CN104549453B - Zirconium-containing beta zeolite and preparation method thereof - Google Patents
Zirconium-containing beta zeolite and preparation method thereof Download PDFInfo
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Abstract
The invention discloses zirconium-containing beta zeolite and a preparation method thereof. Based on mass of oxide, the anhydrous chemical composition of the zirconium-containing beta zeolite is (0-0.2)Na2O.(0.5-15)ZrO2.(0-10)MxOy.(0.5-15) Al2O3.(60-97)SiO2, wherein M is one selected from Ti, Cr, Fe and Ga; x refers to atom number of M; y refers to a number meeting M oxidation state. The preparation method of the zirconium-containing beta zeolite comprises the following steps: using ammonium ions to exchange Na beta zeolite to enable the content of sodium oxide therein to be not higher than 0.2% by weight, in the existence of vapor, roasting the substance, introducing Zr or Zr and one metal element selected from Ti, Cr, Fe and Ga into an organic solvent, roasting, and then acidizing the materials. The modified beta zeolite is higher in hydrocarbon cracking capacity and propylene productivity.
Description
Technical field
The present invention relates to a kind of modified beta zeolite and preparation method thereof, it is furtherly to be related to a kind of modified β containing zirconium
Zeolite and preparation method thereof.
Background technology
β zeolite is synthesized equal to 1967 first by the wadlinger of mobil company, discloses to higgins in 1988 etc.
Its distinctive Three Dimensions Structure, it be uniquely a kind of have intersect 12-membered ring's channel system silica-rich zeolite, parallel to
(001) 12 yuan of annular apertures of the one-dimensional channels of crystal face are 0.75～0.57nm, another two-dimensional channel parallel with (100) crystal face
12 yuan of annular apertures be 0.65～0.56nm.Due to the particularity of its structure, have acid catalysiss characteristic and structure selectivity concurrently, and
There is high heat and hydrothermal stability and anti-wear performance, in a series of catalytic reactions, show good heat and hydrothermally stable
Property, acid resistance, anti-coking and catalysis activity, have therefore developed rapidly in recent years as a kind of new catalysis material.Through changing
Property and can be applicable to be hydrocracked after loading some metallic elements, hydro-isomerization, petroleum refining and the petrochemical industry such as catalytic cracking
In.
At present, the synthesis of metal-modified β zeolite adopts hydrothermal synthesis method mostly, synthesizes the mistake of β zeolite in conventional hydrothermal
In journey, corresponding metallic compound is added in synthetic system.Jp10316417 discloses a kind of ti- β zeolite of being directly synthesized
Method, with butyl titanate as titanium source, silicon source adopts silester, Ludox or gas phase silica gel, is formed and relaxes colloidal sol, with
Teaoh is template, then passes through more than 150 DEG C hydrothermal treatment consists and synthesizes ti- β zeolite.Gained ti- β zeolite can be applicable to various
Catalytic reaction.Cn101353169a also discloses that a kind of synthetic method of ti- β zeolite, and the method includes the steps of: (1) presses
According to sio2: tio2: alcohol=1: (0.01～0.05): the mol ratio of (4.0～15.0) is by the mixing of esters of silicon acis, titanate esters and butanol all
Even, then it is added thereto to sodium hydroxide solution, and after reaction at room temperature～120 DEG C, roasting obtains water silicon sodium stone；(2) press
According to sio2: template: water=1: (0.1～1.0): the mol ratio of (2.0～8.0) is by after the mixing of water silicon sodium stone, template and water
In 120～170 DEG C, crystallization 2～15 days, obtain the former powder of HTS with bea framing structure；(3) in acid pickling step (2)
The former powder of HTS obtaining；(4) the product roasting after pickling is obtained ti- beta-molecular sieve product, the ti- beta-molecular sieve of synthesis
There is relative crystallinity high, fault of construction is few, heat stability is high, the feature of nanocrystal yardstick.Cn1785520a discloses one
β type Si-Al molecular sieve kind containing bi it is characterised in that this Si-Al molecular sieve contain bi and optionally contain selected from b, sn, sb, pb,
One or more of po, zn, mn, ti, v, w element hetero atom, wherein b, sn, sb, pb, po, zn, mn, ti, v, w atom
The mol ratio of summation/bi atom is 0～0.2, sio2The mol ratio of/al is 5～100, sio2The mol ratio of/bi is 10～250,
This molecular sieve is by direct hydrothermal synthesis method, described element to be attached in molecular sieve, and this molecular sieve can be urged as oxidation reaction
Agent.
With respect to hydrothermal synthesis method, the preparation process is simple of liquid-phase ion exchange and infusion process is it is easier to implement.
Cn1098028a discloses a kind of beta-zeolite catalyst for toluene disproportionation and alkylated reaction, and this catalyst is by 10 weight %～90
The β zeolite of weight %, the binding agent of 5 weight %～90 weight %, 0.05 weight %～5 weight % selected from the metals such as ni, co, cu, ag, sn, ga institute group
Become, wherein metal adopts infusion process to load.Cn1043450a proposes a kind of use potassium and phosphorus method of modifying to β zeolite, Ke Yishi
Soak the β zeolite after dealuminzation with neutral or the exchange of alkalescence potassium salt, weakly acidic pH microcosmic salt buffer solution；Can also be to be contained with weakly acidic pH
Potassium, microcosmic salt buffer soak the β zeolite after dealuminzation.Modified β zeolite contains the potassium and 0.01～0.5% of 0.5～2.5 weight %
The phosphorus of weight %, has more preferably hysomer activity.
Cn1872685a discloses a kind of modified beta zeolite it is characterised in that the anhydrous chemical expression of this β zeolite, with oxygen
The quality of compound is calculated as (0～0.3) na2O (0.5～10) al2o3(1.3～10) p2o5(0.7～15) mxoy(70～
97)sio2, wherein, m be selected from one of fe, co, ni, cu, mn, zn and sn, wherein said metal ion be by dipping or
Ion-exchange process is incorporated in zeolite.This zeolite is applied in catalytic cracking, can be used as the activearm of catalyst or auxiliary agent
Point.But the modified y zeolite containing zirconium is prepared with the method disclosed in the patent, not high for its cracking activity of catalytic cracking.
