CN106140289A - A kind of Cracking catalyst containing modified beta zeolite - Google Patents
A kind of Cracking catalyst containing modified beta zeolite Download PDFInfo
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Abstract
A kind of Cracking catalyst containing modified beta zeolite, comprises 10 weight %～the y-type zeolite of 80 weight %, 1 weight %～the modified beta zeolite of 50 weight %, 5 weight %～the clay of 70 weight % and 5 weight %～the heat-resistant inorganic oxide of 60 weight %；The anhydrous chemical expression of wherein said modified beta zeolite, is calculated as with oxide mass: (0～0.2) Na2O (0.5～15) MO2(0.5～15) RE2O3(0.5～15) Al2O3(60～98) SiO2, wherein one or both in the Group IVB metal of M.The preparation method of this catalyst includes the mixing making beating of y-type zeolite, modified beta zeolite, clay, heat-resistant inorganic oxide binding agent and water, the step of spray drying.This catalyst heavy oil cracking ability is strong, and total liquid yield is high, and in liquefied gas, density of propylene is high.
Description
Technical field
The present invention relates to a kind of catalytic cracking catalyst, more specifically to one is containing modified beta zeolite
Cracking catalyst.
Background technology
Along with increasing rapidly of the derivant demands such as polypropylene, the demand of propylene is the most all increased by the whole world.
Fluid catalytic cracking is one of important process producing low-carbon alkene and propylene.For increased low carbon olefine output
And propylene, people add shape-selective molecular sieve the most in the catalyst, as US3758403 disclose with
ZSM-5 and the catalyst that large pore zeolite (mainly y-type zeolite) is active component, improving, gasoline is pungent
Too increasing the productivity of C3, C4 alkene while alkane value, wherein large pore zeolite carries out cracking life to raw material
Becoming gasoline, diesel oil, ZSM-5 shape-selective molecular sieve is cracked into low-carbon alkene further.Although ZSM-5
It is the most conventional auxiliary agent, productivity of propylene can be increased, but the most also reduce feed stock conversion and liquid receipts.
In recent years, β zeolite is applied to catalytic cracking catalyst and produces the report of low-carbon alkene also by people
A lot.β zeolite is a kind of silica-rich zeolite with intersection 12-membered ring's channel system, has acid catalysis concurrently
Characteristic and structure selectivity, and there is the highest heat stability, hydrothermal stability and anti-wear performance,
Therefore in a series of catalytic reactions, show good heat and hydrothermal stability, acid resistance, anti-coking
Property and catalysis activity.
CN1103105A discloses the Cracking catalyst of a kind of high yield of isobutene and iso-amylene, its component and
Content is: (1) 5%～the modified HZSM-5 of silica alumina ratio 20～100 of 25%；(2) 1%～5% silica alumina ratio
It is the high silicon HZSM-5 of 250～450；(3) 5%～the USY zeolite of 20%；(4) 1%～the β zeolite of 5%；
(5) 30%～the natural clay of 60%；(6) 15%～the inorganic oxide of 30%.Its preparation method is
Be added to the molecular sieve pulp after homogenizing in carrier pulp to pull an oar, filter, be dried, molding, prepare and urge
Agent product.This catalyst has the feature of high yield of isobutene and iso-amylene, simultaneously can be high with coproduction
Octane rating gasoline.
CN1354224A discloses a kind of catalytic cracking catalyst, and this catalyst is by 0～70% weight viscous
Soil, the inorganic oxide of 5%～90% weight and the β zeolite of 1%～50% weight or modenite mixture
Composition.This catalyst productivity of propylene and feed stock conversion are higher, but liquid is received relatively low.
CN101310858A discloses a kind of catalyst for heavy oil catalytic cracking, with USY type molecular sieve is
Main, add β zeolite-mercerising eutectic molecular sieve auxiliary agent, on the basis of the percentage by weight of catalyst, USY
The content of type molecular sieve is 10%～50%, and the content of β zeolite mercerising eutectic molecular sieve is
10%～20%, binding agent 5%～50%, clay 10%～75%, described β zeolite-mercerising eutectic molecule
Sieve is to have β zeolite and the molecular sieve of mordenite structure unit.
CN101134172A discloses a kind of Hydrocarban coversion catalysts, on the basis of total catalyst weight,
The heat-resistant inorganic oxide of zeolite mixture, 5%～99% containing 1%～60% and 0～the clay of 70%,
On the basis of zeolite mixture gross weight, in described zeolite mixture containing 1%～75% by phosphorus and transition
The zeolite with MFI structure of β zeolite, 25%～99% that metal M is modified and 0～the large pore zeolite of 74%,
Wherein, the anhydrous chemical expression of the described β zeolite modified by phosphorus and transition metal M is with oxide institute
When the quality percentage accounted for represents it is: (0～0.3) Na2O (0.5～10) Al2O3(1.3～10)
P2O5(0.7～15) MxOy(64～97) SiO2, wherein, described transition metal M selected from Fe, Co,
One or more in Ni, Cu, Mn, Zn and Sn.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of Cracking catalyst containing modified beta zeolite, should
Catalyst is applied to catalytic cracking process, can be obviously enhanced the heavy oil conversion performance of catalyst, and improve
Propylene Selectivity.
The present invention provides a kind of catalytic cracking catalyst, with described catalytic cracking catalyst gross weight as base
Standard, described catalytic cracking catalyst contains 10 weight %～the y-type zeolite of 80 weight %, 1 weight %～50
The modified beta zeolite of weight %, 5 weight %～the clay of 70 weight % and 5 weight %～60 weight % resistance to
Hot inorganic oxide.The anhydrous chemical expression of wherein said modified beta zeolite, with oxidation material gauge
For: (0～0.2) Na2O (0.5～15) MO2(0.5～15) RE2O3(0.5～15) Al2O3(60～98)
SiO2, wherein M one or more preferred Ti and/or Zr in Group IVB metal.
The catalytic cracking catalyst that the present invention provides, can be by containing 10 weight %～the Y of 80 weight %
Type zeolite, 1 weight %～the modified beta zeolite of 50 weight %, 5 weight %～the clay of 70 weight % and 5
The heat-resistant inorganic oxide composition of weight %～60 weight %, or possibly together with other zeolite, such as MFI
Structural zeolite.Preferably, on the basis of total catalyst weight, described catalyst contains 10%～60%
Y-type zeolite, the modified beta zeolite of 2%～30%, the clay of 5%～50% and 5%～the heat resistant inorganic of 50%
Oxide.The anhydrous chemical expression of wherein said modified beta zeolite, with the preferred model of oxidation material gauge
Enclose for (0～0.2) Na2O (1～10) MO2(1～10) RE2O3(1～10) Al2O3(70～95)
SiO2, wherein one or more in Group IVB metal of M, preferably Ti and/or Zr.
