CN106669793B - A kind of modified zsm-5 zeolite and its preparation method and application - Google Patents
A kind of modified zsm-5 zeolite and its preparation method and application Download PDFInfo
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Abstract
The present invention discloses a kind of modified zsm-5 zeolite and its preparation method and application.The modified zsm-5 zeolite, by weight percentage, containing 3.0~5.0% zirconium dioxide, 0.1~0.5% iridium dioxide and 0.2~0.5% SO4 2‑, remaining is ZSM-5 molecular sieve.The preparation method includes: containing zirconium and iridium ZSM-5 molecular sieve preparation process, containing zirconium and iridium ZSM-5 molecular sieve acidification and stabilization process.It is high to have the advantages that low temperature active is high, product liquid receives high and octane number in the non-hydrogen modification for n-butene skeletal isomerization production isobutene byproduct in process gasoline for the non-hydrogen modifying catalyst of above-mentioned modified zsm-5 zeolite preparation.
Description
Technical field
The present invention relates to a kind of modified zsm-5 zeolites and its preparation method and application, it is more particularly related to
It is a kind of can be used for n-butene skeletal isomerization production isobutene process by-product gasoline non-hydrogen modification modified zsm-5 zeolite and
Preparation method and application.
Background technique
Continuous growth with market to high-knock rating gasoline demand, to the methyl- tert as octane enhancers of incorporation
The demand of butyl ether (MTBE) also increases.The total output of China MTBE in 2011 is more than 4,500,000 tons, and country MTBE is filled
The average utilization of capacity set is only 60%, and the insufficient supply of raw material isobutene has become the bottleneck of MTBE industry development.
With the lighting of ethylene cracking material, and by the impact of ethane cracking route and methanol-to-olefins project.Closely
The yield of Nian Lai, the cracking carbon-4 as main isobutene source reduce year by year.On the other hand, methanol-to-olefins project
It grows rapidly, by-product carbon four provides more n-butene resources again for market.Therefore, by cheap and resourceful positive fourth
Alkene is raw material, is reacted by skeletal isomerization n-butene tautomerizing to isobutene, is re-used as the raw material of MTBE synthesis, will solve now
The stage MTBE most economical approach that there is lack of raw materials.It is reported that by the end of the end of the year 2013, n-butene skeletal isomerization that China has invested to build
The total raw material treating capacity of device has been more than 3,800,000 tons/year.
During n-butene skeletal isomerization produces isobutene, the more or less a certain amount of gasoline of by-product of meeting, this kind of by-product
The olefin(e) centent of gasoline is usually above 50%, cannot be used directly for reconciliation gasoline product.N-butene skeletal isomerization byproduct in process
Gasoline yield depends on used catalyst type, operating condition and raw material composition etc..For example, CN1068320 discloses one
Series directly forms manufactured catalyst using unmodified ferrierite, SAPO, MeAlPO molecular sieve with binder, and is used for
The method that n-butene skeletal isomerization produces isobutene reaction, by adjusting the conditions such as reaction temperature, pressure and olefin partial pressures, the party
Method highest can by-product 63.36% gasoline.
Improve the utility value of the inferior patrol of n-butene skeletal isomerization byproduct in process, it will further increase n-butene
The Technical Economy of skeletal isomerization technique.It is a kind of improve n-butene skeletal isomerization technology economy method be reduce it is existing
The inferior patrol yield of technique.For example, US5132484 discloses a kind of method of n-butene skeletal isomerization production isobutene, it should
Gasoline yield can be reduced to 10% or less by 50% or more for catalyst by the AlPO-11 type molecular sieve that method uses iron modified.
