CN106145136A - A kind of modified beta zeolite and preparation method thereof - Google Patents
A kind of modified beta zeolite and preparation method thereof Download PDFInfo
- Publication number
- CN106145136A CN106145136A CN201510181520.1A CN201510181520A CN106145136A CN 106145136 A CN106145136 A CN 106145136A CN 201510181520 A CN201510181520 A CN 201510181520A CN 106145136 A CN106145136 A CN 106145136A
- Authority
- CN
- China
- Prior art keywords
- zeolite
- roasting
- compound
- weight
- modified beta
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
A kind of modified beta zeolite and preparation method thereof, the anhydrous chemical of described modified beta zeolite consists of and is calculated as with oxide mass: (0～0.2) Na2O (0.5～15) ZrO2(0～10) MxOy(1～10) P2O5(0.5～15) Al2O3(60～98) SiO2, wherein M one in Ti, Cr, Fe, Ga, x represents the atomic number of M, and y represents the number met needed for oxidation state of M.A kind of preparation method of described modified beta zeolite includes: is swapped by Na β zeolite ammonium ion and makes sodium oxide content therein be not higher than 0.2 weight %, roasting the most in the presence of water vapor, introduce Zr or Zr and the modified metal of one or more in Ti, Cr, Fe, Ga in organic solvent, process with acid and phosphorus-containing compound after roasting.This modified beta zeolite has higher cracking hydrocarbon ability and productivity of propylene.
Description
Technical field
The present invention relates to a kind of modified beta zeolite and preparation method thereof, furtherly, relate to one
Metal and the composite modified β zeolite of phosphorus and preparation method thereof.
Background technology
β zeolite is equal within 1967, synthesize first, to Higgins in 1988 by the Wadlinger of Mobil company
Etc. disclosing its distinctive Three Dimensions Structure, it is that unique one has intersection 12-membered ring's passage body
The silica-rich zeolite of system, 12 yuan of annular apertures of the one-dimensional channels being parallel to (001) crystal face are 0.75～0.57nm,
12 yuan of annular apertures of another two-dimensional channel parallel with (100) crystal face are 0.65～0.56nm.Due to it
The particularity of structure, has acid catalysis characteristic and structure selectivity concurrently, and has high heat and hydro-thermal is steady
Qualitative and anti-wear performance, shows good heat and hydrothermal stability, resistance in a series of catalytic reactions
Acidity, anti-coking and catalysis activity, developed rapidly the most as a kind of novel catalysis material
Material.Through modified and can be applicable to after loading some metallic element to be hydrocracked, hydro-isomerization, catalysis
In the petroleum refinings such as cracking and petrochemical industry.
At present, the synthesis of metal-modified β zeolite uses hydrothermal synthesis method mostly, i.e. closes at conventional hydrothermal
During becoming β zeolite, corresponding metallic compound is joined in synthetic system.JP10316417 is public
Having opened a kind of method being directly synthesized Ti-β zeolite, with butyl titanate for titanium source, silicon source uses silicic acid
Ethyl ester, Ludox or gas phase silica gel, formed and relax colloidal sol, with TEAOH as template, then lead to
Cross more than 150 DEG C hydrothermal treatment consists synthesis Ti-β zeolites.It is anti-that gained Ti-β zeolite can be applicable to various catalysis
Should.CN101353169A also discloses that the synthetic method of a kind of Ti-β zeolite, and the method comprises following step
Rapid: (1) is according to SiO2: TiO2: alcohol=1: (0.01～0.05): the mol ratio of (4.0～15.0)
By esters of silicon acis, titanate esters and butanol mix homogeneously, then it is added thereto to sodium hydroxide solution, and
At room temperature～120 DEG C after reaction, roasting obtains water silicon sodium stone；(2) according to SiO2: template: water=
1: (0.1～1.0): the mol ratio of (2.0～8.0) water silicon sodium stone, template and water are mixed after in
120～170 DEG C, crystallization 2～15 days, obtain the former powder of HTS with BEA framing structure；(3)
The former powder of HTS obtained in acid pickling step (2)；(4) the product roasting after pickling is obtained
Ti-beta-molecular sieve product, it is high that the Ti-beta-molecular sieve of synthesis has relative crystallinity, and fault of construction is few, and heat is steady
Qualitative height, the feature of nanocrystal yardstick.CN1785520A discloses a kind of β type sial containing Bi and divides
Son sieve, it is characterised in that this Si-Al molecular sieve contain Bi and optionally containing selected from B, Sn, Sb, Pb, Po,
One or more hetero atoms in Zn, Mn, Ti, V, W element, wherein B, Sn, Sb, Pb,
The mol ratio of the summation of Po, Zn, Mn, Ti, V, W atom/Bi atom is 0～0.2, SiO2/ Al's
Mol ratio is 5～100, SiO2The mol ratio of/Bi is 10～250, and this molecular sieve is to be closed by Direct Hydrothermal
Described element is attached in molecular sieve by one-tenth method, and this molecular sieve can be as oxidation reaction catalyst.
