CN106669793A - Modified ZSM-5 molecular sieve and preparation method and application thereof - Google Patents
Modified ZSM-5 molecular sieve and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a modified ZSM-5 molecular sieve and a preparation method and an application thereof. The modified ZSM-5 molecular sieve comprises the following components by weight percentage: 3.0-5.0% of zirconium dioxide, 0.1-0.5% of iridic oxide, 0.2-0.5% of SO4<2->, and the balance of the ZSM-5 molecular sieve. The preparation method comprises the following steps: preparing the zirconium and iridium-containing ZSM-5 molecular sieve, processing the zirconium and iridium-containing ZSM-5 molecular sieve, and stabilizing the zirconium and iridium-containing ZSM-5 molecular sieve. The non-hydrogen modified catalyst prepared by the ZSM-5 molecular sieve has the advantages of high low-temperature activity, high product yield and high octane number when used for non-hydrogen modification of a by-product gasoline during an isobutene heterogeneous production process by n-butene skeleton.
Description
Technical field
The present invention relates to a kind of modified zsm-5 zeolite and its preparation method and application, it is more particularly related to a kind of modified zsm-5 zeolite of non-hydrogen modification that can be used for n-butene skeletal isomerization production isobutene process by-product gasoline and its preparation method and application.
Background technology
With continuous growth of the market to high-knock rating gasoline demand, to the methyl tertiary butyl ether(MTBE) as octane enhancers for mixing（MTBE）Demand also increase.The total output of China MTBE in 2011 is more than 4,500,000 tons, and the average utilization of capacity of country's MTBE devices is only 60%, and the insufficient supply of raw material isobutene has become the bottleneck of MTBE industry developments.
With the lighting of ethylene cracking material, and impacted by ethane cracking route and methanol-to-olefins project.In recent years, reduce year by year as the yield of the cracking carbon-4 in main isobutene source.On the other hand, the fast development of methanol-to-olefins project, its by-product carbon four provides more n-butene resources for market again.Therefore, it is raw material by cheap and resourceful n-butene, n-butene is tautomerized to by isobutene by skeletal isomerization reaction, be re-used as the raw material of MTBE synthesis, will solve the most economical approach that there is lack of raw materials of MTBE at this stage.It is reported that, by the end of the end of the year 2013, the total raw material treating capacity of the n-butene skeletal isomerization device that China has invested to build has exceeded 3,800,000 tons/year.
During n-butene skeletal isomerization production isobutene, a certain amount of gasoline of the more or less by-product of meeting, the olefin(e) centent of this kind of by-product gasoline is usually above 50%, it is impossible to be directly used in mediation gasoline product.The gasoline yield of n-butene skeletal isomerization byproduct in process depends on adopted catalyst type, operating condition and raw material composition etc..For example, CN1068320 disclose it is a series of using unmodified ferrierite, SAPO, MeAlPO molecular sieve directly with binding agent shaping made by catalyst, and for the method for n-butene skeletal isomerization production isobutene reaction, by adjusting the conditions such as reaction temperature, pressure and olefin partial pressures, the method highest can by-product 63.36% gasoline.
Improve the value of the inferior patrol of n-butene skeletal isomerization byproduct in process, it will further improve the Technical Economy of n-butene skeletal isomerization technique.A kind of method for improving n-butene skeletal isomerization technology economy is the inferior patrol yield for reducing existing process.For example, US5132484 discloses a kind of method that n-butene skeletal isomerization produces isobutene, and the method adopts the modified AlPO-11 types molecular sieve of iron for catalyst, gasoline yield can be reduced into less than 10% by more than 50%.