The method that another kind improves the Technical Economy of n-butene skeletal isomerization technique is to convert the inferior patrol of by-product
For good gasoline blend component, such as it is used to improve the octane number of gasoline product.Inferior patrol higher for olefin(e) centent, is adopted
Alkene is converted into aromatic hydrocarbons or isoparaffin is most competitive conversion scheme with non-hydrogen aromatization modified.It is existing
Inferior patrol non-hydrogenation upgrading technology, the ZSM-5 molecular sieve for generalling use ZSM-5 molecular sieve or modification is catalyst, is being reacted
Pressure is that normal pressure arrives 5.0MPa, under conditions of reaction temperature is 300-550 DEG C, the skill that contacts feed gasoline directly with catalyst
Art scheme, such as CN93102129, CN101812318, CN102698790 and CN101081997.If prior art is used for
The non-hydrogen of n-butene skeletal isomerization byproduct in process gasoline modifies reaction, because needing to react at high temperature, certainly will will lead to and split
Yield of venting one's spleen is excessively high, reduces product gasoline yield.According to being reacted under existing catalyst low temperature (300 DEG C or less), because of catalyst
Acid strength is relatively low, is unable to satisfy ideal conversion rate, and it is low lesser with product octane number amplification that there are olefin conversions
It is insufficient.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of modified zsm-5 zeolite and preparation method thereof, and uses
Non-hydrogen of the catalyst of modified zsm-5 zeolite preparation provided by the invention in n-butene skeletal isomerization byproduct in process gasoline
Application in modification.
A kind of preparation method of modified zsm-5 zeolite, including following preparation step:
(1) aqueous solution containing zirconates and iridium salt is configured, be added to and in the immiscible organic solvent of water, is made containing zirconates and iridium
The volume ratio of saline solution and organic solvent is 1:20~1:40, forms suspension A, and under conditions of continuously stirring, meter is added
The Hydrogen ZSM-5 molecular sieve powder of amount, stirring form slurries B；
(2) organic solvent being evaporated in slurries B obtained in step (1) obtains dry glue C, and resulting dry glue is through at room temperature
After dry, drying, is roasted 5~10 hours at 500~550 DEG C, obtain the ZSM-5 molecular sieve D containing zirconium and iridium；
(3) using 0.1~0.5 mol/L inorganic acid or inorganic acid ammonium solution to obtained in step (2) contain zirconium and iridium
ZSM-5 molecular sieve D impregnated, soaking time be 1~5 hour, to the ZSM-5 molecular sieve D containing zirconium and iridium after immersion
It is eluted, gained filter cake roasts 5~10 hours at 500~550 DEG C after drying, and obtain acidified processing contains zirconium and iridium
ZSM-5 molecular sieve E.
(4) the ZSM-5 molecular sieve E of acidified processing obtained in step (3) is passed through at normal pressure, 300~350 DEG C
Stabilization processes reagent carries out processing 5~10 hours to it, obtains the modification of stabilized processing through drying, roasting after processing
ZSM-5 F。
In the method for the present invention step (1), the ZSM-5 molecular sieve can be commercial goods, can also be by existing method
Preparation.The zirconates is selected from one of zirconyl nitrate, zirconium acetate, zirconium chloride, zirconium-n-butylate, zirconium-n-propylate or a variety of, excellent
Select zirconyl nitrate.The iridium salt is selected from one of chloro-iridic acid, iridium chloride, ammonium chloroiridate or a variety of, preferably chloro-iridic acid.It is described
Organic solvent be normal pressure under boiling point in 50~90 DEG C of alkane or cycloalkane, specially n-hexane, hexamethylene, 2- methylpent
One of alkane, 3- methylpentane, 2- methyl hexane, 3- methyl hexane, methyl cyclopentane are a variety of, preferably n-hexane and hexamethylene
Alkane.
The addition volume of the method for the present invention aqueous solution as described in step (1) containing zirconates and iridium salt is equal to ZSM-5 molecule
The total pore volume of sieve.
Inorganic acid described in the method for the present invention step (3) is selected from one of sulfuric acid, nitric acid and hydrochloric acid or a variety of, preferably
Sulfuric acid.The inorganic acid ammonium is selected from one or more, the preferably sulfuric acid ammonium of ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate and ammonium chloride.
The concentration of the inorganic acid or inorganic acid ammonium solution is 0.1~0.5 mol/L.
It is roasted at 500~550 DEG C and roasts 5~10 hours in the method for the present invention step (4).The stabilization processes examination
Agent is raw material used in the zeolite product application process.As present invention further optimization, walked in the method for the present invention
Suddenly in (4), the stabilization processes reagent refers specifically to the vapour inferior of n-butene skeletal isomerization production isobutene byproduct in process
Oil.