The present invention provide catalyst in, described clay be selected from Kaolin, rectorite, kieselguhr,
One or several mixture in montmorillonite, bentonite, meerschaum.
In the catalyst that the present invention provides, described heat-resistant inorganic oxide includes that heat-resistant inorganic oxide is originally
Body is or/and heat-resistant inorganic oxide precursor.Heat-resistant inorganic oxide itself can be selected from urging as cracking
One or more in the heat-resistant inorganic oxide of agent substrate and binder component, such as aluminium oxide, oxygen
One or more in SiClx, amorphous silicon aluminium；Heat-resistant inorganic oxide precursor refers in the present invention
Can form the material of heat-resistant inorganic oxide in catalyst preparation process, the precursor such as aluminium oxide is optional
In Alumina gel, boehmite, boehmite, Alumina hydrate, amorphous hydroted alumina
One or more；The precursor of described silicon oxide is selected from Ludox, Silica hydrogel and waterglass
Plant or several.These heat-resistant inorganic oxides itself are or/and heat-resistant inorganic oxide precursor and preparation thereof
Method is well known to those skilled in the art.
The present invention provide catalyst in, described y-type zeolite can be ultrastable, phosphorous and
/ or the y-type zeolite of rare earth, the phosphorous and/or overstable gamma zeolite of rare earth in one or more.
In the catalyst that the present invention provides, described modified beta zeolite, its anhydrous chemical expression, with
The preferred scope of oxidation material gauge is: (0～0.2) Na2O (1～10) MO2(1～10)
RE2O3(1～10) Al2O3(70～95) SiO2, wherein M one in the Group IVB metal or
Multiple, preferably Ti and/or Zr.
Described modified beta zeolite, can be prepared by the method comprised the following steps:
(1) solution of sodium form β zeolite rare earths salt or rare-earth salts and inorganic ammonium salt is carried out ion
Exchange, then filters, washs, and in 300～700 DEG C, 0～100% roasting under water vapour, obtains dilute
The β zeolite of land reform, the sodium oxide content in the β zeolite that gained is rare earth modified is not higher than 0.2 weight %；
(2) the rare earth modified β zeolite impregnating metal in organic solvent step (1) obtained；
(3) β zeolite step (2) obtained obtains in 350～800 DEG C of roastings or by step (2)
β Zeolite dehydration, be then not less than 0.5 hour in 350～800 DEG C of roastings, preferably roasting time,
For example, 0.5～5 hour；
(4) with aqueous acid contact procedure (3) gained β zeolite, in aqueous acid, acid is dense
Degree is with H+It is calculated as 0.1～2.0mol/L；By the β zeolite washing after contact, optionally drying, obtain modified β
Zeolite (also referred to as Group IVB metal and rare earth composite modified β zeolite).
In the preparation method of described modified beta zeolite, in step (1), described ion exchange is permissible
For according to rare-earth salts (with RE2O3Meter): ammonium salt: sodium form β zeolite (in terms of butt): deionization
Water=0.01～0.15:0～0.6:1:1～50, preferably 0.01～0.10:0～0.4:1:2～30
Weight ratio by the mixing making beating of rare-earth salts, ammonium salt, sodium form β zeolite and deionized water uniformly, 25～
150 DEG C, exchange at least 0.3 hour at preferably 25～90 DEG C such as 0.5～5 hour, preferably 0.5～3
Hour.The sintering temperature of described roasting is 350～800 DEG C, and roasting time is more than 0.5 hour, such as
It it is 0.5～8 hour or 0.5～5 hour；Step (1) described roasting be preferably in 350～800 DEG C, 1～
Under 100 volume % water vapour atmospheres at least 0.5 hour, for example, 0.5～8 hour, preferably sintering temperature
Being 450～650 DEG C, roasting time is 1～6 hour.Described ammonium salt is selected from ammonium chloride, ammonium sulfate, sulphuric acid
In hydrogen ammonium, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate and ammonium phosphate one or several.Institute
The rare-earth salts stated is one or more in the chloride of rare earth, nitrate and sulfate, preferably chloride.
Wherein said rare earth preferably includes lanthanum and/or cerium or is lanthanum and/or cerium.The zeolite that step (1) obtains
Water content be preferably more than 5% weight, preferably more than 3 weight %.
In the preparation method of described modified beta zeolite, in step (2), described by step (1)
The rare earth modified β zeolite impregnating metal in organic solvent arrived, including by dissolved with the metallization of IV B race
The rare earth modified β zeolite that the organic solvent of compound obtains with step (1) mixes, and keeps more than 0.5 hour
Such as 0.5～12 hour, such as, stir or stand (not stirring) more than 0.5 hour preferably 0.5～12 little
Time, the process then carrying out next step such as carries out step (3) or repeats the leaching described in step (2)
Stain.The rare earth modified β zeolite (in terms of butt) that wherein step (1) obtains is consolidated with organic solvent
Liquor ratio (weight ratio) can be 1:(0.5～5) for example, 1:(1～2).Can pass through once or many
The secondary β of being immersed in zeolite introduces described Group IVB metal.The β that in step (2), single-steeping obtains
Zeolite can also impregnate Group IVB metallic compound further, the most repeatedly impregnates.Described Group IVB
One or more in Ti, Zr, Hf, Rf of metal, preferably one or both in Ti, Zr,
Described IV B race metallic compound is the compound of Ti, the compound of Zr, the compound of Hf, Rf
The compound of for example, Ti of one or more in compound and/or the compound of Zr.IV described B
Race's metallic compound can be inorganic salt and/or the organo-metallic compound, such as titanium of IV B race metal
Compound can be titanium sulfate, titanyl sulfate, titanium tetrachloride, titanous chloride., butyl titanate, fluorine
One or more in titanium acid ammonium.The compound of zirconium can be Zirconium tetrachloride., Disulfatozirconic acid., zirconium nitrate,
One or more in zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide.
In the preparation method of described modified beta zeolite, in step (2), the water of described organic solvent contains
Amount is less than 5 weight %, and preferably more than 3 weight % are such as less than 1 weight %.Organic solvent is permissible
One or more in alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane, described in have
The normal boiling point of machine solvent preferably 40～100 DEG C.The preferred normal hexane of described organic solvent, hexamethylene, heptan
One in alkane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, chloroform or
Multiple.