Content of the invention
It is an object of the invention to provide a kind of be applied to modified beta zeolite of catalytic cracking reaction and preparation method thereof.
The modified beta zeolite that the present invention provides, modified with other metal m by zr or zr, its anhydrous chemical expression, to aoxidize
Amount of substance is calculated as: (0～0.2) na2O (0.5～15) zro2(0～10) mxoy(0.5～15) al2o3(60～97)
sio2, wherein m is selected from one of ti, cr, fe, ga, and x represents the atomic number of m, and y represents meeting needed for m oxidation state
Number.
The modified beta zeolite that the present invention provides, its anhydrous chemical expression, the preferred scope with oxidation material gauge is: (0
～0.2) na2O (1～10) zro2(0～8) mxoy(1～10) al2o3(70～95) sio2.
The present invention provides a kind of preparation method of described modified beta zeolite, comprising:
(1) sodium form β zeolite is carried out ammonium ion exchange, make the sodium oxide content in β zeolite be not higher than 0.2 weight %, optionally
Roasting；
(2) the zeolite impregnating metal in organic solvent that step (1) is obtained；
(3) the β zeolite obtaining step (2) is in 350～800 DEG C of roastings or the β Zeolite dehydration that obtains step (2), so
After 350～800 DEG C of roastings, preferably roasting time is not less than 0.5 hour, for example, 0.5～5 hour；
(4) use aqueous acid contact procedure (3) gained β zeolite, the concentration of acid is calculated as 0.1～2.0mol/l with h+；
(5) roasting is at least under 350～800 DEG C, 1～100% water vapour for the β zeolite after contacting step (3) gained with acid
0.5 hour such as 0.5～5 hour, obtain modified beta zeolite.
Sodium form β zeolite is carried out ammonium ion exchange described in (1) by step, makes the sodium oxide content in β zeolite be not higher than 0.2
Weight %, then carries out roasting or does not carry out roasting.Wherein, if carrying out roasting, the sintering temperature of described roasting is 350～800
DEG C, roasting time more than 0.5 hour, for example, 0.5～8 hour or be 0.5～5 hour；Described roasting is preferably in 350～
800 DEG C, at least 0.5 hour under 1～100 volume % water vapour atmosphere, for example, 0.5～8 hour, preferably sintering temperature be 450～
650 DEG C, roasting time is 1～6 hour.Described ion exchange can be: according to zeolite: ammonium salt: water=1:(0.1～1): (5～
15) weight, than mixing, stirs 0.5～5 hour, then filtration, optionally drying, optional roasting (this at room temperature～100 DEG C
Roasting in bright referred to as exchange process), this process can be repeated once multiple, makes na on zeolite2O content is not more than 0.2 weight
Amount %；When described exchange process carries out multiple, on carrying out once before exchange process by molecular sieve roasting or not roasting, carry out
Roasting, such as 350～700 DEG C of described sintering temperature, roasting time such as 1～5 hour.The water of the zeolite that step (1) obtains
Content is preferably more than 5% weight, preferably more than 3 weight %.
The zeolite impregnating metal in organic solvent described in step (2) obtaining step (1), including the compound with zr
Or the compound of metal of the compound with zr and one of ti, cr, fe, ga and the mixture of organic solvent and above-mentioned steps
(1) the β zeolitic contact obtaining, keeps more than 0.5 hour, is generally stirring or standing 0.5～24 hour example of (not stirring) holding
As 0.5～12 hour, preferably keep 0.5～24 hour such as 0.5～12 hour under agitation, impregnated.Can be by once
Or repeatedly it is immersed in the modified metal described in introducing in β zeolite, can also be dried or moist, wherein after impregnating each time
Impregnate each time, can be using excessive infusion process or equivalent impregnation method (equi-volume impregnating), preferably equivalent impregnation method；For example, institute
The zeolite impregnating metal in organic solvent that step (1) is obtained stated, the process of optionally drying can carry out one or many,
If described process is carried out once, preferably it is dried, if described process carries out repeatedly, preferably carrying out described mistake for the last time
Journey is dried.Impregnating metal for example can use zirconium compoundss or zirconium chemical combination to the zeolite that step (1) is obtained in organic solvent
The zeolite that thing is obtained with step (1) with the mixture of organic solvent with the compound of one of ti, cr, fe or ga mixes.Described zr
Compound can be the organo-metallic compound of zirconium or the inorganic compound of zirconium, described zirconium compoundss such as Zirconium tetrachloride., sulfur
One or more of sour zirconium, zirconium nitrate, zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide.The chemical combination of one of described ti, cr, fe or ga
Thing can be selected from their inorganic salt and/or their organic compound, described inorganic salt such as sulfate, nitrate, chlorate
One of, the compound of such as titanium can selected from one of butyl titanate, titanyl sulfate, Titanium Nitrate, titanium tetrachloride or
Multiple, the compound of described chromium can be selected from one or more of chromic nitrate, Chlorizate chromium, chromic sulfate, chromic anhydride；The change of described ferrum
Compound can be selected from one or more of iron sulfate, ferric nitrate, iron chloride, ferrous sulfate, ferrous chloride, the change of described gallium
Compound can be selected from one or more of Ganite (Fujisawa)., gallium chloride, potassium sulfate；The compound of described zr, ti, cr, fe or ga
In can contain or not contain water of crystallization.Described organic solvent can be alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, in halogenated alkane
One or more, preferably 40～100 DEG C of the normal boiling point of described organic solvent, the preferred normal hexane of described organic solvent, ring
One or more of hexane, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, chloroform etc..Described have
The water content of machine solvent is less than 5 weight %, and preferably more than 3 weight % are for example less than 1 weight %.