It is a kind of using the above method prepare modified zsm-5 zeolite, by weight percentage, containing 3.0~5.0% two
Zirconium oxide, 0.1~0.5% iridium dioxide and 0.2~0.5% SO4 2-, remaining is ZSM-5 molecular sieve.
Application of the modified zsm-5 zeolite of the present invention in the non-hydrogen modification of inferior patrol, by modified ZSM-5 molecule
Straight forming is sieved, or by modified ZSM-5 molecular sieve and binder kneading and compacting well-known to those skilled in the art, is made non-
Face hydrogen modifying catalyst.It is mixed using modified zsm-5 zeolite and aluminium hydroxide binder as present invention further optimization
It pinches, and extrusion molding is made used in the present invention and faces hydrogen modifying catalyst, but the non-hydrogen lid catalyst in the present invention is simultaneously
It is not limited to be made using extruding forming method, it can also be well-known to those skilled in the art using powder, bead, extrudate etc.
Forming method.As it is of the invention still more preferably, in the non-hydrogen modifying catalyst, by weight percentage, change
Property ZSM-5 molecular sieve accounts for 50~90%.The suitable reaction condition that non-hydrogen for inferior patrol modifies: reaction temperature 200
~400 DEG C, preferably 200~300 DEG C；Pressure is 0.05~0.5 MPa, preferably 0.05~0.2 MPa；Weight (hourly) space velocity (WHSV) be 0.5~
10 h-1, preferably 0.5~2 h-1.The inferior patrol is generally mass content produced in various process and is higher than
30% gasoline.As present invention further optimization, the bad gasoline produces different from n-butene skeletal isomerization
By-product gasoline during butylene, in this kind of gasoline, alkene total weight content is not less than 50%.
Compared with prior art, the present invention has the advantage that
(1) IrO introduced in modified zsm-5 zeolite2Significantly improve ZrO2To SO4 2-The volume of holding, and then improve change
Property after ZSM-5 molecular sieve acid site quantity, particularly improved in the strong acid of modified zsm-5 zeolite using the method for the present invention
The quantity of the heart；
(2) stabilization processes step avoids acidified modified ZSM-5 molecular sieve F5 in direct application process, because of SO4 2-It is de-
Fall, blocking catalyst duct and lead to the rapid decrease of catalyst activity, enhance the stability of catalyst substantially.
(3) the non-hydrogen modifying catalyst of modified zsm-5 zeolite preparation is producing isobutyl for n-butene skeletal isomerization
In the non-hydrogen modification of alkene byproduct in process gasoline, it is high to have the advantages that low temperature active is high, product liquid receives high and octane number.
Detailed description of the invention
Fig. 1 is the NH of modified zsm-5 zeolite of the present invention3- TPD spectrogram.
Wherein, F1- presses the modified zsm-5 zeolite of the method for the present invention preparation, and F4- is free of iridium by the method for the present invention preparation
Modified zsm-5 zeolite, F5- press the method for the present invention preparation the modified zsm-5 zeolite without stabilization processes.
Specific embodiment
The effect and effect of the method for the present invention, but following embodiment are further illustrated below by Examples and Comparative Examples
It is not construed as limiting the invention.
Hydrogen type ZSM 5 molecular sieve as used in the following examples is commercial goods.The chemical reagent used is such as without special
It indicates, is analytical reagents.Binder used in catalyst preparation be aluminium hydrate powder, 0.47~0.53 ml/g of Kong Rongwei,
It is greater than 250 m than table2/ g, average pore size are 7.5~8.5 nm.
In the present invention, using the composition of gasoline family's composition method (PONA method) analysis feed gasoline and product, using research
Method octane number (RON) indicates the octane number of feed gasoline and product.The activity that catalyst is indicated using olefin conversion, is adopted
Gasoline products liquid is represented with cracking gas yield receives (cracking gas yield is lower, and liquid is received higher).