In the preparation method of described modified beta zeolite, in step (2), described dipping, wherein with dry
The β zeolite of base meter and the solid-to-liquid ratio of organic solvent can be 1:(1～4) weight ratio, for example, 1:
(1.1～1.6).Temperature during dipping makes organic solvent be liquid.Described dipping can use equal-volume to soak
Stain method or excess dipping method.Dipping temperature does not has particular/special requirement can be such as to impregnate under room temperature.
In the preparation method of described modified beta zeolite, in step (3), to obtained by step (2)
The zeolite of impregnating metal carry out roasting or dry roasting, described sintering temperature is 350～800 DEG C, roasting
The burning time is more than 0.5 hour, and roasting time is 0.5～5 hour, and such as sintering temperature is 450～650 DEG C,
Roasting time is 1～4 hour.Described calcination atmosphere is dry air, noble gas, preferably indifferent gas
Body.Described noble gas such as nitrogen, helium, in described dry air, vapour content is less than 0.5
Volume %, such as less than 0.3 volume %.If the product obtained in step (2) is without being dried,
The step being dried is preferably included before described roasting, to reduce the content of organic solvent in zeolite, described dry
It is dry that can be the zeolite that step (2) obtained be room temperature～100 DEG C of drying times are 4～48 little in temperature
Time.
In the preparation method of described modified beta zeolite, step (4) middle aqueous acid (is called for short acid
Solution) process step (3) gained β zeolite, including the β zeolite described step (3) obtained
Contact with acid solution and such as the β zeolite that described step (3) obtains is mixed with acid solution, then mistake
Filter, wash and be optionally dried；The temperature of contact is room temperature～100 DEG C, and time of contact is preferably not less than
0.2 hour, preferably 0.5～5 hour, solid-to-liquid ratio (zeolite and the mass ratio of acid solution) was 1:5～20,
In aqueous acid, the concentration of acid is with H+It is calculated as 0.1～2mol/L, preferably 0.5～2mol/L such as
0.5～1.5mol/L.Described acid is selected from hydrochloric acid, sulphuric acid, nitric acid, oxalic acid, acetic acid, formic acid, Fructus Citri Limoniae
One or more in one or more in acid, preferably hydrochloric acid, oxalic acid, formic acid, citric acid.Room
Temperature for example, 15～40 DEG C.Zeolite after contacting with acid can be washed with water to wash away free by described washing
Acid, then filters.The filter cake being filtrated to get can be dried or moist, be dried can use drying,
Pneumatic conveying drying or spray drying, to reduce the water content in zeolite.Step (4) is dried to obtain
Zeolite can be with roasting or not roasting.Washing and the method being dried are existing method, the method such as washed
Can be that β zeolite is mixed according to the weight ratio of 1:5～20 with water, then filter；The method being dried
Can be that filter cake is dried at 100～200 DEG C such as drying, pneumatic conveying drying.The method of roasting refers to
Existing method of roasting, such as can be by zeolite 450～700 roasting temperatures 0.5～5 hours, described roasting
Burning can in atmosphere or 1～100% carry out under volume of water steam atmosphere.
In the preparation method of the modified beta zeolite that the present invention provides, to sodium form β zeolite, first pass through rare earth
Ion exchanges, then uses the Group IVB metal described in the introducing of organic solvent dipping method, is finally entered
Row acid treatment, can obtain the β zeolite with high hydrothermal stability, and it has high cracking hydrocarbon ability,
High Propylene Selectivity.In described modified beta zeolite, the content of Group IVB metal-oxide is 0.5～15
Weight %, the content of rare earth oxide is 0.5～15 weight %, and the content of aluminium oxide is 0.5～15 weight
%, the content of silicon oxide is 60～98 weight % such as 65～98 weight %, and the content of sodium oxide is 0～0.2
Weight %.Further, the content of described Group IVB metal-oxide is 1～10 weight %, described rare earth
The content of oxide is 1～10 weight % such as 2～8 weight %, and the content of aluminium oxide is 1～10 weight %,
The content of silicon oxide is 70～95 weight % such as 75～95 weight %, and the content of sodium oxide is 0～0.2 weight
Amount %.
The preparation method of the Cracking catalyst that the present invention provides, including: formed and include described modified β boiling
Stone, Y zeolite, clay, heat-resistant inorganic oxide and/or its precursor and the serosity of water, spray dried
Roasting dry, optional, optionally washing and be dried.A kind of specific embodiment is as follows: by deionized water,
Clay, heat-resistant inorganic oxide and/or the mixing making beating of its precursor, then add Y in gained serosity
Type zeolite and the mixture of modified beta zeolite, (such as stir) after homogenizing spray drying, roasting,
Obtain the catalyst that the present invention provides.Wherein, before adding zeolite mixture, described clay is added
Before or after, it is also possible to adding acid in serosity, regulation slurry pH value is 1～5 such as 2～4,
Aging 0.5～5 hour in 30～90 DEG C.Described acid can be dissolved in the mineral acid of water and organic acid
Plant or several, preferably one or more in hydrochloric acid, nitric acid, phosphoric acid.
In the method for preparing catalyst that the present invention provides, the method for described spray drying and condition are ability
Well known to field technique personnel, being spray-dried gained catalyst, also can carry out roasting, the temperature of roasting is
350～800 DEG C, preferably 400～650 DEG C, the time of roasting is 0.5～6 hour, preferably 1～4
Hour；Described roasting can be carried out in any atmosphere, carries out the most in atmosphere.
The catalytic cracking catalyst that the present invention provides, containing the β that rare earth and Group IVB metal composite are modified
Zeolite, has higher heavy oil cracking ability, has considerably higher total liquid yield and liquefied gas yield,
And density of propylene significantly improves in liquefied gas.
Detailed description of the invention
The following examples illustrate the present invention further, it is intended to helps reader to be more fully understood that this
The essence place of invention and the beneficial effect brought, but should not be construed as the model implemented to the present invention
Any restriction enclosed.