It is that the inferior patrol of by-product is converted into the gasoline blend component of high-quality that another kind improves the method for the Technical Economy of n-butene skeletal isomerization technique, is such as used to improve the octane number of gasoline product.The inferior patrol higher for olefin(e) centent, using it is non-hydrogen aromatization modified by alkene be converted into aromatic hydrocarbons or isoparaffin be most competitiveness conversion scheme.Existing inferior patrol non-hydrogenation upgrading technology, generally ZSM-5 molecular sieve or modified ZSM-5 molecular sieve are adopted for catalyst, it is normal pressure to 5.0MPa in reaction pressure, reaction temperature is under conditions of 300-550 DEG C, make the technical scheme of feed gasoline and catalyst directly contact, such as CN93102129, CN101812318, CN102698790 and CN101081997.If prior art, because needing to react at high temperature, will certainly cause cracking gas yield too high for the non-hydrogen modification reaction of n-butene skeletal isomerization byproduct in process gasoline, product gasoline yield is reduced.According to existing catalyst low temperature（Less than 300 DEG C）Lower reaction, because catalyst acid intensity it is relatively low, it is impossible to meet preferable conversion rate, there is that olefin conversion is low and the less deficiency of product octane number amplification.
The content of the invention
For the deficiencies in the prior art, the present invention provides a kind of modified zsm-5 zeolite and preparation method thereof, and adopts the application of catalyst prepared by the modified zsm-5 zeolite that the present invention is provided in the non-hydrogen modification of n-butene skeletal isomerization byproduct in process gasoline.
A kind of preparation method of modified zsm-5 zeolite, including following preparation process：
（1）The aqueous solution of the configuration containing zirconates and iridium salt, it is 1 to be added to and in the immiscible organic solvent of water, make containing zirconates and iridium saline solution and the volume ratio of organic solvent:20～1:40, suspension A is formed, under conditions of continuously stirring, add the Hydrogen ZSM-5 molecular sieve powder of metering, stirring to form slurries B；
（2）It is evaporated step（1）Organic solvent in the slurries B of middle gained, obtains dry glue C, and Jing after being dried under room temperature, dry, roasting 5～10 hours at 500～550 DEG C obtain the ZSM-5 molecular sieve D containing zirconium and iridium to the dry glue of gained；
（3）Using the inorganic acid or inorganic acid ammonium solution of 0.1～0.5 mol/L to step（2）The ZSM-5 molecular sieve D containing zirconium and iridium of middle gained is soaked, soak time is 1～5 hour, immersion carries out drip washing after terminating to the ZSM-5 molecular sieve D containing zirconium and iridium, gained filter cake roasting 5～10 hours at 500～550 DEG C after drying, obtain the ZSM-5 molecular sieve E containing zirconium and iridium of acidified process.
（4）By step（3）The ZSM-5 molecular sieve E of the acidified process of middle gained is passed through stabilization processes reagent at normal pressure, 300～350 DEG C, and process is carried out 5～10 hours to it, and Jing is dried after process, roasting obtains the modified ZSM-5 F of stabilized process.
The inventive method step（1）In, described ZSM-5 molecular sieve can be commercial goods, it is also possible to prepare by existing method.Described zirconates is selected from one or more in zirconyl nitrate, zirconium acetate, zirconium chloride, zirconium-n-butylate, zirconium-n-propylate, preferred zirconyl nitrate.Described iridium salt is selected from one or more in chloro-iridic acid, iridium chloride, ammonium chloroiridate, preferred chloro-iridic acid.Described organic solvent is alkane or cycloalkane of the boiling point at 50～90 DEG C under normal pressure, one or more specially in n-hexane, hexamethylene, 2- methylpentanes, 3- methylpentanes, 2- methyl hexanes, 3- methyl hexanes, methyl cyclopentane, preferred n-hexane and hexamethylene.
The inventive method step（1）Described in the addition volume containing zirconates and the aqueous solution of iridium salt be equal to ZSM-5 molecular sieve total pore volume.
The inventive method step（3）Described in one or more in sulfuric acid, nitric acid and the hydrochloric acid of inorganic acid, preferably sulfuric acid.Described inorganic acid ammonium is selected from one or more of ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate and ammonium chloride, preferably sulfuric acid ammonium.Described inorganic acid or the concentration of inorganic acid ammonium solution is 0.1～0.5 mol/L.
The inventive method step（4）In be roasted to 500～550 DEG C at roasting 5～10 hours.Described stabilization processes reagent is the raw material used in the zeolite product application process.As present invention further optimization, in the inventive method step（4）In, described stabilization processes reagent refers specifically to the inferior patrol that n-butene skeletal isomerization produces isobutene byproduct in process.
Modified zsm-5 zeolite prepared by a kind of employing said method, 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.