Embodiment 1
The specific preparation process of modified zsm-5 zeolite F1 is as follows: (1) 5.7 g zirconyl nitrates and 0.7g chloro-iridic acid are molten
In the deionized water of 22 ml, gained saline solution is added in the n-hexane solvent of 650 ml, is continuously stirred 1 hour, formed
Suspension A1.The Si/Al molar ratio that 114.5 g are added into suspension A1 is 76,0.19 cm of Kong Rongwei3The Hydrogen ZSM-5 of/g
Molecular sieve stirs 2 hours under room temperature (25 DEG C), obtains slurries B1.(2) it by slurries B1 dislocation Rotary Evaporators, is evaporated just
Hexane solvent obtains dry glue C1, dries 12 hours at 24 hours, 120 DEG C dry under room temperature (25 DEG C), then at 550 DEG C
Roasting 5 hours, obtains the ZSM-5 molecular sieve D1 containing zirconium and iridium.(3) ammonium sulfate that D1 is moved into 0.1 mol/L of 500 ml is molten
In liquid, immersion treatment 5 hours, after required soaking time to be achieved, ammonium sulfate is filtered out, and thoroughly drenched with deionized water
Molecular sieve is washed, obtained filter cake is dried 12 hours at drying 24 hours, 120 DEG C under room temperature (25 DEG C), then at 530 DEG C
Roasting 8 hours, obtains the ZSM-5 molecular sieve E1 of acidified processing.(4) under the conditions of normal pressure, 350 DEG C, E1 is stabilized
Processing is passed through bad gasoline used in present invention application (composition is referring to table 2), and the processing time is 8 hours, to be achieved
It after the required processing time, cools the temperature to room temperature (25 DEG C), and is dried at drying 24 hours, 120 DEG C under room temperature (25 DEG C)
It 12 hours, is then roasted 10 hours at 500 DEG C, obtains final modified zsm-5 zeolite F1.
Embodiment 2
The specific preparation process of modified zsm-5 zeolite F2 is as follows: (1) 7.7 g zirconyl nitrates and 0.2 g chloro-iridic acid are molten
In the deionized water of 26 ml, gained saline solution is added in the cyclohexane solvent of 520 ml, is continuously stirred 1 hour, formed
Suspension A2.The Si/Al molar ratio that 113.0 g are added into suspension A2 is 54,0.23 cm of Kong Rongwei3The Hydrogen ZSM-5 of/g
Molecular sieve stirs 2 hours under room temperature (25 DEG C), obtains slurries B2.(2) by slurries B2 dislocation Rotary Evaporators, it is evaporated ring
Hexane solvent obtains dry glue C2, dries 12 hours at 24 hours, 120 DEG C dry under room temperature (25 DEG C), then at 500 DEG C
Roasting 10 hours, obtains the ZSM-5 molecular sieve D2 containing zirconium and iridium.(3) ammonium sulfate that D2 is moved into 0.5 mol/L of 500 ml is molten
In liquid, immersion treatment 1 hour, after required soaking time to be achieved, ammonium sulfate is filtered out, and thoroughly drenched with deionized water
Molecular sieve is washed, obtained filter cake is dried 12 hours at drying 24 hours, 120 DEG C under room temperature (25 DEG C), then at 550 DEG C
Roasting 5 hours, obtains the ZSM-5 molecular sieve E2 of acidified processing.(4) under the conditions of normal pressure, 300 DEG C, E2 is stabilized
Processing is passed through bad gasoline used in present invention application (composition is referring to table 2), and the processing time is 5 hours, to be achieved
It after the required processing time, cools the temperature to room temperature (25 DEG C), and is dried at drying 24 hours, 120 DEG C under room temperature (25 DEG C)
It 12 hours, is then roasted 8 hours at 550 DEG C, obtains final modified zsm-5 zeolite F2.