Prepare raw materials used in catalyst being described as follows: Kaolin is produced by Kaolin of Suzhou company, admittedly contain
Amount is 76 weight %；Alumina content in Alumina gel is 21.5 weight %；Boehmite is by Shandong
Aluminium manufacturer produces, and solid content is 62.0 weight %；Acidification pseudo-boehmite solid content is 12.0 weight %,
Hydrochloric acid is acidified, and during acidifying, acid (HCl) is 0.15 with the mol ratio of aluminium oxide；Overstable gamma zeolite used
DASY (2.0) is that Shandong catalyst plant is produced, and solid content 94.7%, lattice constant isWith weight
Amount degree meter, Na2O content is 1.3%, RE2O3Content is 2.5%；Overstable gamma zeolite
DASY (6.0) is that Shandong catalyst plant is produced, and solid content 84.8%, lattice constant isWith weight
Amount degree meter, Na2O content is 1.6%, RE2O3Content is 6.2%；Phosphorous Y zeolite PREHY
Producing for Shandong catalyst plant, solid content 92.4%, lattice constant isWith percentage by weight
Content meter, Na2O content is 1.5%, RE2O3Content is 8.5%.Remaining reagent is by traditional Chinese medicines grouping of the world economy
Learning reagent company limited to produce, specification is analytical pure.Sodium form β zeolite, middle Effect of Catalysis In Petrochemistry agent Shandong
Branch company produces, SiO2/Al2O3=25 (mol ratios), butt accounts for 75 weight %.
Embodiment 1
(Sinopec catalyst asphalt in Shenli Refinery produces, SiO to take 200g sodium form β zeolite2/Al2O3=25
(mol ratio), butt accounts for 75 weight %), after pulling an oar with 1500g deionized water, add 45 grams
(NH4)2SO4With 45 milliliters of RECl3Solution (RE2O3Concentration 270 grams per liter, lower same), heat up
Exchange 1 hour to 90 DEG C, filter and be washed with deionized, in 600 DEG C, roast under 100% water vapour
Burn 2 hours, obtain the β zeolite after rare earth exchanged, water content 3 weight %, be designated as A-1；
By 5.23g zirconium nitrate Zr (NO3)4·5H2O is dissolved in 150g ethanol (analytical pure) and being impregnated
Liquid, then mixs homogeneously above-mentioned impregnation liquid with the β Wessalith CS-1 after rare earth exchanged, stands 24 hours,
Dry 24 hours for 100 DEG C, in nitrogen atmosphere, roasting 4 hours at 500 DEG C, be designated as AC-1；
β Wessalith CS C-1 after above-mentioned roasting is joined the mineral acid that 2000g acid concentration is 1.0mol/L
In aqueous solution (dilute hydrochloric acid solution), mix homogeneously, it is warmed up to 80 DEG C and stirs 3 hours, then filter,
It is washed with deionized (the washing water yield is 15 times of zeolite butt weight), filters, be dried, obtain
The modified beta zeolite that the present invention provides, is designated as B1.Element chemistry consists of
0.1Na2O·1.0ZrO2·7.8RE2O3·6.7Al2O3·84.4SiO2(weight composition).
By modified beta zeolite B1 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, use XRD
Detecting the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is
Relative crystallinity after hydrothermal aging and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in
Table 1.
Embodiment 2
Take 200g sodium form β zeolite (ibid), after pulling an oar with 2000g deionized water, add 35 grams
Ammonium chloride and 22.2 milliliters of RECl3Solution (RE2O3Concentration 270 grams per liter), it is warmed up to 85 DEG C of exchanges
1.5 hours, filter and be washed with deionized, in 550 DEG C, roasting 3 hours under 100% water vapour,
Obtain the β zeolite after rare earth exchanged, water content 3 weight %, be designated as A-2；
15.7g zirconium oxychloride is dissolved in 200g ethanol, then by after gained solution and rare earth exchanged
β Wessalith CS-2 mix homogeneously, stirs 24 hours, dries 24 hours for 100 DEG C, nitrogen atmosphere, 550 DEG C
Lower roasting 3 hours, obtains the β Wessalith CS C-2 after roasting；
β Wessalith CS C-2 after above-mentioned roasting is joined the oxalic acid water that 1500g acid concentration is 2.0mol/L
In solution, it is warmed up to 90 DEG C and continues stirring 1 hour, then filter, be washed with deionized (washing
The water yield is 15 times of molecular sieve butt weight), take out filtration cakes torrefaction, obtain the modification that the present invention provides
β zeolite, is designated as B2.Element chemistry consists of 0.05Na2O·3.8ZrO2·3.9RE2O3
·7.5Al2O3·84.75SiO2(weight composition).
By modified beta zeolite B2 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, use XRD
Detecting the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is
Relative crystallinity after hydrothermal aging and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in
Table 1.
Embodiment 3
Take 200g sodium form β zeolite (ibid), after pulling an oar with 3000g deionized water, add 30 grams
Ammonium chloride and 33.4 milliliters of RECl3Solution (RE2O3Concentration 270 grams per liter), it is warmed up to 80 DEG C of exchanges
2 hours, filter and be washed with deionized, in 500 DEG C, roasting 2 hours under 100% water vapour,
β zeolite after rare earth exchanged, water content 2 weight %, it is designated as A-3；
28.3g zirconium iso-propoxide is dissolved in 200g ethanol, then by above-mentioned solution and obtained rare earth
β Wessalith CS-3 mix homogeneously after exchange, stands 12 hours post-dryings；Nitrogen atmosphere, 600 DEG C
Lower roasting 2 hours, obtains the β zeolite after roasting, is designated as AC-3；
β Wessalith CS C-3 after above-mentioned roasting is joined the hydrochloric acid water that 1000g acid concentration is 0.5mol/L
In solution, stir 3 hours at 80 DEG C, then filter, be washed with deionized and (wash the water yield for dividing
20 times of son sieve butt weight), take out filter cake and dry, obtain the modified beta zeolite that the present invention provides
B3, element chemistry consists of 0.1Na2O·5.9ZrO2·5.7RE2O3·5.2Al2O3·83.1SiO2(weight
Composition).
By modified beta zeolite B3 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, use XRD
Detecting the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is
Relative crystallinity after hydrothermal aging and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in
Table 1.
