalite-1 zeolite molecular sieves of loading ZnO, ZnO load capacity is 0.5~
20wt%.Further, ZnO load capacity is 1~10wt%.Under this load capacity, the acid of Silicalite-1 zeolite molecular sieves
Property can be increased considerably.
Originally it returns and a kind of Silicalite-1 zeolite molecular sieves of loading ZnO are provided are reacted for paraffin dehydrogenation, alkane
Hydrocarbon dehydrogenation reaction device is fixed bed or moving bed or fluid bed；The alkane is propane or iso-butane；Reaction temperature is
450~700 DEG C；Reaction pressure is normal pressure or negative pressure；Reaction mass air speed is 100~3000h-1, further, reaction temperature is
500~600 DEG C of reaction mass air speeds are 500~2000h-1。
It invents the Silicalite-1 zeolite molecular sieves being related to and formula in the patent and document having disclosed can be used
It carries out.Such as patent EP0494535 (A1)；Such as periodical literature Microporous and Mesoporous Materials, 101
(2007)153–160；Microporous and Mesoporous Materials,182(2013)220–228；
J.Phys.Chem, 1992,96,4985-4990；Chin.J.Catal, 2001,22,513-514 etc..The Silicalite-1
Zeolite molecular sieve grain size can be between 100nm~5 μm, preferably 100~300nm.The engineer for being familiar with this field can adopt
With the technical method reported in open source literature and patent, the synthesis of Silicalite-1 zeolite molecular sieves is carried out.It will in step A
It is impregnated again after the drying of Silicalite-1 zeolite molecular sieves, roasting.Drying temperature be 110 DEG C, drying time be 1~for 24 hours,
Further, drying time is 6~12h；Calcination temperature be 450~550 DEG C, roasting time be 1~for 24 hours, further, roasting
Temperature is 500 DEG C, and roasting time is 3~6h.
The method provided by the invention transition metal ZnO being carried on Silicalite-1 zeolite molecular sieves, can make
Acidity, the acid amount of Silicalite-1 zeolite molecular sieves significantly increase, and the acid centre of generation is different from ZSM-5 zeolite, has
Unique catalytic performance.Acid site caused by this method is mainly the Lewis acid centers of moderate strength, but also has Bu Langsi
Taide acid site.The quantity in acid site with ZnO load capacity positive correlations, can be adjusted in a certain range with ZnO load capacity.This
ZnO/Silicalite-1 catalyst prepared by invention can be used for being catalyzed propane or dehydrogenation of isobutane reaction, have reactivity
Height, olefine selective are good, crack dry gas (C1+C2) remarkable advantages are waited less.
Description of the drawings
Fig. 1 be comparative example 3, ZnO/Silicalite-1 of the present invention NH3-TPD。
Fig. 2 is the NH of comparative example 1, comparative example 2 and the embodiment of the present invention 33-TPD。
Specific implementation mode
The specific implementation mode of technical solution of the present invention is described in detail below, but is retouched the present invention is not limited to following
State content：Comparative example 1
The preparation of 6.0%ZnO/HZSM-5 (containing 6.0wt%ZnO) catalyst
(1) cf. publication Microporous and Mesoporous Materials 183 (2014) 30-36 are closed
At HZSM-5 zeolite molecular sieves.Waterglass and aluminum sulfate are used as silicon source and silicon source, and n-butylamine (NBA) is template, a small amount of sodium
Salt is auxiliary agent.Specific synthesis step is as follows：First, it is dissolved in deionized water after aluminum sulfate and sodium salt mixing, generates Sol A,
N-butylamine and sodium silicate dissolving generate sol B in deionized water；Then Sol A is added drop-wise in sol B and is stirred, dripped
Finish and be stirred for 2h, obtains the colloidal solution of following molar ratios：2Na2O：1Al2O3：31.2SiO2：830H2O：12NBA：18NaCl；
Above-mentioned colloidal solution is placed in stainless steel water heating kettle crystalline substance China 48h at 170 DEG C and obtains NaZSM-5 zeolite precursor bodies；Further filtering,
It washs, then the dry 12h in 110 DEG C of air atmospheres, roasts 6h in 550 DEG C of air atmospheres, obtain nanometer NaZSM-5 zeolites point
Son sieve.NaZSM-5 zeolites are exchanged 3 times with aqueous ammonium nitrate solution, obtain Nano-sized HZSM-5 zeolite molecular sieve.