In step (3), roasting is carried out to the zeolite of the impregnating metal obtained by step (2), described sintering temperature be 350～
800 DEG C, roasting 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
The burning time is 1～4 hour.The β zeolite roasting in step (3), step (2) being obtained or dry roasting；Sintering temperature is 350
～800 DEG C, roasting time is more than 0.5 hour, for example, 0.5～5 hour.Described calcination atmosphere is dry air, indifferent gas
Body, preferably noble gases.Described noble gases such as nitrogen, helium, in described dry air, vapour content is less than 0.5 body
Long-pending %, for example, be less than 0.3 volume %.If the product obtaining in step (2), without drying, preferably includes to do before described roasting
Dry step, to reduce the water content in zeolite, described drying can be zeolite that step (2) is obtained in temperature for room temperature～
100 DEG C of drying times are 4～48 hours.
In the preparation method of modified beta zeolite provided by the present invention, in step (4), use aqueous acid process step (3)
Gained β zeolite, is contacted with acid solution including the β zeolite obtaining described step (3) and for example to obtain described step (3)
β zeolite is mixed with acid solution, then filters, washs and optional drying；The temperature of contact is room temperature～100 DEG C, time of contact
It is preferably not less than 0.2 hour, preferably 0.5～5 hour, solid-to-liquid ratio (mass ratio of zeolite and acid solution) was 1:5～20, and sour is dense
Degree is with h+It is calculated as 0.1～2mol/l, preferably 0.5～2mol/l such as 0.5～1.5mol/l.Acid described in step (4) is selected from
One or more of hydrochloric acid, sulphuric acid, nitric acid, oxalic acid, acetic acid, formic acid, citric acid, preferably hydrochloric acid, oxalic acid, formic acid, citric acid
One or more of.For example, 15～40 DEG C of room temperature.Described washing can wash the zeolite after contacting with acid to wash with water
Remove free acid, be then dried or moist, drying using drying or can be spray-dried, to reduce the water content in zeolite.
The β zeolite roasting in step (5) obtaining step (4), obtains modified beta zeolite.The temperature of roasting is 350～800 DEG C
Such as 450～660 DEG C, 1～100% water vapour atmosphere preferably 100% water vapour atmosphere, roasting time be at least 0.5 hour for example
Roasting time is 0.5～5 hour.
In the modified beta zeolite that the present invention provides, zirconic content is 0.5～15 weight %, described other metal-oxide
Content be 0～10 weight %, the content of aluminium oxide is 0.5～15 weight %, and the content of silicon oxide is 60～97 weight % such as 65
～97 weight %, the content of sodium oxide is 0～0.2 weight %.Further, described zirconic content is 1～10 weight %, described
The content of other modified metals is 0～8 weight % such as 0.5～8 weight %, and the content of aluminium oxide is 1～10 weight %, silicon oxide
Content be in 70～95, to carry % such as 75～95 weight %, the content of sodium oxide is 0～0.2 weight %.
Compared with prior art, the modified beta zeolite that the present invention provides has a higher hydrothermal stability, higher specific surface
Amass and pore volume, can apply in catalytic cracking of hydrocarbon, as the active component of catalyst or auxiliary agent.The present invention provides
Modified beta zeolite, is to be modified with one of ti, cr, fe, ga through zr or zr, and its cracking hydrocarbon ability significantly improves, simultaneously
Improve the productivity of propylene of crackate.
Specific embodiment
The following examples illustrate the present invention further it is intended to help reader to more fully understand the reality of the present invention
Matter is located and the beneficial effect brought, but should not be construed as to the present invention can practical range any restriction.
Prepare raw materials used in catalyst being described as follows: Kaolin is produced by Kaolin of Suzhou company, solid content is 76 weights
Amount %；Alumina content in Alumina gel is 21.5 weight %；Boehmite is produced by Shandong Aluminum Plant, and solid content is 62.0 weights
Amount %；Acidification pseudo-boehmite solid content is 12.0 weight %, and hydrochloric acid is acidified, and during acidifying, sour (hcl) with the mol ratio of aluminium oxide is
0.15；Super steady y zeolite dasy (2.0) used is produced for Shandong catalyst plant, solid content 94.7%, and lattice constant is
, in terms of weight percent content, na2O content is 1.3%, re2o3Content is 2.5%；Super steady y zeolite dasy (6.0) is urged for Shandong
Agent factory produces, solid content 84.8%, and lattice constant is, in terms of weight percent content, na2O content is 1.6%,
re2o3Content is 6.2%；Phosphorous y zeolite prehy produces for Shandong catalyst plant, solid content 92.4%, and lattice constant is
, in terms of weight percent content, na2O content is 1.5%, re2o3Content is 8.5%.Remaining reagent is by Chinese medicines group chemical reagent
Company limited produces, and it is pure that specification is analysis.Sodium form β zeolite, sinopec catalyst asphalt in Shenli Refinery produces, sio2/al2o3=25
(mol ratio), 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
Account for 75 weight %), mix making beating with 3000g deionized water and 45g ammonium chloride, stir 2 hours at 80 DEG C, then filter, repeat above-mentioned
Process 3 times, makes the na in zeolite2O content is less than 0.2 weight %, roasting 2 hours under 600 DEG C, 100% water vapour, obtains ammonium and hands over
β zeolite after changing, is designated as a-1；
By 52.3g zirconium nitrate zr (no3)4·5h2O is dissolved in 150g ethanol (analysis is pure) and obtains impregnation liquid, then will be above-mentioned
β zeolite a-1 after the exchange of impregnation liquid and ammonium is mixed homogeneously, and stands 24 hours, dries 24 hours for 100 DEG C, nitrogen atmosphere, 500
At DEG C, roasting 4 hours, are designated as ac-1；
β zeolite ac-1 after above-mentioned roasting is added to inorganic acid aqueous solution (dilute salt that 2000g acid concentration is 1.0mol/l
Acid solution) in, stir 3 hours at 80 DEG C, then filter, be washed with deionized and (wash the water yield for molecular sieve butt weight
15 times), filter, filter cake is placed in 600 DEG C, roasting 1 hour in 100% water vapour, obtains the modified beta zeolite of present invention offer, note
For b1.Element chemistry consists of 0.1na2o·9.9zro2·5.6al2o3·84.4sio2(weight composition).
By modified beta zeolite b1 aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detected before its hydro-thermal with xrd,
Relative crystallinity afterwards, and calculate crystallization reservation degree, crystallization reservation degree is the relative crystallinity after hydrothermal aging and hydrothermal aging
The ratio of front relative crystallinity.Its data is listed in table 1.