Embodiment 4
Take 200g sodium form β zeolite, after pulling an oar with 2000g deionized water, add 60 grams of ammonium hydrogen carbonate
With 5.6 milliliters of RECl3Solution (RE2O3Concentration 270 grams per liter), it is warmed up to 85 DEG C and exchanges 2 hours,
Filter and be washed with deionized, in 600 DEG C of roastings 2 hours, obtain β Wessalith CS-4 after ammonium exchange,
Its water content 1.5 weight %；
47.2g zirconium iso-propoxide is dissolved in 250g ethanol, then by after gained solution and above-mentioned exchange
β Wessalith CS-4 mixes, and stands 12 hours；Then in 100 DEG C dry 24 hours, nitrogen atmosphere,
Roasting 3 hours at 450 DEG C；Obtain the β Wessalith CS C-4 after roasting；
β Wessalith CS C-4 after above-mentioned roasting is joined the sulphuric acid water that 1000g acid concentration is 0.2mol/L
In solution, stir 2 hours at 80 DEG C, then filter, be washed with deionized and (wash the water yield for dividing
Son sieve 10 times of butt weight), take out filter cake and be placed in 550 DEG C, roasting 2 hours in 100% water vapour,
Obtaining the modified beta zeolite B4 that the present invention provides, its anhydrous chemical consists of
0.1Na2O·9.6ZrO2·1.0RE2O3·5.8Al2O3·83.5SiO2(weight composition).
By modified beta zeolite B4 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, use XRD
Detecting the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is
Relative crystallinity after hydrothermal aging and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in
Table 1.
Embodiment 5
Take 200g sodium form β zeolite (ibid), after pulling an oar with 3000g deionized water, add 50 grams
Ammonium chloride and 5.6 milliliters of RECl3Solution (RE2O3Concentration 270 grams per liter), it is warmed up to 90 DEG C of exchanges 1
Hour, filter and be washed with deionized, in 650 DEG C, roasting 1 hour under 100% water vapour.?
β Wessalith CS-5 after exchange, water content 2.0 weight %；
51.2g butyl titanate is dissolved in 300g hexamethylene, after then above-mentioned solution impregnation being exchanged
β Wessalith CS-5, stir 6 hours, dry 24 hours in 100 DEG C, at nitrogen atmosphere, at 650 DEG C
Roasting 1 hour, obtains the β Wessalith CS C-5 after roasting；
β Wessalith CS C-5 after above-mentioned roasting is joined the oxalic acid water that 2000g acid concentration is 1.5mol/L
In solution, mix homogeneously, it is warmed up to 90 DEG C and continues stirring 1 hour, then filter, use deionized water
Washing (the washing water yield is 20 times of molecular sieve butt weight), takes out filter cake and dries.Obtain the present invention
The modified beta zeolite B5 provided；Element chemistry consists of
0.1Na2O·8.0TiO2·1.0RE2O3·2.8Al2O3·88.4SiO2(weight composition).
By modified beta zeolite B5 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, use XRD
Detecting the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is
Relative crystallinity after hydrothermal aging and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in
Table 1.
Embodiment 6
Take 200g sodium form β zeolite (ibid), after pulling an oar with 3000g deionized water, add 50 grams
Ammonium chloride and 11.1 milliliters of RECl3Solution (RE2O3Concentration 270 grams per liter), it is warmed up to 90 DEG C of exchanges
1 hour, filter and be washed with deionized, in 500 DEG C, roasting 3 hours under 100% water vapour,
β Wessalith CS-6 after exchange, water content 3.0 weight %；
7.13g titanium tetrachloride and 10.5g zirconium nitrate are dissolved in 250g ethanol, then by above-mentioned solution
Dipping exchange after β zeolite, stands 24 hours, in 100 DEG C drying 24 hours, nitrogen atmosphere,
Roasting 2 hours at 500 DEG C, obtain the β zeolite after roasting；
β zeolite after gained roasting is joined the citric acid that 3000g acid concentration is 1.0mol/L water-soluble
In liquid, mix homogeneously, it is warmed up to 85 DEG C and continues stirring 2 hours, then filter, be washed with deionized water
Wash (the washing water yield is 20 times of molecular sieve butt weight), take out filter cake and dry.Obtain the present invention to carry
The modified beta zeolite B6 of confession.Element chemistry consists of 0.1Na2O·2.0ZrO2·1.9TiO2·1.8RE2O3
·6.3Al2O3·87.9SiO2(weight composition).
By modified beta zeolite 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, examine with XRD
Surveying the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is water
Relative crystallinity after heat ageing and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in table
1。
Comparative example 1
The preparation of this comparative example explanation contrast modified beta zeolite.
Take 200g sodium form β zeolite (ibid), mix with 2000g deionized water and 45g ammonium chloride and beat
Slurry, is warmed up to 80 DEG C and stirs 1 hour, then filter, repeat said process 3 times, Na to zeolite2O
Content is less than 0.2 weight %, in 600 DEG C, roasting 1 hour under 100% water vapour.By above-mentioned ammonium modification β
Zeolite, after continuing to pull an oar with 2000g deionized water, adds 45g ammonium chloride, little in 80 DEG C of exchanges 1
Time, in 600 DEG C, roasting 1 hour under 100% water vapour after filtration washing, obtain contrasting modified β boiling
Stone, is designated as DB1.Element chemistry consists of 0.1Na2O·5.8Al2O3·94.1SiO2(weight composition).
Will contrast modified beta zeolite DB1 800 DEG C, under the conditions of 100% water vapour after aging 8 hours,
Detecting, with XRD, the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization is protected
Office Copy is the ratio of the relative crystallinity after hydrothermal aging and the relative crystallinity before hydrothermal aging.Its number
According to being listed in table 1.
Comparative example 2
This comparative example illustrates the preparation of rare earth modified β zeolite.
Take 200g sodium form β zeolite (ibid), with 2000g deionized water and 35g ammonium chloride and 22.2
Milliliter RECl3Solution (RE2O3Concentration 270 grams per liter), mixing making beating, it is warmed up to 80 DEG C of stirrings 1
Hour, then filter, in 600 DEG C, roasting 1 hour under 100% water vapour.Obtain rare earth modified β
Zeolite, is designated as DB2.Element chemistry consists of 0.1Na2O·3.9RE2O3·6.3Al2O3·89.7SiO2(weight
Amount composition).
By DB2 800 DEG C, under the conditions of 100% water vapour after aging 8 hours, detect it with XRD
The relative crystallinity that hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is that hydro-thermal is old
Relative crystallinity after change and the ratio of the relative crystallinity before hydrothermal aging.Its data are listed in table 1.
Comparative example 3
The explanation of this comparative example uses modified zirconia β zeolite prepared by aqueous impregnation method.