Application of the modified zsm-5 zeolite of the present invention in the non-hydrogen modification of inferior patrol, by modified ZSM-5 molecular sieve straight forming, or by modified ZSM-5 molecular sieve and binding agent kneading and compacting well-known to those skilled in the art, non-hydrogen modifying catalyst is obtained.As present invention further optimization, using modified zsm-5 zeolite and aluminium hydroxide binding agent kneading, and extrusion molding is obtained and used in the present invention faces hydrogen modifying catalyst, but the non-hydrogen lid catalyst in the present invention is not limited to be obtained using extruding forming method, can also be using forming methods well-known to those skilled in the art such as powder, bead, extrudates.As the present invention still more preferably, in described non-hydrogen modifying catalyst, by weight percentage, modified zsm-5 zeolite accounts for 50～90%.For the suitable reaction condition that the non-hydrogen of inferior patrol is modified：Reaction temperature is 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) is 0.5～10 h-1, preferably 0.5～2 h-1.Described inferior patrol is generally gasoline of the mass content produced in various process higher than 30%.Used as present invention further optimization, described bad gasoline comes from the by-product gasoline during n-butene skeletal isomerization production isobutene, and in this kind of gasoline, alkene gross weight content is not less than 50%.
Compared with prior art, the invention has the advantages that：
（1）The IrO introduced 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, the quantity of the strong acid center of modified zsm-5 zeolite is especially improve using the inventive method；
（2）Stabilization processes step avoids acidified modified ZSM-5 molecular sieve F5 in direct application process, because of SO4 2-Come off, blocking catalyst duct and cause the rapid decrease of catalyst activity, making the stability of catalyst significantly strengthens.
（3）Non-hydrogen modifying catalyst prepared by modified zsm-5 zeolite, in the non-hydrogen modification that isobutene byproduct in process gasoline is produced for n-butene skeletal isomerization, has the advantages that low temperature active is high, product liquid receives high and octane number high.
Description of the drawings
Fig. 1 is the NH of modified zsm-5 zeolite of the present invention3- TPD spectrograms.
Wherein, the modified zsm-5 zeolite that F1- is prepared by the inventive method, the modified zsm-5 zeolite without iridium that F4- is prepared by the inventive method, the modified zsm-5 zeolite without stabilization processes that F5- is prepared by the inventive method.
Specific embodiment
The effect and effect of the inventive method are further illustrated below by embodiment and comparative example, but following examples are not construed as limiting the invention.
Hydrogen type ZSM 5 molecular sieve used in following embodiments is commercial goods.The chemical reagent for using such as is indicated without special, is AR.Binding agent used by catalyst preparation is aluminium hydrate powder, and pore volume is 0.47～0.53 ml/g, and than table 250 m are more than2/ g, average pore size is 7.5～8.5 nm.
In the present invention, method is constituted using gasoline family（PONA methods）The composition of analysis feed gasoline and product, using research octane number (RON)（RON）To represent the octane number of feed gasoline and product.The activity of catalyst is represented using olefin conversion, gasoline products liquid receipts are represented using cracking gas yield（Cracking gas yield is lower, and liquid is received higher）.
Embodiment 1
The concrete preparation process of modified zsm-5 zeolite F1 is as follows：（1）5.7 g zirconyl nitrates and 0.7g chloro-iridic acids are dissolved in the deionized water of 22 ml, gained saline solution is added in the n-hexane solvent of 650 ml, continuously stirred 1 hour, form suspension A1.It is 0.19 cm that the Si/Al mol ratios that 114.5 g are added in suspension A1 are 76, pore volume3The Hydrogen ZSM-5 molecular sieve of/g, in room temperature（25℃）Lower stirring 2 hours, obtains slurries B1.（2）By in slurries B1 dislocation Rotary Evaporators, n-hexane solvent is evaporated, dry glue C1 is obtained, in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 5 hours at 550 DEG C, obtain the ZSM-5 molecular sieve D1 containing zirconium and iridium.（3）In the ammonium sulfate of 0.1 mol/L that D1 is moved into 500 ml, immersion treatment 5 hours after required soak time to be achieved, filters out ammonium sulfate, and the thorough drip washing molecular sieve of deionized water, by the filter cake for obtaining in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 8 hours at 530 DEG C, obtain the ZSM-5 molecular sieve E1 of acidified process.（4）Under the conditions of normal pressure, 350 DEG C, stabilization processes are carried out to E1, the bad gasoline being passed through used in present invention application（Composition is referring to table 2）, process time is 8 hours, after required process time to be achieved, cools the temperature to room temperature（25℃）, and in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 10 hours at 500 DEG C, obtain final modified zsm-5 zeolite F1.