Embodiment 2
Take 200g sodium form β zeolite (ibid), mix making beating with 2000g deionized water and 45g ammonium chloride, stir 1 at 80 DEG C
Hour, then filter, repeat said process 3 times, roasting 2 hours under 650 DEG C, 100% water vapour, obtain the β boiling after ammonium exchanges
Stone a-2；Na in zeolite a-22O content is less than 0.2 weight %, water content 1 weight %；
18.9g zirconium iso-propoxide is dissolved in 450g ethanol, then resulting solution is mixed with the β zeolite a-2 after ammonium exchange
Uniformly, stir 24 hours, dry 24 hours for 100 DEG C, roasting 3 hours at nitrogen atmosphere, 550 DEG C, obtain the β zeolite after roasting
ac-2；
β zeolite ac-2 after above-mentioned roasting is added in the oxalic acid aqueous solution that 1500g acid concentration is 2.0mol/l, 90
DEG C continue stirring 1 hour, then filter, be washed with deionized (the washing water yield is 15 times of molecular sieve butt weight), take out
Filter cake is placed in 500 DEG C, roasting 2 hours in 100% water vapour, obtains the modified beta zeolite of present invention offer, is designated as b2.Element
Consist of 0.05na2o·3.8zro2·7.0al2o3·89.2sio2(weight composition).
By modified beta zeolite b2 aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detected before its hydro-thermal with xrd,
Relative crystallinity afterwards, and calculate crystallization reservation degree, crystallization reservation degree is the relative crystallinity after hydrothermal aging and hydrothermal aging
The ratio of front relative crystallinity.Its data is listed in table 1.
Embodiment 3
Take 200g sodium form β zeolite (ibid), mix making beating with 2000g deionized water and 60g ammonium chloride, stir 3 at 90 DEG C
Hour, then filter, repeat said process 2 times, na on zeolite2O content is less than 0.2 weight %, in 500 DEG C of roastings 5 hours, obtains
β zeolite a-3 after ammonium exchange；
By 10.5g zirconium nitrate zr (no3)4·5h2O is dissolved in 200g ethanol, then hands over above-mentioned solution with obtained ammonium
β zeolite mix homogeneously after changing, stands 12 hours post-dryings；Zeolite after drying with by 25.6g butyl titanate and 200g second
The impregnation liquid mixing of alcohol composition, stands 12 hours, then dries 24 hours in 100 DEG C, roasting 2 is little at nitrogen atmosphere, 600 DEG C
When, obtain the β zeolite after roasting, be designated as ac-3；
β zeolite ac-3 after above-mentioned roasting is added in the aqueous hydrochloric acid solution that 1000g acid concentration is 0.5mol/l, 80
DEG C stirring 3 hours, then filters, is washed with deionized (the washing water yield is 20 times of molecular sieve butt weight), take out filter cake
It is placed in 500 DEG C, roasting 3 hours in 100% water vapour, obtain the modified beta zeolite b3 of present invention offer, element chemistry consists of
0.1na2o·2.0zro2·4.1tio2·6.0al2o3·87.8sio2(weight composition).
By modified beta zeolite b3 aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detected before its hydro-thermal with xrd,
Relative crystallinity afterwards, and calculate crystallization reservation degree, crystallization reservation degree is the relative crystallinity after hydrothermal aging and hydrothermal aging
The ratio of front relative crystallinity.Its data is listed in table 1.
Embodiment 4
Take 200g sodium form β zeolite (ibid), mix making beating with 2000g deionized water and 45g ammonium sulfate, be warmed up to 85 DEG C and stir
Mix 3 hours, then filter, repeat said process 3 times, the na to zeolite2O content is less than 0.2 weight %, in 500 DEG C of roastings 1 hour,
Obtain the β zeolite a-4 after ammonium exchanges；
By 15.7g zirconium oxychloride zrocl2·8h2O is dissolved in 250g ethanol, after then exchanging resulting solution with above-mentioned ammonium
β zeolite mixing, stand 12 hours, dry；Zeolite after drying with by 15.2g ferric nitrate fe (no3)3·9h2O and 250g second
The impregnation liquid mixing of alcohol composition, standing is soaked for 12 hours, then dries 24 hours in 100 DEG C, at nitrogen atmosphere, 450 DEG C
Roasting 3 hours；Obtain the β zeolite ac-4 after roasting；
β zeolite ac-4 after above-mentioned roasting is added in the inorganic acid aqueous solution that 1000g acid concentration is 0.5mol/l, mixes
Close uniformly, stir 2 hours at 80 DEG C, then filter, be washed with deionized and (wash the water yield for the 10 of molecular sieve butt weight
Times), take out filter cake and be placed in 500 DEG C, roasting 2 hours in 100% water vapour, obtain the modified beta zeolite b4 of present invention offer, it is no
Water chemistry consists of 0.06na2o·4.1zro2·1.9fe2o3·3.8al2o3·90.2sio2(weight composition).
By modified beta zeolite b4 aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detected before its hydro-thermal with xrd,
Relative crystallinity afterwards, and calculate crystallization reservation degree, crystallization reservation degree is the relative crystallinity after hydrothermal aging and hydrothermal aging
The ratio of front relative crystallinity.Its data is listed in table 1.
Embodiment 5
Take 200g sodium form β zeolite (ibid), mix making beating with 3000g deionized water and 50g ammonium chloride, be warmed up to 75 DEG C and stir
Mix 3 hours, then filter, repeat said process 3 times, the na to zeolite2O content is less than 0.2 weight %, in 600 DEG C, 100% water steaming
Roasting 1 hour under vapour.Obtain the β zeolite a-5 of ammonium exchange；
By 28.3g zirconium iso-propoxide and 9.4g chromic nitrate cr (no3)3·9h2O is dissolved in 500g hexamethylene, then will be above-mentioned molten
β zeolite a-5 after the exchange of liquid homogeneous impregnation ammonium, stirs 6 hours, dries 24 hours in 100 DEG C, roasts at nitrogen atmosphere, 650 DEG C
Burn 1 hour, obtain the β zeolite ac-5 after roasting；
β zeolite ac-5 after above-mentioned roasting is added in the oxalic acid aqueous solution that 2000g acid concentration is 1.5mol/l, mixing
Uniformly, it is warmed up to 90 DEG C and continues stirring 1 hour, then filter, be washed with deionized that (the washing water yield is molecular sieve butt weight
20 times), take out filter cake and be placed in 600 DEG C, roasting 2 hours in 100% water vapour.The modified beta zeolite b5 of present invention offer is provided；
Element chemistry consists of 0.1na2o·5.8zro2·1.9cr2o3·2.7al2o3·89.5sio2(weight composition).