(2) the specific preparation process of carrying transition metal oxide ZnO is as follows on Nano-sized HZSM-5 zeolite molecular sieve：It is first
First prepare 0.0918mol/L zinc nitrate aqueous solutions；Then Nano-sized HZSM-5 zeolite molecular sieve dry, after roasting is taken to be placed in nitric acid
In zinc aqueous solution, liquid-solid ratio 10：1 (ml/g) stirs 6h at 60 DEG C；110 DEG C are warming up to, steams deionized water under stirring
It is dry, obtain the Nano-sized HZSM-5 zeolite molecular sieve solid content of load zinc salt；By dry 12h, 550 DEG C of air at 110 DEG C of solid content
6h is roasted in atmosphere, obtains the 6.0%ZnO/HZSM-5 catalyst that ZnO content is 6.0Wt%.
Comparative example 2
6.0%ZnO/SiO2The preparation of (containing 6.0wt%ZnO) catalyst
In white carbon (SiO2) on carrying transition metal oxide ZnO specific preparation process it is as follows：It prepares first
0.0918mol/L zinc nitrate aqueous solutions；Then SiO dry, after roasting is taken2It is placed in zinc nitrate aqueous solution, liquid-solid ratio 10：
1 (ml/g) stirs 6h at 60 DEG C；110 DEG C are warming up to, is evaporated deionized water under stirring, obtains the SiO of load zinc salt2
Solid content；By dry 12h at 110 DEG C of solid content, 6h is roasted in 550 DEG C of air atmospheres, it is 6.0Wt%'s to obtain ZnO content
6.0%ZnO/SiO2Catalyst.
Comparative example 3
The preparation of Silicalite-1 zeolite molecular sieves
Cf. publication Chin.J.Catal., 2001,22,513-514 synthesis total silicon Silicalite-1 zeolite molecules
Sieve.Ethyl orthosilicate (TEOS) and tetrapropylammonium hydroxide (TPAOH) and deionized water are pressed into following molar ratio SiO2:
0.3TPAOH:30H2O is mixed, and 3h is stirred at 60 DEG C；It is subsequently placed in stainless steel water heating kettle that crystallization obtains total silicon for 24 hours at 170 DEG C
Silicalite-1 zeolite precursor bodies；Further filtering is washed, then dry 12h, 550 DEG C of air in 110 DEG C of air atmospheres
6h is roasted in atmosphere, obtains Silicalite-1 zeolite molecular sieves.
Embodiment 1
The preparation of 1.0%ZnO/Silicalite-1 (containing 1.0wt%ZnO) catalyst
(1) the present embodiment uses the Silicalite-1 zeolite molecular sieves that comparative example 3 obtains.
(2) the specific preparation process of carrying transition metal oxide ZnO is as follows on Silicalite-1 zeolite molecular sieves：
0.0123mol/L zinc nitrate aqueous solutions are prepared first；Then Silicalite-1 zeolite molecular sieves dry, after roasting is taken to be placed in
In zinc nitrate aqueous solution, liquid-solid ratio 10：1 (ml/g), stirring dipping 6h at 60 DEG C；90 DEG C are then heated to steam aqueous solution
It is dry, and the further dry 12h at 110 DEG C, obtain the Silicalite-1 zeolite solid contents of load zinc salt；By solid content 550
6h is roasted in DEG C air atmosphere, obtains the 1.0%ZnO/Silicalite-1 catalyst that ZnO content is 1.0Wt%.
