CN106673945B - A kind of method that n-butene prepares propylene - Google Patents
A kind of method that n-butene prepares propylene Download PDFInfo
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Abstract
The present invention discloses a kind of method by n-butene production propylene, raw material containing n-butene contacts under the conditions of catalytic cracking reaction with catalyst for cracking, reaction temperature is 450~550 DEG C, it is preferred that 450~500 DEG C, reacting stagnation pressure (absolute pressure) is 0~0.5MPa, it is preferred that 0~0.15MPa, weight space velocity is 1~10h‑1, preferably 2~4 h‑1The wherein catalyst for cracking, by weight percentage, FER molecular sieve and modified zsm-5 zeolite content are not less than 50%, the mass ratio of FER molecular sieve and modified zsm-5 zeolite is 1:1~3:1, modified zsm-5 zeolite, by weight percentage, containing 4.5~6.0% zirconium dioxide, 0.2~0.5% iridium dioxide and 0.15~0.45% SO4 2‑, remaining is ZSM-5 molecular sieve, and the silica alumina ratio of FER molecular sieve is 50~100.This method has the advantages that reaction temperature is low, propylene one-way yield is high in the industrial process for four raw material of the carbon of mixing containing n-butene production propylene.
Description
Technical field
The present invention relates to a kind of methods for preparing propylene as raw material using n-butene.
Background technique
China's propylene total output in 2011 is 14,680,000 tons, and China's propylene Apparent con- sumption in 2011 is 16,430,000 tons, from
It is only 89.3% to rate.It is expected that China's propylene Apparent con- sumption in 2015 is up to 22,000,000 tons.
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 of ethylene by-product propylene as main propylene source will reduce year by year.On the other hand, methanol-to-olefins item
Purpose is grown rapidly, and by-product carbon four provides more n-butene resources again for market.Therefore, with cheap and resourceful
N-butene is raw material, converts propylene for n-butene cracking by catalytic cracking reaction, will solve propylene unbalanced supply-demand
More economical approach.
The method for being currently used for the production propylene of raw material containing n-butene, or frequently referred to four or more olefins by catalytic cracking of carbon four and carbon
The method for producing propylene, generallys use the technical solution contacted under raw material and molecular sieve catalyst high-temperature low-pressure.
Catalyst for the reaction mainly have ZSM-5 molecular sieve (such as CN1611470, CN1915928, CN1915929,
CN1927786, CN102060648 etc.), there are also using ZSM-48(such as CN1506343), SAPO-11(such as CN1927783) and
SAPO-34(such as CN1927783) molecular sieve be catalyst technical solution.
A kind of method that CN1413966 discloses carbon four and above olefins by catalytic cracking production propylene, the process employs
Using the ZSM-5 molecular sieve of steam treatment as catalyst, pass through steam treatment, it is suppressed that the hydrogen transfer activity of catalyst makes
The one-pass yield of propylene increases up to 28.8% by 24.4%.
A kind of method that CN1506342 discloses carbon four and above olefins by catalytic cracking production propylene, the process employs
Using alkali-earth metal modified ZSM-5 molecular sieve as catalyst, the one-pass yield of propylene can be made to be increased to 34%.
CN1704389 disclose it is a kind of for olefins by catalytic cracking production propylene, ethylene method, the process employs with
Rare-earth metal modified ZSM-5 molecular sieve is catalyst, and the one-pass yield of propylene can be made to be increased to 34% or more.
CN103030501 discloses a kind of method for producing propylene, and the process employs metal-modified with group VIII
ZSM-5 molecular sieve is catalyst, and the one-pass yield of propylene is made to be increased to 32.9%.
CN1676499 discloses a kind of method of catalytic pyrolysis preparing low-carbon olefins, the process employs with rare earth metal,
The ZSM-5 molecular sieve that alkaline-earth metal and phosphorous oxides are modified is catalyst, and dilutes raw material using vapor, improves propylene
One-pass yield.