Embodiment 2
The concrete preparation process of modified zsm-5 zeolite F2 is as follows：（1）7.7 g zirconyl nitrates and 0.2 g chloro-iridic acids are dissolved in the deionized water of 26 ml, gained saline solution is added in the cyclohexane solvent of 520 ml, continuously stirred 1 hour, form suspension A2.It is 0.23 cm that the Si/Al mol ratios that 113.0 g are added in suspension A2 are 54, pore volume3The Hydrogen ZSM-5 molecular sieve of/g, in room temperature（25℃）Lower stirring 2 hours, obtains slurries B2.（2）By in slurries B2 dislocation Rotary Evaporators, cyclohexane solvent is evaporated, dry glue C2 is obtained, in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 10 hours at 500 DEG C, obtain the ZSM-5 molecular sieve D2 containing zirconium and iridium.（3）In the ammonium sulfate of 0.5 mol/L that D2 is moved into 500 ml, immersion treatment 1 hour after required soak time to be achieved, filters out ammonium sulfate, and the thorough drip washing molecular sieve of deionized water, by the filter cake for obtaining in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 5 hours at 550 DEG C, obtain the ZSM-5 molecular sieve E2 of acidified process.（4）Under the conditions of normal pressure, 300 DEG C, stabilization processes are carried out to E2, the bad gasoline being passed through used in present invention application（Composition is referring to table 2）, process time is 5 hours, after required process time to be achieved, cools the temperature to room temperature（25℃）, and in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 8 hours at 550 DEG C, obtain final modified zsm-5 zeolite F2.
Embodiment 3
The concrete 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 dissolved in the deionized water of 23.7 ml, gained saline solution is added in the cyclohexane solvent of 950 ml, continuously stirred 1 hour, form suspension A3.It is 0.21 cm that the Si/Al mol ratios that 114.5 g are added in suspension A3 are 93, pore volume3The Hydrogen ZSM-5 molecular sieve of/g, in room temperature（25℃）Lower stirring 2 hours, obtains slurries B3.（2）By in slurries B3 dislocation Rotary Evaporators, cyclohexane solvent is evaporated, dry glue C3 is obtained, in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 10 hours at 530 DEG C, obtain the ZSM-5 molecular sieve D3 containing zirconium and iridium.（3）In the sulfuric acid solution of 0.3 mol/L that D3 is moved into 500 ml, immersion treatment 3 hours after required soak time to be achieved, filters out sulfuric acid solution, and the thorough drip washing molecular sieve of deionized water, by the filter cake for obtaining in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 10 hours at 500 DEG C, obtain the ZSM-5 molecular sieve E3 of acidified process.（4）Under the conditions of normal pressure, 330 DEG C, stabilization processes are carried out to E3, the bad gasoline being passed through used in present invention application（Composition is referring to table 2）, process time is 10 hours, after required process time to be achieved, cools the temperature to room temperature（25℃）, and in room temperature（25℃）Lower drying 24 hours, dries 12 hours at 120 DEG C, and then roasting 10 hours at 530 DEG C, obtain final modified zsm-5 zeolite F3.
Comparative example 1
In order to further illustrate the performance and effect of modified zsm-5 zeolite of the present invention, the method as shown in embodiment 1 is prepared for the modified zsm-5 zeolite F4 without iridium, and its specific preparation process is identical with embodiment 1, simply in step（1）In be added without chloro-iridic acid.
Comparative example 2
In order to further illustrate the performance and effect of modified zsm-5 zeolite of the present invention, the method as shown in embodiment 1 is prepared for without the ZSM-5 molecular sieve F5 of stabilization processes, i.e., by embodiment 1（1）、（2）With（3）Step prepares the ZSM-5 molecular sieve E1 of acidified process.