By modified beta zeolite b5 aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detected before its hydro-thermal with xrd,
Relative crystallinity afterwards, and calculate crystallization reservation degree, crystallization reservation degree is the relative crystallinity after hydrothermal aging and hydrothermal aging
The ratio of front relative crystallinity.Its data is listed in table 1.
Embodiment 6
Take 200g sodium form β zeolite (ibid), mix making beating with 2000g deionized water and 45g ammonium chloride, be warmed up to 80 DEG C and stir
Mix 1 hour, then filter, repeat said process 3 times, the na to zeolite2O content is less than 0.2 weight %, in 500 DEG C, 100% water steaming
Roasting 3 hours under vapour, obtain the β zeolite after ammonium exchanges；By 41.8g zirconium nitrate zr (no3)4·5h2O and 6.7g Ganite (Fujisawa). ga
(no3)3·9h2O is dissolved in 200g ethanol, then by the β zeolite after the exchange of above-mentioned solution homogeneous impregnation ammonium, stands 24 hours, in
Dry 24 hours for 100 DEG C, roasting 2 hours at nitrogen atmosphere, 500 DEG C, obtain the β zeolite after roasting；By the β boiling after gained roasting
Stone is added in the aqueous citric acid solution that 3000g acid concentration is 1.0mol/l, mix homogeneously, is warmed up to 80 DEG C of continuation stirrings 2 little
When, then filter, be washed with deionized (the washing water yield is 20 times of molecular sieve butt weight), take out filter cake be placed in 550 DEG C,
Roasting 3 hours in 100% water vapour.The modified beta zeolite of present invention offer is provided.Element chemistry consists of 0.1na2o·
8.0zro2·0.9ga2o3·8.8al2o3·82.2sio2(weight composition).
By modified beta zeolite aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detect that its hydro-thermal is forward and backward with xrd
Relative crystallinity, and calculate crystallization reservations degree, before crystallization reservations degree is for the relative crystallinity after hydrothermal aging and hydrothermal aging
Relative crystallinity ratio.Its data is listed in table 1.
Comparative example 1
Take 200g sodium form β zeolite (ibid), mix making beating with 2000g deionized water and 45g ammonium chloride, be warmed up to 80 DEG C and stir
Mix 1 hour, then filter, repeat said process 3 times, the na to zeolite2O content is less than 0.2 weight %, in 600 DEG C, 100% water steaming
Roasting 1 hour under vapour.Continue above-mentioned ammonium modified beta zeolite with, after the making beating of 2000g deionized water, adding 45g ammonium chloride, in 80
DEG C exchange 1 hour, filtration washing roasting 1 hour under 600 DEG C, 100% water vapour, obtain modified beta zeolite.Element chemistry group
Become 0.05na2o·5.8al2o3·94.2sio2(weight composition).
By modified beta zeolite aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detect that its hydro-thermal is forward and backward with xrd
Relative crystallinity, and calculate crystallization reservations degree, before crystallization reservations degree is for the relative crystallinity after hydrothermal aging and hydrothermal aging
Relative crystallinity ratio.Its data is listed in table 1.
Comparative example 2
According to the method for embodiment 1, except for the difference that, by 52.3g zirconium nitrate zr (no3)4·5h2O is dissolved in 150g deionized water
In.Finally obtain modified beta zeolite, element chemistry consists of 0.1na2o·9.7zro2·5.4al2o3·84.8sio2(weight group
Become).
By modified beta zeolite aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detect that its hydro-thermal is forward and backward with xrd
Relative crystallinity, and calculate crystallization reservations degree, before crystallization reservations degree is for the relative crystallinity after hydrothermal aging and hydrothermal aging
Relative crystallinity ratio.Its data is listed in table 1.
Comparative example 3
According to the method for embodiment 1, except for the difference that, the β zeolite after roasting is without the acid treatment of final step.Element
Consist of 0.3na2o·9.9zro2·5.9al2o3·83.9sio2(weight composition).
By modified beta zeolite aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detect that its hydro-thermal is forward and backward with xrd
Relative crystallinity, and calculate crystallization reservations degree, crystallization reservation degree for hydro-thermal old
Relative crystallinity after change and the ratio of the relative crystallinity before hydrothermal aging.Its data is listed in table 1.
Comparative example 4
According to the method for embodiment 3, except for the difference that: by 10.5g zirconium nitrate zr (no3)4·5h2O and 25.6g metatitanic acid four fourth
Ester is dissolved in 200g deionized water, with 12 hours roasting 2 hours under 500 DEG C, 100% water vapour of filter cake hybrid infusion, obtains
Modified beta zeolite.Element chemistry consists of 0.1na2o·1.8zro2·4.0tio2·7.7al2o3·86.4sio2.
By modified beta zeolite aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, detect that its hydro-thermal is forward and backward with xrd
Relative crystallinity, and calculate crystallization reservations degree, before crystallization reservations degree is for the relative crystallinity after hydrothermal aging and hydrothermal aging
Relative crystallinity ratio.Its data is listed in table 1.
The physicochemical data of table 1 modified beta zeolite
From table 1, (for example comparative example carries the modified beta zeolite that the modified beta zeolite that the present invention provides is obtained with existing method
For modified beta zeolite) compare, crystallization reservations degree significantly improve, show the present invention prepare modified beta zeolite there is higher hydro-thermal
Stability；The modified beta zeolite of present invention preparation has higher specific surface area and pore volume.
Embodiment 7～12
The modified beta zeolite that embodiment 7～12 explanation is provided using the present invention is used for stone as one of catalyst activity component
Impact in petroleum hydrocarbon catalytic cracking, to heavy oil conversion performance and productivity of propylene.