Embodiment 2
The preparation of 3.0%ZnO/S-1 (containing 3.0wt%ZnO) catalyst
Embodiment 1 is repeated, but nitric acid zinc concentration in zinc nitrate aqueous solution is configured to 0.0369mol/ in step (2)
L obtains the 3.0%ZnO/Silicalite-1 catalyst that ZnO content is 3.0Wt%.
Embodiment 3
The preparation of 6.0%ZnO/Silicalite-1 (containing 6.0wt%ZnO) catalyst
Embodiment 1 is repeated, but nitric acid zinc concentration in zinc nitrate aqueous solution is configured to 0.0738mol/ in step (2)
L obtains the 6.0%ZnO/Silicalite-1 catalyst that ZnO content is 6.0Wt%.
Embodiment 4
The preparation of 8.0%ZnO/Silicalite-1 (containing 8.0wt%ZnO) catalyst
Embodiment 1 is repeated, but nitric acid zinc concentration in zinc nitrate aqueous solution is configured to 0.0984mol/ in step (2)
L obtains the 8.0%ZnO/Silicalite-1 catalyst that ZnO content is 8.0Wt%.
Embodiment 5
The preparation of 12.0%ZnO/Silicalite-1 (containing 12.0wt%ZnO) catalyst
Embodiment 1 is repeated, but nitric acid zinc concentration in zinc nitrate aqueous solution is configured to 0.148mol/ in step (2)
L obtains the 12.0%ZnO/Silicalite-1 catalyst that ZnO content is 12.0Wt%.
Embodiment 6
The preparation of 0.5%ZnO/Silicalite-1 (containing 0.5wt%ZnO) catalyst
Embodiment 1 is repeated, but configures nitric acid zinc concentration in zinc nitrate aqueous solution in step (2)
0.00615mol/L obtains the 0.5%ZnO/Silicalite-1 catalyst that ZnO content is 0.5Wt%.
Embodiment 7
The preparation of 20%ZnO/Silicalite-1 (containing 20.0wt%ZnO) catalyst
Embodiment 1 is repeated, but configures nitric acid zinc concentration in zinc nitrate aqueous solution in step (2)
0.246mol/L obtains the 20%ZnO/Silicalite-1 catalyst that ZnO content is 20.0Wt%.
Embodiment 8
Embodiment 1 is repeated, but zinc nitrate is replaced with into zinc chloride in step (2), zinc chloride in solder(ing)acid
Concentration is configured to 0.005mol/L, liquid-solid ratio 1：1 (ml/g) stirs 0.2h at 90 DEG C.
Embodiment 9
Embodiment 1 is repeated, but zinc nitrate is replaced with into zinc carbonate in step (2), zinc carbonate in zinc carbonate aqueous solution
Concentration is configured to 1.0mol/L, liquid-solid ratio 20：1 (ml/g) stirs 100h at 10 DEG C.
Embodiment 10
Embodiment 1 is repeated, but liquid-solid ratio is 3 in step (2)：1 (ml/g) stirs 6h at 30 DEG C.
Embodiment 11
Comparison study implements 1, comparative example 2, comparative example 3, series ZnO/Silicalite-1 catalysis of the invention
The NH of agent3- TPD such as Fig. 1 and Fig. 2.As seen from Figure 1, for total silicon Silicalite-1 zeolites after modified, acid amount and acid are strong
Degree all dramatically increases.And HZSM-5 zeolites are after modified, strong acid amount is reduced, and weak acid amount dramatically increases；White carbon is through zinc
Salt is modified, and total acid content also has increase, but the acid amount of not modified total silicon Silicalite-1 zeolites increases obviously.