Embodiment 3
The specific preparation process of modified zsm-5 zeolite F3 is as follows: (1) 9.3 g zirconyl nitrates and 1.1 g chloro-iridic acids are molten
In the deionized water of 23.7 ml, gained saline solution is added in the cyclohexane solvent of 950 ml, continuously stirs 1 hour, shape
At suspension A3.The Si/Al molar ratio that 114.5 g are added into suspension A3 is 93,0.21 cm of Kong Rongwei3The Hydrogen of/g
ZSM-5 molecular sieve stirs 2 hours under room temperature (25 DEG C), obtains slurries B3.(2) it by slurries B3 dislocation Rotary Evaporators, steams
Dry cyclohexane solvent obtains dry glue C3, dries 12 hours at 24 hours, 120 DEG C dry under room temperature (25 DEG C), then 530
It is roasted 10 hours at DEG C, obtains the ZSM-5 molecular sieve D3 containing zirconium and iridium.(3) D3 is moved into the sulfuric acid of 0.3 mol/L of 500 ml
In solution, immersion treatment 3 hours, after required soaking time to be achieved, sulfuric acid solution is filtered out, and thoroughly drenched with deionized water
Molecular sieve is washed, obtained filter cake is dried 12 hours at drying 24 hours, 120 DEG C under room temperature (25 DEG C), then at 500 DEG C
Roasting 10 hours, obtains the ZSM-5 molecular sieve E3 of acidified processing.(4) under the conditions of normal pressure, 330 DEG C, E3 is stabilized
Processing is passed through bad gasoline used in present invention application (composition is referring to table 2), and the processing time is 10 hours, wait reach
It to after the required processing time, cools the temperature to room temperature (25 DEG C), and is dried at drying 24 hours, 120 DEG C under room temperature (25 DEG C)
It is 12 hours dry, it is then roasted 10 hours at 530 DEG C, obtains final modified zsm-5 zeolite F3.
Comparative example 1
The performance and effect of modified zsm-5 zeolite in order to further illustrate the present invention, by method shown in embodiment 1, system
For the modified zsm-5 zeolite F4 without iridium, specific preparation process is identical with embodiment 1, only in step (1)
In be added without chloro-iridic acid.
Comparative example 2
The performance and effect of modified zsm-5 zeolite in order to further illustrate the present invention, by method shown in embodiment 1, system
The standby ZSM-5 molecular sieve F5 without stabilization processes, i.e., prepare acidified place by (1), (2) and (3) step in embodiment 1
The ZSM-5 molecular sieve E1 of reason.
Using the modified zsm-5 zeolite F1-F3 and comparative example prepared in x-ray fluorescence spectrometry embodiment 1-3
The composition of the modified zsm-5 zeolite F4 without iridium in the 1-2 and modified zsm-5 zeolite F5 without stabilization processes,
In terms of weight percentage, as a result it is listed in table 1.
Table 1
As shown in table 1, F1 and F4 is compared, it can be found that the IrO that the present invention introduces in modified zsm-5 zeolite2Significantly
Improve ZrO2To SO4 2-The volume of holding, and then improve the acid site quantity of modified ZSM-5 molecular sieve, particularly use this hair
Bright method improves the quantity (as shown in Figure 1) of the strong acid center of modified zsm-5 zeolite.
Embodiment 4~5
Respectively by F1 and F5 and aluminium hydroxide binder kneading and compacting, catalyst Z 1 and Z2 is made.Above two catalyst
In molecular sieve quality score be 50%.
Use the gasoline of by-product in a kind of n-butene skeletal isomerization production isobutene technique for raw material (composition is listed in table 2),
To evaluate the reactivity worth of catalyst Z 1 and Z2.
Table 2
Before carrying out evaluating catalyst, catalyst need to first be pre-processed 2 hours in 350 DEG C of nitrogen atmosphere, then be cooled to
Reaction temperature.It is 300 DEG C, reaction pressure 0.15MPa in reaction temperature, air speed is 2 h using above-mentioned gasoline as raw material-1Item
Non-hydrogen modification reaction is carried out under part, reaction result is listed in table 3.
Table 3
It has been technology contents well-known to those skilled in the art using the method that sulphation handles enhancing acidity of catalyst,
But the SO introduced4 2-It is also well known to those of ordinary skill in the art for being easy to be lost in catalyst application process.Such as Fig. 1 institute
Show, compares the NH of F1 and F53- TPD spectrogram, it can be found that stabilization processes step through the invention, the modification after making acidification
The acid site quantity of ZSM-5 molecular sieve F5 decreases, and particularly reduces the quantity of middle strong acid center, and makes the overwhelming majority
Strong acid center is retained.Present invention employs the modified molecular screen used raw material in the application, temperature is more in than application
The stabilization processes for carrying out " original position " under high more harsh conditions relatively to the modified zsm-5 zeolite after acidification, have washed off appearance
SO easy to fall off4 2-(as shown in table 1), and again passed by high-temperature roasting processing.As shown in table 3, the stabilisation that the present invention uses
Beneficial effect brought by processing step first is that, avoid acidified modified ZSM-5 molecular sieve F5 in direct application process, because
SO4 2-Fall off, blocking catalyst duct and lead to the rapid decrease of catalyst activity.In addition, modified zsm-5 zeolite of the present invention
Another beneficial effect be that stabilization processes through the invention enhance the stability of catalyst substantially.