The modified beta zeolite of embodiment 1～6 preparation is carried out 800 DEG C, 100% water steaming respectively on fixed bed aging equipment
Aging 4 hours of vapour, then industrial poising agent and the shape-selective molecular sieve hzsm- with docp catalyst (production of Chang Ling catalyst plant)
5(silica alumina ratio 25) according to docp: modified beta zeolite: the ratio mix and convert of shape-selective molecular sieve=85:5:10 uniformly, respectively obtains and urges
Agent c1, c2, c3, c4, c5, c6.
Catalyst, appreciation condition: 500 DEG C of reaction temperature, weight are evaluated on catalytic cracking small fixed micro-reactor
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 5～8
The modified beta zeolite that comparative example 1～4 is obtained is that one of catalyst activity component is used for oil by comparative example 5～8 explanation
In hydrocarbon catalytic cracking, yield on c2～c4 alkene and selective affect.
According to the method for embodiment 7, prepare comparative catalyst dc1, dc2, dc3, dc4.
Catalytic cracking fixed bed micro- anti-on evaluate catalyst, appreciation condition is 500 DEG C of reaction temperature, oil ratio 2.94,
Catalyst inventory 5g, raw material oil nature is shown in Table 2.Evaluation result is shown in Table 3.
Table 2 raw material oil nature
Table 3 evaluation result
From table 3, compared with the β zeolite adding existing method to obtain, catalytic cracking catalyst adds the present invention
After the metal-modified β zeolite providing, in liquefied gas, density of propylene significantly improves, and heavy oil conversion ratio significantly improves, and productivity of propylene increases
Plus.
Embodiment 13
The modified beta zeolite b21(preparation method that the preparation present invention provides refers to embodiment 1).The element chemistry composition of b21
For 0.1na2o·5.2zro2·8.0al2o3·86.7sio2.
3.3kg Kaolin, 4.7kg Alumina gel and 8.0kg decationized Y sieve water are added in making beating tank and pull an oar, be subsequently adding
16.7kg acidification pseudo-boehmite, after stirring 60 minutes, adds dasy (6.0) zeolite (butt) of 4.1kg and 1.0kg(does
Base) serosity that formed of above-mentioned modified beta zeolite b21 and the making beating of 7.6 kilograms of deionized waters, homogenous disperse (stirring) 30 minutes, then
By the serosity obtaining spray drying forming, in 500 DEG C of roastings 2 hours, obtain Cracking catalyst c21 of present invention offer.C21's
Composition is shown in Table 4.
Embodiment 14
The method of reference implementation example 3 changes proportioning and prepares the modified beta zeolite b22 that the present invention provides.The element chemistry group of b22
Become 0.05na2o·3.8zro2·3.5tio2·5.6al2o3·87.1sio2.
Then according to the method for embodiment 13 prepares catalyst, except for the difference that replace b21 with modified beta zeolite b22.Obtain this
Cracking catalyst c22 that invention provides.The composition of c22 is shown in Table 4.
Embodiment 15
The modified beta zeolite b23(that the preparation present invention provides refers to embodiment 3).The element chemistry of b23 consists of
0.1na2o·6.1zro2·1.9fe2o3·8.4al2o3·83.5sio2.
Then according to the method for embodiment 13 prepares catalyst, except for the difference that replace b21 with modified beta zeolite b23.Obtain this
Cracking catalyst c23 that invention provides.The composition of c23 is shown in Table 4.
Embodiment 16
The method of reference implementation example 3 prepares the modified beta zeolite b24 that the present invention provides, except for the difference that, metal oxide-impregnated
When, by 10.5g zirconium nitrate zr (no3)4·5h2O is dissolved in 0.15kg ethylene glycol, then exchanges above-mentioned solution homogeneous impregnation ammonium
β zeolite afterwards, stands 12 hours post-dryings；Zeolite after drying uses 9.4g chromic nitrate cr (no again3)3·9h2O and 0.15kg second
The impregnation liquid of glycol composition carries out homogeneous impregnation, stands 12 hours roasting 2 hours under 550 DEG C, 100% water vapour.B24's
Element consists of 0.08na2o·2.0zro2·1.9cr2o3·7.8al2o3·88.3sio2.
Then according to the method for embodiment 13 prepares catalyst, except for the difference that replace b21 with modified beta zeolite b24.Obtain this
Cracking catalyst c24 that invention provides.The composition of c24 is shown in Table 4.
Embodiment 17
Take 2kg sodium form β zeolite (ibid), mix making beating with 15kg decationized Y sieve water and 0.4kg ammonium sulfate, be warmed up to 60 DEG C
Stirring 2 hours, then filters, and repeats said process, the na to zeolite2O content is less than 0.2 weight %, in 600 DEG C, 100% water vapour
Lower roasting 1 hour.By 157g zirconium oxychloride zrocl2·8h2O and 67g Ganite (Fujisawa). ga (no3)3·9h2O is dissolved in system in 2kg ethanol
Become impregnation liquid, then by the β zeolite after the exchange of above-mentioned solution impregnation ammonium, wherein dip time is standing 24 hours；
β zeolite ac-1 after above-mentioned roasting is added to inorganic acid aqueous solution (dilute salt that 20kg acid concentration is 1.0mol/l
Acid solution) in, stir 3 hours at 80 DEG C, then filter, be washed with deionized and (wash the water yield for molecular sieve butt weight
15 times), then roasting 2 hours under 650 DEG C, 100% water vapour, the modified beta zeolite b25 of present invention offer is provided.The unit of b25
Plain chemical composition is 0.1na2o·4.2zro2·2.0ga2o3·6.8al2o3·86.9sio2.
Then according to the method for embodiment 13 prepares catalyst, except for the difference that replace b21 with modified beta zeolite b25.Obtain this
Cracking catalyst c25 that invention provides.The composition of c25 is shown in Table 4.