CN101033166 discloses a kind of method of carbon four and four or more preparing propylene by catalytic cracking olefin of carbon, and this method is adopted
With using the modified ZSM-5 molecular sieve of heteropoly acid as catalyst, the one-pass yield of propylene is improved.
CN102166529 discloses the catalyst and application method of a kind of C _ 4 alkene catalytic pyrolysis preparing ethylene and propylene, should
Method is used using the ZSM-5 molecular sieve of P Modification as catalyst, and dilutes raw material using vapor, to propylene one-pass yield
Raising has certain facilitation.
There are still purpose product propylene one-way yield is low for ZSM-5 molecular sieve catalyst employed in prior art
Deficiency can properly increase the one-pass yield of propylene, but productivity of propylene still has by catalyst modification method described in above-mentioned document
Space to be further increased.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method of n-butene production propylene.This method is for containing
Four raw material of n-butene mixing carbon produces in the industrial process of propylene, has the advantages that reaction temperature is low, propylene one-way yield is high.
A method of propylene being produced by n-butene, the raw material containing n-butene is urged under the conditions of catalytic cracking reaction with cracking
Agent contact, reaction temperature be 450~550 DEG C, preferably 450~500 DEG C, reaction stagnation pressure (absolute pressure) be 0~0.5MPa, preferably 0
~0.15MPa, weight space velocity are 1~10h-1, preferably 2~4 h-1, wherein the catalyst for cracking, by weight percentage,
Not less than 50%, the mass ratio of FER molecular sieve and modified zsm-5 zeolite is for FER molecular sieve and modified zsm-5 zeolite content
1:1~3:1, modified zsm-5 zeolite, by weight percentage, containing 4.5~6.0% zirconium dioxide, 0.2~0.5% dioxy
Change the SO of iridium and 0.15~0.45%4 2-, remaining is ZSM-5 molecular sieve, and the silica alumina ratio of FER molecular sieve is 50~100.
Also contain adhesive aluminium oxide, by weight percentage, FER molecular sieve and modified ZSM-5 in catalyst of the present invention
Molecular sieve quality content is 50~90%.
In the method for the present invention, methyl tertiary butyl ether(MTBE) device of the raw material containing n-butene from refinery or petrochemical plant
Carbon four after ether, wherein n-butene mass content is 10~95%, preferably 30~90%, more preferable 45~90%.
The preparation method of catalyst for cracking of the present invention mixes the FER molecular sieve of metering and modified zsm-5 zeolite
Straight forming after conjunction, or after the FER molecular sieve of metering and modified zsm-5 zeolite are mixed with it is well known to those skilled in the art
Binder kneading and compacting, catalyst for cracking of the present invention is made.As present invention further optimization, using FER points
Son sieve and modified zsm-5 zeolite and aluminium hydroxide binder kneading, and cracking and catalyzing of the present invention is made in extrusion molding
Agent, but catalyst of the present invention is not limited to be made using extruding forming method, it can also be using powder, bead, extrudate etc. originally
Forming method known to the technical staff of field.
In the preparation method of above-mentioned catalyst, FER molecular sieve can be commercial goods, can also prepare by existing method.
The preparation step of modified zsm-5 zeolite described in the method for the present invention is as follows:
(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.
One of effect and benefit of the invention are that the highly selective skeletal isomerization of n-butene can be made by both containing in catalyst
For the FER type molecular sieve component of isobutene, and contain the modified zsm-5 zeolite group that can make to mix four raw material of carbon and be converted into propylene
Point.Have reaction temperature low and propylene during for n-butene production propylene using catalyst made from the method for the present invention
The high advantage of one-pass yield；Two be, the IrO introduced in modified zsm-5 zeolite2Significantly improve ZrO2To SO4 2-Hold
The amount of having, and then the acid site quantity of modified ZSM-5 molecular sieve is improved, modified ZSM-5-is particularly improved using the method for the present invention
The quantity of the strong acid center of 5 molecular sieves, stabilization processes step avoid acidified modified ZSM-5 molecular sieve in direct application process
In, because of SO4 2-Fall off, blocking catalyst duct and lead to the rapid decrease of catalyst activity, increase the stability of catalyst substantially
By force.