Embodiment 6~8
By shaping of catalyst method as described in example 4, by the modified zsm-5 zeolite F1 prepared in Examples 1 to 3,
With aluminium hydroxide binder kneading and compacting, catalyst Z 3, Z4 and Z5 is made respectively in F2 and F3.It is modified in above-mentioned three kinds of catalyst
The mass fraction of ZSM-5 molecular sieve is respectively 60%, 90% and 70%.
Using identical gasoline stocks used in embodiment 4, change reaction condition, evaluation catalyst Z 3, Z4, Z5 and Z6
Reactivity worth.Reaction condition is listed in table 4, and reaction result and product form are listed in table 5.
Comparative example 3
The performance and effect of modified zsm-5 zeolite in order to further illustrate the present invention, by used in embodiment 1 not
Modified Hydrogen ZSM-5 molecular sieve and aluminium hydroxide binder kneading and compacting, is made catalyst Z 6, wherein unmodified Hydrogen
Mass fraction shared by ZSM-5 molecular sieve is 60%.
Using identical gasoline stocks used in embodiment 4, the reactivity worth of catalyst Z 6 is evaluated.Reaction condition is listed in table
4, reaction result and product form are listed in table 5.
Table 4
Table 5
As shown in table 5, modified zsm-5 zeolite of the present invention is secondary during for n-butene skeletal isomerization production isobutene
Steam oil non-hydrogen upgrading processes in, under 200~300 DEG C of reaction temperature, can make the octane number of inferior patrol improve to
91 or more, highest can make octane number be increased to 97.1.
Claims (18)
1. a kind of preparation method of modified zsm-5 zeolite, it is characterised in that: including following preparation step:
(1) aqueous solution containing zirconates and iridium salt is prepared, be added to and in the immiscible organic solvent of water, is made containing zirconates and iridium salt
The volume ratio of aqueous solution and organic solvent is 1:20~1:40, forms suspension A, and under conditions of continuously stirring, metering is added
Hydrogen ZSM-5 molecular sieve powder, stirring form slurries B；
(2) organic solvent being evaporated in slurries B obtained in step (1), obtains dry glue C, resulting dry glue through at room temperature it is dry,
It after drying, is roasted 5~10 hours at 500~550 DEG C, obtains the ZSM-5 molecular sieve D containing zirconium and iridium；
(3) using the inorganic acid of 0.1~0.5 mol/L or inorganic acid ammonium solution to obtained in step (2) containing zirconium and iridium
ZSM-5 molecular sieve D is impregnated, soaking time be 1~5 hour, after immersion to the ZSM-5 molecular sieve D containing zirconium and iridium into
Row elution, gained filter cake roasts 5~10 hours at 500~550 DEG C after drying, obtain acidified processing containing zirconium and iridium
ZSM-5 molecular sieve E；
(4) the ZSM-5 molecular sieve E of acidified processing obtained in step (3) is passed through stabilization at normal pressure, 300~350 DEG C
Change reagent treatment, processing is carried out 5~10 hours to it, obtains the modified ZSM-5 of stabilized processing through drying, roasting after processing
F；
Stabilization processes reagent is the inferior patrol that n-butene skeletal isomerization produces isobutene byproduct in process in step (4).
2. according to the method described in claim 1, it is characterized by: ZSM-5 molecular sieve is commercial goods or presses existing method
Preparation.
3. according to the method described in claim 1, it is characterized by: zirconates is selected from zirconyl nitrate, zirconium acetate, zirconium chloride, positive fourth
One of alcohol zirconium, zirconium-n-propylate are a variety of.
4. according to the method described in claim 1, it is characterized by: iridium salt in chloro-iridic acid, iridium chloride, ammonium chloroiridate one
Kind is a variety of.