According to the method for embodiment 2, except for the difference that, by the zirconium oxychloride ZrOCl of equivalent2·8H2O is dissolved in
In 200g deionized water, then gained solution is mixed homogeneously with the β zeolite after exchange, stand 24 little
Time, dry 24 hours for 100 DEG C, in air atmosphere, roasting 3 hours at 550 DEG C.Finally obtain contrast
Modified beta zeolite, is designated as DB3, and element chemistry consists of 0.05Na2O·3.8ZrO2·3.9RE2O3
·7.4Al2O3·84.85SiO2(weight composition).
Will contrast modified beta zeolite DB3 800 DEG C, under the conditions of 100% water vapour after aging 8 hours,
Detecting, with XRD, the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization is protected
Office Copy is the ratio of the relative crystallinity after hydrothermal aging and the relative crystallinity before hydrothermal aging.Its number
According to being listed in table 1.
Comparative example 4
The explanation of this comparative example does not use acid treatment, the modified beta zeolite of preparation.
According to the method for embodiment 2, except for the difference that, the β zeolite after roasting is without the acid of final step
Process.Element chemistry consists of 0.1Na2O·3.9ZrO2·3.9RE2O3·7.8Al2O3·84.3SiO2(weight
Composition), it is designated as DB4.
Will contrast modified beta zeolite DB4 800 DEG C, under the conditions of 100% water vapour after aging 8 hours,
Detecting, with XRD, the relative crystallinity that its hydrothermal aging is forward and backward, and calculate crystallization reservation degree, crystallization is protected
Office Copy is the ratio of the relative crystallinity after hydrothermal aging and the relative crystallinity before hydrothermal aging.Its number
According to being listed in table 1.
Comparative example 5
According to the method for comparative example 2, prepare the rare earth modified Y molecular sieve that content of rare earth is 8 weight %,
Being designated as DB5, its weight consists of 0.05Na2O·7.8RE2O3·7.3Al2O3·84.85SiO2.By its
800 DEG C, under the conditions of 100% water vapour after aging 8 hours, detect its hydrothermal aging with XRD forward and backward
Relative crystallinity, and calculate crystallization reservations degree, crystallization reservations degree is relatively crystallizing after hydrothermal aging
The ratio of the relative crystallinity before degree and hydrothermal aging.Its data are listed in table 1.
Table 1
From table 1, the modified beta zeolite that the modified beta zeolite that the present invention provides obtains with existing method
(modified beta zeolite that such as comparative example provides) is compared, and crystallization reservation degree significantly improves, and shows this
The modified beta zeolite of bright preparation has higher hydrothermal stability；Modified beta zeolite tool prepared by the present invention
There are higher specific surface area and pore volume.
Embodiment 7～12
Embodiment 7～12 explanation use the present invention provide modified beta zeolite as catalyst activity component it
One in catalytic cracking of petroleum hydrocarbon, on heavy oil conversion performance and the impact of productivity of propylene.
By embodiment 1～6 prepare modified beta zeolite carry out on fixed bed aging equipment respectively 800 DEG C,
100% steam aging 4 hours, then with the work of DOCP catalyst (production of Chang Ling catalyst plant)
Industry poising agent and shape-selective molecular sieve HZSM-5 (silica alumina ratio 25) are according to DOCP: modified β
Zeolite: the ratio of shape-selective molecular sieve=85:5:10 is mixed to be converted uniformly, respectively obtain catalyst C1, C2,
C3、C4、C5、C6。
Catalytic cracking small fixed micro-reactor is evaluated catalyst, appreciation condition: reaction temperature
500 DEG C, weight oil ratio 2.94, weight (hourly) space velocity (WHSV) (weight space velocity) 16h-1, catalyst inventory 5g, raw material
Oil nature is shown in Table 2.Evaluation result is shown in Table 3.
Comparative example 6～10
The modified beta zeolite that comparative example 1～5 is prepared by comparative example 6～10 explanation is catalyst activity component
One of in catalytic cracking of petroleum hydrocarbon, on heavy oil conversion performance and the impact of productivity of propylene.
According to the method for embodiment 7, prepare comparative catalyst DC1, DC2, DC3, DC4, DC5.
Catalytic cracking fixed bed micro-anti-on evaluate catalyst, appreciation condition is reaction temperature 500 DEG C, agent
Oil ratio 2.94, catalyst inventory 5g, raw oil character is shown in Table 2.Evaluation result is shown in Table 3.
Table 2 raw oil character
Table 3 evaluation result
From table 3, compared with adding the β zeolite that existing method obtains, at catalytic cracking catalyst
After the modified beta zeolite that the middle addition present invention provides, in liquefied gas, density of propylene significantly improves, and heavy oil turns
Rate significantly improves, and gasoline and productivity of propylene increase.
Embodiment 13
The modified beta zeolite B21 (preparation method refers to embodiment 1) that the preparation present invention provides.B21
Element chemistry consist of 0.1Na2O·5.2ZrO2·2.5RE2O3·7.8Al2O3·84.4SiO2(weight group
Become).
3.3Kg Kaolin, 4.7Kg Alumina gel are joined in making beating tank with 8.0Kg decationized Y sieve water
Making beating, is subsequently adding 16.7Kg acidification pseudo-boehmite, after stirring 60 minutes, adds 4.1Kg
DASY (0.0) zeolite (butt) and 1.0Kg (butt) above-mentioned modified beta zeolite B21 and 7.6 public
The serosity that jin deionized water making beating is formed, homogenous disperse (stirring) 30 minutes, the slurry that then will obtain
Liquid spray drying forming, in 500 DEG C of roastings 2 hours, obtains Cracking catalyst C21 that the present invention provides.
The composition of C21 is shown in Table 4.
Embodiment 14
The method of reference example 6 changes proportioning and prepares the modified beta zeolite B22 that the present invention provides.B22
Element chemistry consist of 0.05Na2O·3.8ZrO2·3.5TiO2·1.5RE2O3·5.2Al2O3·85.95SiO2
(weight composition).
Then according to the method for embodiment 13 prepares catalyst, except for the difference that with modified beta zeolite B22 generation
For B21.Obtain Cracking catalyst C22 that the present invention provides.The composition of C22 is shown in Table 4.
Embodiment 15
The method of reference example 2 changes proportioning and prepares the modified beta zeolite B23 that the present invention provides.B23
Element chemistry consist of 0.1Na2O·6.1ZrO2·1.9RE2O3·8.1Al2O3·83.8SiO2(weight group
Become).
Then according to the method for embodiment 13 prepares catalyst, except for the difference that with modified beta zeolite B23 generation
For B21.Obtain Cracking catalyst C23 that the present invention provides.The composition of C23 is shown in Table 4.