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 and Hydrogen ZSM-22 molecular sieve as used in the following examples is commercial goods.Make
Chemical reagent is such as indicated without special, is analytical reagents.Binder used in catalyst preparation is aluminium hydrate powder, hole
Holding is 0.47~0.53 ml/g, is greater than 250 m than table2/ g, average pore size are 7.5~8.5 nm.
Embodiment 1
The specific preparation process of modified zsm-5 zeolite F1 is as follows: (1) 8.5 g zirconyl nitrates and 0.8g 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 650 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 630 DEG C
Roasting 8 hours, obtains the ZSM-5 molecular sieve E1 of acidified processing.(4) under the conditions of normal pressure, 550 DEG C, E1 is stabilized
Processing is passed through four raw material of carbon (composition is referring to table 1) after ether used in the present invention, and the processing time is 8 hours, to be achieved required
It after handling the time, cools the temperature to room temperature (25 DEG C), and is dried 12 hours at drying 24 hours, 120 DEG C under room temperature (25 DEG C),
Then it is roasted 10 hours at 600 DEG C, obtains final modified zsm-5 zeolite F1.
Table 1
Embodiment 2
The specific preparation process of modified zsm-5 zeolite F2 is as follows: (1) 9.5 g zirconyl nitrates and 0.5 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 600 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 650 DEG C
Roasting 5 hours, obtains the ZSM-5 molecular sieve E2 of acidified processing.(4) under the conditions of normal pressure, 530 DEG C, E2 is stabilized
Processing is passed through four raw material of carbon (composition is referring to table 1) after ether used in the present invention, and the processing time is 5 hours, to be achieved required
It after handling the time, cools the temperature to room temperature (25 DEG C), and is dried 12 hours at drying 24 hours, 120 DEG C under room temperature (25 DEG C),
Then it is roasted 8 hours at 650 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) by 11.2 g zirconyl nitrates and 1.1 g chloro-iridic acids
It is dissolved in the deionized water of 23.7 ml, gained saline solution is added in the cyclohexane solvent of 950 ml, is continuously stirred 1 hour,
Form 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 630
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 600 DEG C
Roasting 10 hours, obtains the ZSM-5 molecular sieve E3 of acidified processing.(4) under the conditions of normal pressure, 500 DEG C, E3 is stabilized
Processing is passed through four raw material of carbon (composition is referring to table 1) after ether used in the present invention, and the processing time is 10 hours, needed for be achieved
The processing time after, cool the temperature to room temperature (25 DEG C), and drying 12 is small at dry 24 hours, 120 DEG C under room temperature (25 DEG C)
When, it is then roasted 10 hours at 630 DEG C, obtains final modified zsm-5 zeolite F3.
Comparative example 1
The performance and effect of the modified zsm-5 zeolite used in order to further illustrate the present invention, by side shown in embodiment 1
Method is prepared for the modified zsm-5 zeolite F4 without iridium, and specific preparation process is identical with embodiment 1, only in step
Suddenly chloro-iridic acid is added without in (1).
Comparative example 2
The performance and effect of the modified zsm-5 zeolite used in order to further illustrate the present invention, by side shown in embodiment 1
Method is prepared for the ZSM-5 molecular sieve F5 without stabilization processes, i.e., by (1), (2) and (3) step in embodiment 1 prepare through
The ZSM-5 molecular sieve E1 of acidification.
Using the modified zsm-5 zeolite F1-F3 and comparative example prepared in x-ray fluorescence spectrometry Examples 1 to 3
The composition of the modified zsm-5 zeolite F4 without iridium in 1~2 and modified zsm-5 zeolite F5 without stabilization processes,
In terms of weight percentage, as a result it is listed in table 2.