Using the composition of the modified zsm-5 zeolite F4 without iridium in the modified zsm-5 zeolite F1-F3 and comparative example 1-2 prepared in the x-ray fluorescence spectrometry embodiment 1-3 and modified zsm-5 zeolite F5 without stabilization processes, in weight percent, as a result it is listed in table 1.
Table 1
As shown in table 1, F1 and F4 is contrasted, it can be found that the IrO that the present invention is introduced 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, the quantity of the strong acid center of modified zsm-5 zeolite is especially improve using the inventive method（As shown in Figure 1）.
Embodiment 4～5
Respectively by F1 and F5 and aluminium hydroxide binding agent kneading and compacting, catalyst Z 1 and Z2 are made.Molecular sieve quality fraction in above two catalyst is 50%.
A kind of gasoline of by-product in n-butene skeletal isomerization production isobutene technique is adopted 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 first need to be pre-processed 2 hours in 350 DEG C of nitrogen atmosphere, then be cooled to reaction temperature.It it is 300 DEG C in reaction temperature with above-mentioned gasoline as raw material, reaction pressure is 0.15MPa, air speed is 2 h-1Under conditions of carry out non-hydrogen modification reaction, reaction result is listed in table 3.
Table 3
The method for strengthening acidity of catalyst using sulphation process has been technology contents well-known to those skilled in the art, but the SO for introducing4 2-It is also well known to those of ordinary skill in the art to be easy to be lost in catalyst application process.As shown in figure 1, the NH of contrast F1 and F53- TPD spectrograms, it can be found that by the stabilization processes step of the present invention, the acid site quantity for making the modified zsm-5 zeolite F5 after acidifying decreases, particularly reduce the quantity of middle strong acid center, and are retained the strong acid center of the overwhelming majority.The modified molecular screen used raw material in the application is present invention employs, the stabilization processes of " original position " are carried out under the higher more harsh conditions relatively of temperature to the modified zsm-5 zeolite after acidifying in than application, has been washed off and easily come off SO4 2-（As shown in table 1）, and again passed by high-temperature roasting process.As shown in table 3, one of beneficial effect for being brought of stabilization processes step that the present invention is adopted is, it is to avoid acidified modified ZSM-5 molecular sieve F5 in direct application process, because of SO4 2-Come off, blocking catalyst duct and cause the rapid decrease of catalyst activity.Additionally, another beneficial effect of modified zsm-5 zeolite of the present invention is, by the stabilization processes of the present invention, making the stability of catalyst significantly strengthens.
Embodiment 6～8
Shaping of catalyst method as described in embodiment 4, by embodiment 1～3 prepare modified zsm-5 zeolite F1, F2 and F3 respectively with aluminium hydroxide binding agent kneading and compacting, make catalyst Z 3, Z4 and Z5.In above-mentioned three kinds of catalyst, the mass fraction of modified zsm-5 zeolite is respectively 60%, 90% and 70%.
Using identical gasoline stocks used in embodiment 4, change reaction condition, evaluate the reactivity worth of catalyst Z 3, Z4, Z5 and Z6.Reaction condition is listed in table 4, and reaction result and product form are listed in table 5.
Comparative example 3
In order to further illustrate the performance and effect of modified zsm-5 zeolite of the present invention, by the unmodified Hydrogen ZSM-5 molecular sieve used in embodiment 1 and aluminium hydroxide binding agent kneading and compacting, catalyst Z 6 is made, wherein mass fraction shared by unmodified Hydrogen 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, and 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 in the non-hydrogen upgrading processes that isobutene byproduct in process gasoline is produced for n-butene skeletal isomerization, under 200～300 DEG C of reaction temperature, the octane number that can make inferior patrol is improved to more than 91, and highest can make octane number bring up to 97.1.