Embodiment 16
The method of reference example 5 changes proportioning and prepares the modified beta zeolite B24 that the present invention provides.B24
Element chemistry consist of 0.1Na2O·4.2TiO2·2.0RE2O3·6.7Al2O3·87.0SiO2(weight group
Become).
Then according to the method for embodiment 13 prepares catalyst, except for the difference that with modified beta zeolite B24 generation
For B21.Obtain Cracking catalyst C24 that the present invention provides.The composition of C24 is shown in Table 4.
Comparative example 11
Take 200g sodium form β zeolite (ibid), mix with 1500g decationized Y sieve water and 40g ammonium sulfate
Making beating, is warmed up to 80 DEG C and stirs 1 hour, then filter, repeat said process, Na to zeolite2O
Content is less than 0.2 weight %, in 600 DEG C, roasting 1 hour under 100% water vapour.By above-mentioned ammonium modification β
Zeolite, adds 40g ammonium sulfate after continuing to pull an oar with 1500g decationized Y sieve water, little in 80 DEG C of stirrings 1
Time, in 550 DEG C, roasting 2 hours under 100% water vapour after filtration washing, obtain changing without metal
The β zeolite DB21 of property.The element chemistry of DB21 consists of 0.1Na2O·5.5Al2O3·94.4SiO2。
Then according to the method for embodiment 13 prepares catalyst, except for the difference that with without metal-modified
β zeolite DB21 replaces B21.Obtain the comparative catalyst DC21 that the present invention provides.The composition of DC21
It is shown in Table 4.
Comparative example 12
Modified beta zeolite is prepared, except for the difference that by the zirconium nitrate of equivalent according to the method for embodiment 13
Zr(NO3)4·5H2O is dissolved in 150g decationized Y sieve water, finally obtains modified beta zeolite DB22.DB22
Element chemistry consists of 0.1Na2O·5.0ZrO2·2.5RE2O3·7.0Al2O3·85.4SiO2。
Then according to the method for embodiment 13 prepares catalyst, except for the difference that modified beta zeolite DB22 generation
For B21.Obtain the comparative catalyst DC22 that the present invention provides.The composition of DC22 is shown in Table 4.
The composition of table 4 catalyst
Embodiment 17～20
The catalytic performance of the Cracking catalyst that this embodiment explanation present invention provides.
Catalyst C21～C24 is carried out in advance on fixed bed aging equipment 800 DEG C, 100% water vapour
Aging 17 hours, being then evaluated on small fixed fluidized bed unit, reaction raw materials is military mixed three
(character is shown in Table 2), reaction temperature 500 DEG C, agent weight of oil ratio is 5.92, weight (hourly) space velocity (WHSV) 16h-1.Its
In, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield；Total liquid yield=liquefaction
Gas yield+yield of gasoline+diesel yield；Density of propylene=propene yield/yield of liquefied gas.Evaluation result
It is shown in Table 5.
Comparative example 13～14
The catalytic performance of this comparative example explanation comparative catalyst.
According to the method for embodiment 17, use same raw oil to carry out catalytic cracking, evaluate comparative example
Reference catalyst DC21 of preparation～DC22, evaluation result is shown in Table 5.
Table 5 evaluation result
* in table 5, % is weight %.
By table 5 visible (comparing with comparative example), the heavy oil of the Cracking catalyst that the present invention provides converts
Ability strengthens, and gasoline yield improves, and total liquid yield increases, liquefied gas yield increases, propylene in liquefied gas
Concentration significantly improves, and coke yield reduces.The modified beta zeolite that the visible present invention obtains has stronger
Heavy oil conversion performance and Propylene Selectivity.
Embodiment 21
4.2Kg Kaolin is mixed making beating with 19.8Kg decationized Y sieve water, adds 3.2Kg and intend thin water
Aluminum stone, is 3.5 with dilute hydrochloric acid regulation slurry pH value, stands aging 1 in 60 DEG C after stirring 30 minutes
Hour, add 3.7Kg Alumina gel, after stirring, add and boiled by the DASY (2.0) of 3.7Kg
Stone and 0.5Kg (butt) above-mentioned modified beta zeolite B21 and 9.0 kilograms of decationized Y sieve water making beating are formed
Serosity, average dispersion 30 minutes, the serosity spray drying forming that will obtain is little in 550 DEG C of roastings 2
Time, obtain Cracking catalyst C25 that the present invention provides.The composition of C25 is shown in Table 6.
Embodiment 22
After 3.9Kg Kaolin is mixed with 6.6Kg decationized Y sieve water making beating, add 16.7Kg acidifying and intend
Boehmite and 4.7Kg Alumina gel, stir 60 minutes, adds by DASY (2.0) zeolite of 2.4Kg
The slurry formed with 2.0Kg (butt) above-mentioned modified beta zeolite B21 and 9.0 kilograms of decationized Y sieve water making beating
Liquid, after stirring 60 minutes, the serosity spray drying forming that will obtain, in 600 DEG C of roastings 1.5 hours,
Obtain Cracking catalyst C26 that the present invention provides.The composition of C26 is shown in Table 6.
Embodiment 23
After 4.2Kg Kaolin is mixed with 9.0Kg decationized Y sieve water making beating, add 3.2Kg acidifying and intend
Boehmite and 3.7Kg Alumina gel, stir 60 minutes, is subsequently adding and is boiled by the PREHY of 3.8Kg
The slurry that stone and 0.5Kg (butt) above-mentioned modified beta zeolite B22 and 8.0 kilograms of deionized water making beating are formed
Liquid, after stirring 60 minutes, the serosity spray drying forming that will obtain, in 500 DEG C of roastings 3 hours,
Obtain Cracking catalyst C27 that the present invention provides.The composition of C27 is shown in Table 6.
Embodiment 24
3.9Kg Kaolin is mixed making beating with 22.0Kg decationized Y sieve water, adds 16.7Kg and intend thin
Diaspore, is 3.0 with dilute hydrochloric acid regulation slurry pH value, stands aging 2 in 60 DEG C after stirring 60 minutes
Hour, add 4.7Kg Alumina gel, after stirring, add by 2.2Kg PREHY zeolite and
The serosity that 2.0Kg (butt) above-mentioned modified beta zeolite B22 and 8.0 kilograms of deionized water making beating are formed,
Average is disperseed 30 minutes, the serosity spray drying forming that will obtain, in 550 DEG C of roastings 1 hour,
Cracking catalyst C28 provided to the present invention.The composition of C28 is shown in Table 6.