Table 2
As shown in table 1, F1 and F4 is compared, it can be found that the IrO introduced in the modified zsm-5 zeolite that the present invention uses2
Significantly improve ZrO2To SO4 2-The volume of holding, and then improve the acid site quantity of modified ZSM-5 molecular sieve, particularly improve
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%.
Using four raw material of carbon (table 1) after identical ether used in embodiment 1, to evaluate the reactivity of catalyst Z 1 and Z2
Energy.Before carrying out evaluating catalyst, catalyst need to first be pre-processed 2 hours in 500 DEG C of nitrogen atmosphere, then be cooled to reaction temperature
Degree.Reaction temperature is 500 DEG C, reaction pressure 0.15MPa, and air speed is 4 h-1Under conditions of carry out catalytic cracking reaction, react
As a result it 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.The present invention is made using in the preparation method of catalyst using the modified molecular screen in the application
Raw material carries out " original to the modified zsm-5 zeolite after acidification under the higher more harsh conditions relatively of temperature in than application
The stabilization processes of position ", have washed off and have been easy to fall off SO4 2-(as shown in table 1), and again passed by high-temperature roasting processing.Such as table
Shown in 3, beneficial effect brought by the stabilization processes step that the present invention uses first is that, avoid acidified modified ZSM-5 point
Son sieve F5 is in direct application process, because of SO4 2-Fall off, blocking catalyst duct and lead to the rapid decrease of catalyst activity.This
Outside, another beneficial effect of modified zsm-5 zeolite of the present invention is that stabilization processes through the invention make the steady of catalyst
It is qualitative substantially to enhance.
Embodiment 6
Silica alumina ratio is mixed for the modified zsm-5 zeolite F1 prepared in 73 Hydrogen FER molecular sieve G1 and embodiment 1
It closes, forms mixed molecular sieve H1.Then H1 and suitable aluminium hydroxide are bonded into kneading and compacting, catalytic cracking catalyst is made
Y1, catalyst composition are listed in table 4.
Embodiment 7
Silica alumina ratio is mixed for the modified zsm-5 zeolite F2 prepared in 93 Hydrogen FER molecular sieve G2 and embodiment 2
It closes, forms mixed molecular sieve H2.Then H2 and suitable aluminium hydroxide are bonded into kneading and compacting, non-hydrogen modifying catalyst is made
Y2, catalyst composition are listed in table 4.
Embodiment 8
Modified zsm-5 zeolite by silica alumina ratio to be prepared in 52 Hydrogen ZSM-22 molecular sieve G3 and embodiment 3
F3 mixing, forms mixed molecular sieve H3.Then H3 and suitable aluminium hydroxide are bonded into kneading and compacting, non-hydrogen modification is made and urges
Agent Y3, catalyst composition are listed in table 4.
Table 4
Embodiment 9~11
Using four raw material of carbon (table 1) after ether used in embodiment 1, change reaction condition, evaluate catalyst Y1 of the present invention,
The reactivity worth of Y2 and Y3.Reaction condition and reaction result at 800 hours are listed in table 5.
Comparative example 3
The performance and effect of catalytic cracking catalyst in order to further illustrate the present invention, change what is prepared in embodiment 1
Property ZSM-5 molecular sieve F1 and appropriate aluminium hydroxide bond kneading and compacting, catalyst Y4 is made.In Y4 catalyst, modified ZSM-5 point
The mass fraction of son sieve F1 is 65%.
By the identical method of embodiment 9, the reactivity worth of catalyst Y4 is evaluated.Reaction condition and reaction at 800 hours
As a result it is listed in table 5.