Claims (19)
1. a kind of preparation method of modified zsm-5 zeolite, it is characterised in that：Including following preparation process：
（1）The aqueous solution of the configuration containing zirconates and iridium salt, it is 1 to be added to and in the immiscible organic solvent of water, make containing zirconates and iridium saline solution and the volume ratio of organic solvent:20～1:40, suspension A is formed, under conditions of continuously stirring, add the Hydrogen ZSM-5 molecular sieve powder of metering, stirring to form slurries B；
（2）It is evaporated step（1）Organic solvent in the slurries B of middle gained, obtains dry glue C, and Jing after being dried under room temperature, dry, roasting 5～10 hours at 500～550 DEG C obtain the ZSM-5 molecular sieve D containing zirconium and iridium to the dry glue of gained；
（3）Using the inorganic acid or inorganic acid ammonium solution of 0.1～0.5 mol/L to step（2）The ZSM-5 molecular sieve D containing zirconium and iridium of middle gained is soaked, soak time is 1～5 hour, immersion carries out drip washing after terminating to the ZSM-5 molecular sieve D containing zirconium and iridium, gained filter cake roasting 5～10 hours at 500～550 DEG C after drying, obtain the ZSM-5 molecular sieve E containing zirconium and iridium of acidified process；
（4）By step（3）The ZSM-5 molecular sieve E of the acidified process of middle gained is passed through stabilization processes reagent at normal pressure, 300～350 DEG C, and process is carried out 5～10 hours to it, and Jing is dried after process, roasting obtains the modified ZSM-5 F of stabilized process.
2. method according to claim 1, it is characterised in that：ZSM-5 molecular sieve is commercial goods or prepares by existing method.
3. method according to claim 1, it is characterised in that：Zirconates is selected from one or more in zirconyl nitrate, zirconium acetate, zirconium chloride, zirconium-n-butylate, zirconium-n-propylate.
4. method according to claim 1, it is characterised in that：Iridium salt is selected from one or more in chloro-iridic acid, iridium chloride, ammonium chloroiridate.
5. method according to claim 1, it is characterised in that：Zirconates is zirconyl nitrate, and iridium salt is chloro-iridic acid.
6. method according to claim 1, it is characterised in that：Organic solvent is alkane or cycloalkane of the boiling point at 50～90 DEG C under normal pressure.
7. method according to claim 1, it is characterised in that：Organic solvent is n-hexane, one or more in hexamethylene, 2- methylpentanes, 3- methylpentanes, 2- methyl hexanes, 3- methyl hexanes, methyl cyclopentane.
8. method according to claim 1, it is characterised in that：Addition volume containing zirconates and the aqueous solution of iridium salt is equal to the total pore volume of ZSM-5 molecular sieve.
9. method according to claim 1, it is characterised in that：Inorganic acid is selected from one or more in sulfuric acid, nitric acid and hydrochloric acid, and inorganic acid ammonium is selected from one or more of ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate and ammonium chloride.
10. the 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. methods according to claim 1, it is characterised in that：Inorganic acid is sulfuric acid, and inorganic acid ammonium is ammonium sulfate.
12. methods according to claim 1, it is characterised in that：Roasting 5～10 hours at being roasted to 500～550 DEG C.
13. methods according to claim 1, it is characterised in that：Stabilization processes reagent is the inferior patrol that n-butene skeletal isomerization produces isobutene byproduct in process.
The arbitrary described molecular sieve of 14. claims 1-13, 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.
The application of molecular sieve described in 15. claims 14, it is characterised in that：By modified ZSM-5 molecular sieve straight forming, or by modified ZSM-5 molecular sieve and binding agent kneading and compacting, non-hydrogen modifying catalyst is obtained, by weight percentage, modified zsm-5 zeolite accounts for 50～90% in non-hydrogen modifying catalyst.
16. applications according to claim 15, it is characterised in that：Non-hydrogen modifying catalyst is used for the non-hydrogen of inferior patrol and modifies, and reaction temperature is 200～400 DEG C；Pressure is 0.05～0.5 MPa；Weight (hourly) space velocity (WHSV) is 0.5～10 h-1。
17. applications according to claim 16, it is characterised in that：Reaction temperature is 200～300 DEG C；Pressure is 0.05～0.2 MPa；Weight (hourly) space velocity (WHSV) is 0.5～2 h-1。
18. applications according to claim 16, it is characterised in that：Inferior patrol is gasoline of the mass content produced in various process higher than 30%.
19. applications according to claim 18, it is characterised in that：Bad gasoline comes from the by-product gasoline during n-butene skeletal isomerization production isobutene, and alkene gross weight content is not less than 50%.
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