Embodiment 12
It uses catalytic dehydrogenation of isobutane to generate isobutene as probe reaction, investigates comparison and implement 1, comparative example 2, comparison
The zeolite molecular sieve catalyst acid catalysis dehydrogenation of load series ZnO prepared by embodiment 3, embodiment 1-5.
Dehydrogenation reaction evaluation carries out on self-built fixed-bed micro-reactor.U-shaped reaction tube in be packed into
ZnO/Silicalite-1 catalyst 0.2g (20~40 mesh) is passed through nitrogen purging, and is warming up to the heating rate of 1 DEG C/min
550 DEG C, continues to keep purging 10min in 550 DEG C of nitrogen, then stop purging.Dehydrogenation of isobutane reaction carries out at 550 DEG C,
Reaction pressure normal pressure, reaction mass air speed 1200h-1, dehydrogenation product application gas-chromatography analyzed.Reaction result such as table 1,
In, X (i-C4 0) be raw material iso-butane conversion ratio, SiRepresent the selectivity of different products.It can be seen that ZnO/Silicalite-
1 catalyst shows excellent dehydrogenation of isobutane and isobutene skeletal isomerization catalytic activity, and dry gas by-product is less；In isobutyl
In the case of alkane conversion ratio 60.2%, total butylene selectively reaches 91% (embodiment 2).
Iso-butane can also be that propane, reaction temperature can be at 450~700 DEG C；Reaction pressure is negative pressure；Reaction mass is empty
Speed is 100~3000h-1。
1 comparative example 1-3 of table, series ZnO/Silicalite-1 catalyst acid catalyzing iso-butane alkane dehydrogenation reactions of the invention
Performance
Examples detailed above is technical concept and technical characterstic to illustrate the invention, can not limit the present invention's with this
Protection domain.The equivalent transformation or modification that all essence according to the present invention is done, should all cover in protection scope of the present invention
Within.
Claims (10)
1. a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity, which is characterized in that include the following steps：
A. Silicalite-1 zeolite molecular sieves are placed in zinc salt solution and are impregnated, dip time is 0.2~100h, dipping temperature
Degree is 10~90 DEG C；
B. the Silicalite-1 zeolite molecular sieves for having impregnated zinc salt solution are dried, obtains the solid content of load zinc salt；
C. solid content is roasted, obtains the Silicalite-1 zeolite molecular sieves of loading ZnO；
A concentration of 0.005~1.0mol/L of zinc salt in the zinc salt solution, zinc salt solution and Silicalite-1 zeolites
It is 1 that the liquid of molecular sieve, which consolidates volume ratio,:1~20:1, unit ml/g.
2. a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity as described in claim 1, which is characterized in that zinc
It is 3 that the liquid of saline solution and Silicalite-1 zeolite molecular sieves, which consolidates volume ratio,:1~10:1.
3. a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity as described in claim 1, which is characterized in that step
Zinc salt described in rapid A is one or more of zinc nitrate, zinc chloride and zinc carbonate.
4. a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity as described in claim 1, which is characterized in that step
Dip time is 0.5~6h in rapid A, and dipping temperature is 30~80 DEG C, and impregnation pressure is normal pressure or negative pressure.
5. a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity as described in claim 1, which is characterized in that step
Dry condition is in rapid B：Drying temperature be 110 DEG C, drying time be 1~for 24 hours.
6. a kind of method of enhancing Silicalite-1 zeolite molecular sieve acidity as described in claim 1, which is characterized in that step
It is 450~550 DEG C that roasting condition, which is calcination temperature, in rapid C, roasting time is 1~for 24 hours.
7. a kind of Silicalite-1 zeolite molecular sieves of loading ZnO prepared by the method as described in claim 1, feature exist
In ZnO load capacity is 0.5~20.0wt%.
8. a kind of Silicalite-1 zeolite molecular sieves of loading ZnO as claimed in claim 7, which is characterized in that ZnO is loaded
Amount is 1~10wt%.