Comparative example 15
Catalyst is prepared, except for the difference that with modified beta zeolite DB21 generation according to method described in embodiment 21
For modified beta zeolite B21.Finally obtain comparative catalyst DC23.The composition of DC23 is shown in Table 6.
Comparative example 16
Catalyst is prepared, except for the difference that with modified beta zeolite DB22 generation according to method described in embodiment 24
For modified beta zeolite B22.Obtain comparative catalyst DC24.The composition of DC24 is shown in Table 6.
The composition of table 6 catalyst
Embodiment 25～28
The catalytic performance of the Cracking catalyst that this embodiment explanation present invention provides.
Catalyst C25～C28 is carried out in advance on fixed bed aging equipment 800 DEG C, 100% water vapour
Aging 17 hours, being then evaluated on small fixed fluidized bed unit, reaction raw materials is military mixed three
(character is shown in Table 2), reaction temperature 500 DEG C, agent weight of oil ratio is 5.92, and weight (hourly) space velocity (WHSV) is 16h-1。
Evaluation result is shown in Table 7.
Comparative example 17～18
The catalytic performance of this comparative example explanation comparative catalyst.
According to the method for embodiment 25, use same raw oil to carry out catalytic cracking, evaluate comparative example
Reference catalyst DC23 of preparation～DC24, evaluation result is shown in Table 7.
Table 7 evaluation result
From table 7, the Cracking catalyst that the present invention provides have considerably higher heavy oil conversion performance,
Having higher conversion ratio, total liquid yield substantially increases, and yield of liquefied gas improves, the propylene in liquefied gas
Concentration significantly improves, and propene yield improves.
Claims (15)
1. a catalytic cracking catalyst, on the basis of the weight of described catalytic cracking catalyst, bag
Containing 10 weight %～the y-type zeolite of 80 weight %, 1 weight %～the modified beta zeolite of 50 weight %, 5 weight
%～the clay of 70 weight % and 5 weight %～the heat-resistant inorganic oxide of 60 weight %；Wherein said modified β
The anhydrous chemical expression of zeolite, is calculated as with oxide mass: (0～0.2) Na2O (0.5～15)
MO2(0.5～15) RE2O3(0.5～15) Al2O3(60～98) SiO2, wherein M is selected from Group IVB
One or more in metal.
2. according to the catalytic cracking catalyst described in claim 1, it is characterised in that described urges
Agent contains the described modified β boiling of 10 weight %～the y-type zeolite of 60 weight %, 2 weight %～30 weight %
Stone, 5 weight %～the clay of 50 weight % and 5 weight %～the heat-resistant inorganic oxide of 50 weight %.
3. according to the catalytic cracking catalyst described in claim 1 or 2, it is characterised in that described in change
The anhydrous chemical expression of property β zeolite, is calculated as with oxide mass: (0～0.2) Na2O (1～10)
MO2(1～10) RE2O3(1～10) Al2O3(70～95) SiO2, wherein M is selected from Group IVB metal
In one or more.
4. a preparation method for catalytic cracking catalyst, including, prepare modified beta zeolite, by Y
Type zeolite, prepared modified beta zeolite, clay, heat-resistant inorganic oxide binding agent and water mixing
Making beating, the step of spray drying；Wherein, the preparation method of described modified beta zeolite includes walking as follows
Rapid:
(1) solution of sodium form β zeolite rare earths salt or rare-earth salts and inorganic ammonium salt is carried out ion
Exchange, then filters, washs, and in 300～700 DEG C, 0～100% roasting under water vapour, obtains dilute
The β zeolite of land reform, the sodium oxide content in described rare earth modified β zeolite is not higher than 0.2 weight %；
(2) the rare earth modified zeolite that step (1) obtains is impregnated IV B metal in organic solvent；
(3) β zeolite step (2) obtained obtains in 350～800 DEG C of roastings or by step (2)
β Zeolite dehydration, then in 350～800 DEG C of roastings；
(4) with aqueous acid contact procedure (3) gained β zeolite, in aqueous acid, acid is dense
Degree is with H+It is calculated as 0.1～2.0mol/L；β zeolite after contact is washed, optionally drying, optional roasting,
Obtain modified beta zeolite.
The most in accordance with the method for claim 4, it is characterised in that step is having described in (2)
Machine solvent impregnates IV B metal include: by IV B race metallic compound and the mixture of organic solvent and institute
State the rare earth modified β zeolitic contact that step (1) obtains, stir 0.5～24 hour or to stand 0.5～24 little
Time, the rare earth modified β zeolite (in terms of butt) that wherein step (1) obtains is consolidated with organic solvent
Liquor ratio is 1:(0.5～5) weight ratio；Described impregnating metal in organic solvent, the process of optionally drying
Carry out one or many.
The most in accordance with the method for claim 4, it is characterised in that described organic solvent be alkane,
One or more in aromatic hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane.
The most in accordance with the method for claim 6, it is characterised in that described organic solvent is just own
Alkane, hexamethylene, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, trichlorine
One or more in methane etc..
The most in accordance with the method for claim 6, it is characterised in that the standard of described organic solvent
Boiling point is 40～100 DEG C.
The most in accordance with the method for claim 4, it is characterised in that the water of described organic solvent contains
Amount is less than 5 weight %.
The most in accordance with the method for claim 4, it is characterised in that ion described in step (1)
It is exchanged for: according to rare-earth salts (with RE2O3Meter): ammonium salt: sodium form β zeolite (in terms of butt): go from
The weight ratio of sub-water=0.01～0.15:0～0.6:1:1～50 by zeolite, ammonium salt, rare-earth salts and
Water mixes, and stirs 0.5～5 hour, then filtration, roasting at room temperature～100 DEG C.
11. in accordance with the method for claim 4, it is characterised in that in step (3), described roasting
In dry air or in inert atmosphere, the temperature of roasting is 350～650 DEG C, roasting time be 0.5～
5 hours.
12. in accordance with the method for claim 4, it is characterised in that acid described in step (4)
With H in aqueous solution+The acid concentration of meter is 0.5～2mol/L.
13. according to the method described in any one of claim 4～12, it is characterised in that described organic molten
The water content of agent is less than 1 weight %.
14. in accordance with the method for claim 5, it is characterised in that the change of IV described B race metal
Compound includes the compound of titaniferous and/or the compound containing zirconium.
15. in accordance with the method for claim 4, it is characterised in that sintering temperature in step (1)
Being 450～650 DEG C, roasting time is 1～6 hour.
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