Comparative example 9
Take 2kg sodium form β zeolite (ibid), mix making beating with 15kg decationized Y sieve water and 0.4kg ammonium sulfate, be warmed up to 80 DEG C
Stirring 1 hour, then filters, and repeats said process, the na to zeolite2O content is less than 0.2 weight %, in 600 DEG C, 100% water vapour
Lower roasting 1 hour.By above-mentioned ammonium modified beta zeolite, continue to add 0.4kg ammonium sulfate with after the making beating of 15kg decationized Y sieve water, in 80
DEG C stirring 1 hour, filtration washing roasting 2 hours under 550 DEG C, 100% water vapour, obtain without metal-modified β zeolite
db21.The element chemistry of db21 consists of 0.1na2o·5.5al2o3·94.5sio2.
Then according to the method for embodiment 13 prepares catalyst, except for the difference that with without metal-modified β zeolite db21
Replace b21.The comparative catalyst dc21 of present invention offer is provided.The composition of dc21 is shown in Table 4
Comparative example 10
Method according to embodiment 13 prepares modified beta zeolite, except for the difference that by 26.2g zirconium nitrate zr (no3)4·5h2O is molten
In 0.15kg decationized Y sieve water, finally obtain modified beta zeolite db22.Db22 element chemistry consists of 0.1na2o·
5.0zro2·6.2al2o3·88.7sio2.
Then according to the method for embodiment 13 prepares catalyst, except for the difference that modified beta zeolite db22 replaces b21.Obtain this
The comparative catalyst dc22 that invention provides.The composition of dc22 is shown in Table 4.
The composition of table 4 catalyst
Embodiment 18～22
This embodiment illustrates the catalytic performance of the Cracking catalyst that the present invention provides.
Catalyst c211～c25 is carried out in advance on fixed bed aging equipment 800 DEG C, 100% steam aging 17 little
When, then evaluated on small fixed fluidized bed unit, reaction raw materials are military mixed three (property is shown in Table 2), reaction temperature 500
DEG C, agent weight of oil than for 5.92, weight (hourly) space velocity (WHSV) 16h-1.Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield
+ coking yield；Total liquid yield=yield of liquefied gas+yield of gasoline+diesel yield；Density of propylene=propene yield/liquefied gas is received
Rate.Evaluation result is shown in Table 5.
Comparative example 11～12
This comparative example illustrates the catalytic performance of comparative catalyst.
According to the method for embodiment 18, carry out catalytic cracking using same raw oil, evaluate the reference of comparative example preparation
Catalyst dc21～dc22, evaluation result is shown in Table 5.
Table 5 evaluation result
* in table 5, % is weight %.
Embodiment 23
4.2kg Kaolin is mixed making beating with 19.8kg decationized Y sieve water, adds 3.2kg boehmite, use dilute salt
It is 3.5 that acid adjusts serosity ph value, and stirring stands aging 1 hour after 60 DEG C in 30 minutes, adds 3.7kg Alumina gel, and stirring is all
After even, add by dasy (2.0) zeolite of 3.7kg and 0.5kg(butt) above-mentioned modified beta zeolite b21 and 9.0 kilograms of decationized Y sieves
The serosity that water making beating is formed, average is disperseed 30 minutes, the serosity obtaining spray drying forming, in 550 DEG C of roastings 2 hours, is obtained
Cracking catalyst c26 providing to the present invention.The composition of c26 is shown in Table 6.
Embodiment 24
3.9kg Kaolin is mixed with 6.6kg decationized Y sieve water making beating after, add 16.7kg acidification pseudo-boehmite and
4.7kg Alumina gel, stirs 60 minutes, adds by dasy (2.0) zeolite of 2.4kg and 2.0kg(butt) above-mentioned modified beta zeolite
The serosity that the making beating of b21 and 9.0 kilogram of decationized Y sieve water is formed, after stirring 60 minutes, by the serosity obtaining spray drying forming, in
600 DEG C of roastings 1.5 hours, obtain Cracking catalyst c27 of present invention offer.The composition of c27 is shown in Table 6.
Embodiment 25
4.2kg Kaolin is mixed with 9.0kg decationized Y sieve water making beating after, add 3.2kg acidification pseudo-boehmite and
3.7kg Alumina gel, stirs 60 minutes, is subsequently adding by the prehy zeolite of 3.8kg and 0.5kg(butt) above-mentioned modified beta zeolite
The serosity that the making beating of b22 and 8.0 kilogram of deionized water is formed, after stirring 60 minutes, by the serosity obtaining spray drying forming, in
500 DEG C of roastings 3 hours, obtain Cracking catalyst c28 of present invention offer.The composition of c28 is shown in Table 6.
Embodiment 26
3.9kg Kaolin is mixed making beating with 22.0kg decationized Y sieve water, adds 16.7kg boehmite, use dilute salt
It is 3.0 that acid adjusts serosity ph value, and stirring stands aging 2 hours after 60 DEG C in 60 minutes, adds 4.7kg Alumina gel, and stirring is all
After even, adding by the prehy zeolite of 2.2kg and 2.0kg(butt) above-mentioned modified beta zeolite b22 pulled an oar with 8.0 kilograms of deionized waters
The serosity being formed, average is disperseed 30 minutes, and the serosity obtaining spray drying forming, in 550 DEG C of roastings 1 hour, obtains this
Cracking catalyst c29 of bright offer.The composition of c29 is shown in Table 6.
Comparative example 13
Prepare catalyst according to embodiment 23 methods described, except for the difference that replace modified beta zeolite with modified beta zeolite db21
b21.Finally obtain comparative catalyst dc23.The composition of dc23 is shown in Table 6.
Comparative example 14
Prepare catalyst according to embodiment 23 methods described, except for the difference that replace modified beta zeolite with modified beta zeolite db21
b22.Obtain comparative catalyst dc24.The composition of dc24 is shown in Table 6.
The composition of table 6 catalyst
Embodiment 27～30
This embodiment illustrates the catalytic performance of the Cracking catalyst that the present invention provides.
Catalyst c26～c29 is carried out in advance on fixed bed aging equipment 800 DEG C, 100% steam aging 17 little
When, then evaluated on small fixed fluidized bed unit, reaction raw materials are military mixed three (property is shown in Table 2), reaction temperature 500
DEG C, for 5.92, weight (hourly) space velocity (WHSV) is 16h-1 to agent weight of oil ratio.Evaluation result is shown in Table 7.
Comparative example 15～16
This comparative example illustrates the catalytic performance of comparative catalyst.