9. a kind of Silicalite-1 zeolite molecular sieves of loading ZnO prepared by the method as described in claim 1 are used for alkane
Hydrocarbon dehydrogenation reaction, which is characterized in that paraffin dehydrogenation reaction unit is fixed bed or moving bed or fluid bed；The alkane is
Propane or iso-butane；Reaction temperature is 450~700 DEG C；Reaction pressure is normal pressure or negative pressure；Reaction mass air speed be 100~
3000h-1。
10. the Silicalite-1 zeolite molecular sieves of loading ZnO as claimed in claim 9 are reacted for paraffin dehydrogenation,
It is characterized in that, reaction temperature is 500~600 DEG C, and reaction mass air speed is 500~2000h-1。
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110496635A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN111672532A (en) * | 2019-03-11 | 2020-09-18 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
| CN111804327A (en) * | 2020-08-11 | 2020-10-23 | 江西农业大学 | Mo-loaded pure silicalite heterogeneous catalyst and preparation method and application thereof |
| CN113058634A (en) * | 2021-03-31 | 2021-07-02 | 陕西师范大学 | Fe modified-Silicalite-1 supported GaN catalyst and catalytic application thereof |
| CN114835545A (en) * | 2022-05-06 | 2022-08-02 | 湘潭大学 | Method for preparing propylene by dehydrogenating propane oxidized by carbon dioxide |
| CN115805097A (en) * | 2022-12-01 | 2023-03-17 | 中触媒新材料股份有限公司 | Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159579A (en) * | 2013-02-07 | 2013-06-19 | 大连理工大学 | Method of light alkane catalytic cracking by using modified molecular sieve catalyst |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
-
2018
- 2018-06-15 CN CN201810617330.3A patent/CN108745406A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159579A (en) * | 2013-02-07 | 2013-06-19 | 大连理工大学 | Method of light alkane catalytic cracking by using modified molecular sieve catalyst |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
Non-Patent Citations (1)
| Title |
|---|
| GUODONG LIU等: "Silicalite-1 zeolite acidification by zinc modification and its catalytic properties for isobutane conversion", 《RSC ADV.》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110496635A (en) * | 2018-05-17 | 2019-11-26 | 中国石油化工股份有限公司 | The method of dehydrogenation of isobutane catalyst and preparation method thereof and preparing isobutene through dehydrogenation of iso-butane |
| CN110496635B (en) * | 2018-05-17 | 2022-01-04 | 中国石油化工股份有限公司 | Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation |
| CN111672532A (en) * | 2019-03-11 | 2020-09-18 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
| CN111804327A (en) * | 2020-08-11 | 2020-10-23 | 江西农业大学 | Mo-loaded pure silicalite heterogeneous catalyst and preparation method and application thereof |
| CN111804327B (en) * | 2020-08-11 | 2023-04-14 | 江西农业大学 | Mo-loaded pure silicalite heterogeneous catalyst and preparation method and application thereof |
| CN113058634A (en) * | 2021-03-31 | 2021-07-02 | 陕西师范大学 | Fe modified-Silicalite-1 supported GaN catalyst and catalytic application thereof |
| CN113058634B (en) * | 2021-03-31 | 2023-07-07 | 陕西师范大学 | Fe modified-Silicalite-1 supported GaN catalyst and catalytic application thereof |
| CN114835545A (en) * | 2022-05-06 | 2022-08-02 | 湘潭大学 | Method for preparing propylene by dehydrogenating propane oxidized by carbon dioxide |
| CN114835545B (en) * | 2022-05-06 | 2024-05-14 | 湘潭大学 | Method for preparing propylene by dehydrogenating carbon dioxide by oxidizing propane |
| CN115805097A (en) * | 2022-12-01 | 2023-03-17 | 中触媒新材料股份有限公司 | Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
| CN115805097B (en) * | 2022-12-01 | 2024-03-01 | 中触媒新材料股份有限公司 | Large-grain Zn@Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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