5. according to the method described in claim 1, iridium salt is chloro-iridic acid it is characterized by: zirconates is zirconyl nitrate.
6. according to the method described in claim 1, it is characterized by: organic solvent is alkane of the boiling point at 50~90 DEG C under normal pressure
Or cycloalkane.
7. according to the method described in claim 1, it is characterized by: organic solvent is n-hexane, hexamethylene, 2- methylpent
One of alkane, 3- methylpentane, 2- methyl hexane, 3- methyl hexane, methyl cyclopentane are a variety of.
8. according to the method described in claim 1, it is characterized by: the addition volume of the aqueous solution containing zirconates and iridium salt is equal to
The total pore volume of ZSM-5 molecular sieve.
9. according to the method described in claim 1, it is characterized by: inorganic acid be selected from one of sulfuric acid, nitric acid and hydrochloric acid or
A variety of, inorganic acid ammonium is selected from the one or more of ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate and ammonium chloride.
10. method described in claim 1, it is characterised in that: the concentration of inorganic acid or inorganic acid ammonium solution is 0.1~0.5
mol/L。
11. according to the method described in claim 1, inorganic acid ammonium is ammonium sulfate it is characterized by: inorganic acid is sulfuric acid.
12. according to the method described in claim 1, being roasted 5~10 hours it is characterized by: being roasted at 500~550 DEG C.
13. the molecular sieve of claim 1-12 any the method preparation, it is characterised in that: by weight percentage, containing 3.0~
5.0% zirconium dioxide, 0.1~0.5% iridium dioxide and 0.2~0.5% SO4 2-, remaining is ZSM-5 molecular sieve.
14. the application of molecular sieve described in claim 13, it is characterised in that: by modified ZSM-5 molecular sieve straight forming, or will
Modified ZSM-5 molecular sieve and binder kneading and compacting, is made non-hydrogen modifying catalyst, by weight percentage, non-hydrogen
Modified zsm-5 zeolite accounts for 50~90% in modifying catalyst.
15. application according to claim 14, it is characterised in that: non-hydrogen modifying catalyst faces for the non-of inferior patrol
Hydrogen modification, reaction temperature are 200~400 DEG C；Pressure is 0.05~0.5 MPa；Weight (hourly) space velocity (WHSV) is 0.5~10 h-1。
16. application according to claim 15, it is characterised in that: reaction temperature is 200~300 DEG C；Pressure be 0.05~
0.2 MPa；Weight (hourly) space velocity (WHSV) is 0.5~2 h-1。
17. application according to claim 15, it is characterised in that: inferior patrol is matter produced in various process
Measure the gasoline that content is higher than 30%.
18. application according to claim 17, it is characterised in that: bad gasoline is raw from n-butene skeletal isomerization
The by-product gasoline during isobutene is produced, alkene total weight content is not less than 50%.
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| CN102286296A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene |
| CN102746081A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene through dehydrogenation and catalytic cracking of light hydrocarbon raw material |
| CN103521257A (en) * | 2013-10-25 | 2014-01-22 | 连云港阳方催化科技有限公司 | ZSM-5 molecular sieve modified catalyst as well as preparation method and application thereof |
| KR20140067564A (en) * | 2012-11-27 | 2014-06-05 | 롯데케미칼 주식회사 | Process for production of olefins |
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| CN101347744A (en) * | 2008-09-05 | 2009-01-21 | 江苏扬农化工股份有限公司 | Catalyst for synthesizing pyridine using microsphere type high-silicon ZSM-5 molecular sieve as carrier and preparation method thereof |
| CN102286296A (en) * | 2010-06-18 | 2011-12-21 | 中国石油化工股份有限公司 | Method for increase production of propylene and ethylene |
| CN102746081A (en) * | 2011-04-20 | 2012-10-24 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene through dehydrogenation and catalytic cracking of light hydrocarbon raw material |
| KR20140067564A (en) * | 2012-11-27 | 2014-06-05 | 롯데케미칼 주식회사 | Process for production of olefins |
| CN103521257A (en) * | 2013-10-25 | 2014-01-22 | 连云港阳方催化科技有限公司 | ZSM-5 molecular sieve modified catalyst as well as preparation method and application thereof |
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