According to the method for embodiment 27, carry out catalytic cracking using same raw oil, evaluate the reference of comparative example preparation
Catalyst dc23～dc24, evaluation result is shown in Table 7.
Table 7 evaluation result
The heavy oil conversion performance of the Cracking catalyst being provided by table 5,7 visible (being compared with comparative example), the present invention is substantially carried
Height, total liquid yield significantly improves, liquefied gas yield improves, and in liquefied gas, density of propylene significantly improves.It can be seen that the gold that the present invention obtains
Belong to oxide modifying β zeolite (zeolite of β containing zirconium) and there is stronger heavy oil conversion performance, there is preferable liquefied gas yield and always
It is subject to, it is possible to increase the density of propylene in liquefied gas.
Claims (17)
1. a kind of zeolite of β containing zirconium, its anhydrous chemical is consisted of and is calculated as with oxide mass: (0～0.2) na2O (0.5～15)
zro2(0～10) mxoy(0.5～15) al2o3(60～97) sio2, wherein m is selected from one of ti, cr, fe, ga, x
Represent the atomic number of m, y represents the number meeting needed for m oxidation state；
The preparation method of the described zeolite of β containing zirconium, comprises the following steps:
(1) sodium form β zeolite is carried out ammonium ion exchange, make the na in zeolite2O content is not more than 0.2 weight %, optional roasting；
(2) the zeolite impregnating metal in organic solvent that step (1) is obtained, optionally drying；
(3) the β zeolite roasting obtaining step (2), the sintering temperature of described roasting is 350～800 DEG C, and roasting time is 0.5
More than hour；
(4) use aqueous acid process step (3) gained β zeolite, the concentration of acid is with h+It is calculated as 0.1～2mol/l,
(5) by with acid contact after β zeolite under 350～800 DEG C, 1～100% water vapour roasting more than 0.5 hour.
2. according to the zeolite of β containing zirconium described in claim 1 it is characterised in that the anhydrous chemical of the described zeolite of β containing zirconium consists of
It is calculated as with oxide mass: (0～0.2) na2O (1～10) zro2(0～8) mxoy(1～10) al2o3(70～95)
sio2.
3. a kind of preparation method of the zeolite of β containing zirconium, comprises the following steps:
(1) sodium form β zeolite is carried out ammonium ion exchange, make the na in zeolite2O content is not more than 0.2 weight %, optional roasting；
(2) the zeolite impregnating metal in organic solvent that step (1) is obtained, optionally drying；
(3) the β zeolite roasting obtaining step (2), the sintering temperature of described roasting is 350～800 DEG C, and roasting time is 0.5
More than hour；
(4) use aqueous acid process step (3) gained β zeolite, the concentration of acid is with h+It is calculated as 0.1～2mol/l,
(5) by with acid contact after β zeolite under 350～800 DEG C, 1～100% water vapour roasting more than 0.5 hour, changed
Property β zeolite:
The described zeolite of β containing zirconium, its anhydrous chemical is consisted of and is calculated as with oxide mass: (0～0.2) na2O (0.5～15)
zro2(0～10) mxoy(0.5～15) al2o3(60～97) sio2, wherein m is selected from one of ti, cr, fe, ga, x
Represent the atomic number of m, y represents the number meeting needed for m oxidation state.
4. in accordance with the method for claim 3 it is characterised in that impregnating metal includes in organic solvent in step (2): use
Zr compound or zr compound and the compound of the metal of one of ti, cr, fe, ga and the mixture of organic solvent with described
The β zeolitic contact that step (1) obtains, stirs 0.5～24 hour or stands 0.5～24 hour, wherein β zeolite and organic solvent
Solid-liquid weight is than for 1:(0.5～5)；The described zeolite impregnating metal in organic solvent that step (1) is obtained, optionally drying
Process carries out one or many.
5. in accordance with the method for claim 3 it is characterised in that described organic solvent be alkane, aromatic hydrocarbon, alcohol, ketone, ether,
One of ester, halogenated alkane or multiple.
6. in accordance with the method for claim 5 it is characterised in that the preferred normal hexane of described organic solvent, hexamethylene, heptane,
One or more of benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, chloroform.
7. in accordance with the method for claim 5 it is characterised in that the normal boiling point of described organic solvent is 40～100 DEG C.
8. in accordance with the method for claim 3 it is characterised in that the water content of described organic solvent is less than 5 weight %.
9. in accordance with the method for claim 3 it is characterised in that ion exchange described in step (1) is according to zeolite: ammonium
Salt: water=1:(0.1～1): the weight of (5～15) mixes than by zeolite, ammonium salt and water, stirs 0.5 at room temperature～100 DEG C
～5 hours, then filter, dry；This process carries out once arriving repeatedly, the na to zeolite2O content is not more than 0.2 weight %, wherein
When carrying out multiple, optionally by molecular sieve roasting before once exchanging on carrying out.
10. in accordance with the method for claim 3 it is characterised in that impregnating for incipient impregnation or excess described in step (2)
Dipping.
11. in accordance with the method for claim 3 it is characterised in that in step (3), described roasting in the in the air being dried or
In inert atmosphere, the temperature of roasting is 350～650 DEG C, and roasting time is 0.5～5 hour.
12. in accordance with the method for claim 3 it is characterised in that with h in aqueous acid described in step (4)+The acid of meter
Concentration is 0.5～2mol/l.
13. according to the method described in any one of claim 3～12 it is characterised in that the water content of described organic solvent does not surpass
Cross 3 weight %.
14. in accordance with the method for claim 13 it is characterised in that the water content of described organic solvent is less than 1 weight %.
15. in accordance with the method for claim 3 it is characterised in that described metal is zirconium or is titanium and zirconium.
16. in accordance with the method for claim 3 it is characterised in that the sintering temperature of roasting described in step (1) be 350～
800 DEG C, at least 0.5 hour under 1～100 volume % water vapour atmosphere.
17. in accordance with the method for claim 16 it is characterised in that the sintering temperature of roasting described in step (1) be 450～
650 DEG C, roasting time is 1～6 hour, and calcination atmosphere is 1～100 volume % water vapour atmosphere.
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