Comparative example 4
The performance and effect of catalytic cracking catalyst in order to further illustrate the present invention, will be used identical in embodiment 6
Silica alumina ratio be 73 Hydrogen FER molecular sieve G1 and appropriate aluminium hydroxide bond kneading and compacting, catalyst Y5 is made.Y5 is urged
In agent, the mass fraction of Hydrogen FER molecular sieve G1 is 65%.
By the identical method of embodiment 9, the reactivity worth of catalyst Y4 is evaluated.Reaction condition and reaction at 800 hours
As a result it is listed in table 5.
Table 5
Claims (19)
1. a kind of method by n-butene production propylene, it is characterised in that: the raw material containing n-butene is in catalytic cracking reaction condition
Lower to contact with catalyst for cracking, reaction temperature is 450~550 DEG C, and reaction stagnation pressure is 0~0.5MPa, and weight space velocity is 1~10h-1, wherein the catalyst for cracking, by weight percentage, FER molecular sieve and modified zsm-5 zeolite content are not less than
50%, the mass ratio of FER molecular sieve and modified zsm-5 zeolite is 1:1~3:1, modified zsm-5 zeolite, with weight percent
Than meter, containing 4.5~6.0% zirconium dioxide, 0.2~0.5% iridium dioxide and 0.15~0.45% SO4 2-, remaining is ZSM-5
Molecular sieve, the silica alumina ratio of FER molecular sieve are 50~100；
The preparation step of the modified zsm-5 zeolite is as follows:
(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 salt water
The volume ratio of solution and organic solvent is 1:20~1:40, forms suspension A and metering is added under conditions of continuously stirring
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。
2. according to the method described in claim 1, it is characterized by: reaction temperature be 450~500 DEG C, reaction stagnation pressure be 0~
0.15MPa, weight space velocity are 2~4 h-1。
3. according to the method described in claim 1, it is characterized by: by weight percentage, FER molecular sieve and modified ZSM-5
Molecular sieve quality content is 50~90%.
4. according to the method described in claim 1, it is characterized by: the raw material containing n-butene comes from refinery or petrochemical plant
Methyl tertiary butyl ether(MTBE) device ether after carbon four, wherein n-butene mass content be 10~95%.
5. according to the method described in claim 1, it is characterized by: the preparation method of catalyst for cracking, by the FER molecule of metering
Straight forming after sieve and modified zsm-5 zeolite mixing, or will be after the FER molecular sieve of metering and modified zsm-5 zeolite mixing
It is made with binder kneading and compacting.
6. according to the method described in claim 5, it is characterized by: using FER molecular sieve and modified zsm-5 zeolite and hydrogen-oxygen
Change al binder kneading, and catalyst for cracking is made in extrusion molding.
7. according to the method described in claim 1, it is characterized by: FER molecular sieve be commercial goods, or press existing method system
It is standby.
8. according to the method described in claim 1, it is characterized by: ZSM-5 molecular sieve is commercial goods or presses existing method
Preparation.
9. 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.
10. according to the method described in claim 1, it is characterized by: iridium salt is in chloro-iridic acid, iridium chloride, ammonium chloroiridate
It is one or more.
11. according to the method described in claim 1, iridium salt is chloro-iridic acid it is characterized by: zirconates is zirconyl nitrate.
12. 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
Hydrocarbon or cycloalkane.
13. according to the method described in claim 1, it is characterized by: organic solvent be n-hexane, hexamethylene, 2- methylpentane,
One of 3- methylpentane, 2- methyl hexane, 3- methyl hexane, methyl cyclopentane are a variety of.
14. 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.
15. 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.
16. 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。
17. according to the method described in claim 1, inorganic acid ammonium is ammonium sulfate it is characterized by: inorganic acid is sulfuric acid.
18. according to the method described in claim 1, being roasted 5~10 hours it is characterized by: being roasted at 500~550 DEG C.
19. according to the method described in claim 1, it is characterized by: stabilization processes reagent is the production of n-butene skeletal isomerization
The inferior patrol of isobutene byproduct in process.
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