Simple relative to the preparation technology of hydrothermal synthesis method, liquid-phase ion exchange and infusion process, it is more easy to
In enforcement.CN1098028A discloses a kind of for toluene disproportionation with the zeolite beta catalyst of alkylated reaction
Agent, this catalyst is by 10 weight %～the β zeolite of 90 weight %, 5 weight %～the binding agent of 90 weight %, 0.05 weight %～5
Weight % is formed selected from metals such as Ni, Co, Cu, Ag, Sn, Ga, and wherein metal uses infusion process
Load.CN1043450A proposes a kind of potassium and the phosphorus method of modifying to β zeolite, can be by neutrality
Or the β zeolite after the exchange of alkalescence potassium salt, weakly acidic pH microcosmic salt buffer solution immersion dealuminzation；Can also be to use
Weakly acidic pH soaks the β zeolite after dealuminzation containing potassium, microcosmic salt buffer.Modified β zeolite contains 0.5～2.5
The potassium of weight % and 0.01～0.5% weighs the phosphorus of %, has more preferably hysomer activity.
CN1872685A discloses a kind of modified beta zeolite, it is characterised in that the anhydrous chemical table of this β zeolite
Reach formula, be calculated as (0～0.3) Na with the quality of oxide2O (0.5～10) Al2O3(1.3～
10)P2O5(0.7～15) MxOy(70～97) SiO2, wherein, M selected from Fe, Co, Ni, Cu, Mn,
One in Zn and Sn, wherein said metal ion is to be incorporated into boiling by dipping or ion-exchange process
Shi Zhong.This zeolite is applied in catalytic cracking, can be as catalyst or the active component of auxiliary agent.
Summary of the invention
It is an object of the invention to provide a kind of modified beta zeolite being applicable to catalytic cracking reaction and preparation thereof
Method.
The modified beta zeolite that the present invention provides, composite modified by Zr, optional other metal M and phosphorus,
Its anhydrous chemical expression, is calculated as with oxide mass: (0～0.2) Na2O (0.5～15) ZrO2(0～10)
MxOy(1～10) P2O5(0.5～15) Al2O3(60～98) SiO2, wherein M selected from Ti, Cr, Fe,
One or more in Ga, x represents the atomic number of M, and y represents met needed for oxidation state of M
Number.
The modified beta zeolite that the present invention provides, its anhydrous chemical expression, excellent with oxidation material gauge
The scope is selected to be: (0～0.2) Na2O (1～10) ZrO2(0～8) MxOy(2～7) P2O5(1～10)
Al2O3(70～95) SiO2。
The present invention provides the preparation method of a kind of described modified beta zeolite, including:
(1) sodium form β zeolite is carried out ammonium ion exchange, make the sodium oxide content in β zeolite not higher than
0.2 weight %, optional roasting；
(2) the zeolite impregnating metal in organic solvent that step (1) is 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 containing phosphorus compound and aqueous acid contact procedure (3) gained β zeolite, phosphorus (with
P2O5Meter) and the weight ratio 0.01～0.1 of β zeolite, in aqueous acid, the concentration of acid is with H+It is calculated as
0.1～2.0mol/L；
(5) will step (4) be boiled with containing the β after phosphorus compound and aqueous acid contact
Stone in 350～800 DEG C, 1～100% roasting at least 0.5 hour such as 0.5～5 hour under water vapour,
To metal and phosphorus composite modified β zeolite.
Sodium form β zeolite ammonium ion is swapped by step (1), makes the sodium oxide in β zeolite contain
Amount not higher than 0.2 weight %, then carries out roasting or does not carry out roasting.Wherein, if carried 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 be preferably in 350～800 DEG C, 1～100 volume % water steam
Under vapour atmosphere at least 0.5 hour, for example, 0.5～8 hour, preferably sintering temperature was 450～650 DEG C,
Roasting time is 1～6 hour.The exchange of described ammonium ion can be: according to zeolite (in terms of butt): ammonium
Salt: water=1:(0.1～1): zeolite, ammonium salt and water are mixed by the weight ratio of (5～15), room temperature～100 DEG C
Lower stirring 0.5～5 hours, then filter, optionally drying, and (present invention is the most exchanged in optional roasting
Roasting in journey), this process may be repeated one or more times, and makes Na in zeolite2O content is not more than 0.2
Weight %；When described exchange process repeats, on carrying out once before exchange process by zeolite roasting
Or not roasting, if carried out roasting, described sintering temperature such as 350～700 DEG C, roasting time is such as
1～5 hour, zeolite (in terms of butt) in exchange every time: ammonium salt: water is preferably 1:(0.1～1): (5～15)
Weight ratio.The water content of the zeolite that step (1) obtains is preferably more than 5% weight, and preferably more than 3
Weight %.Preferably, the contents on dry basis of the zeolite that step (1) obtains is not less than 95 weight %, preferably
It is not less than 97 weight % for example, 97～99 weight %.
The preparation method of the described modified beta zeolite that the present invention provides, a kind of embodiment, step (1)
Described in sodium form β zeolite carried out ammonium ion exchange include: according to sodium form β zeolite (butt meter):
Ammonium salt: water=1:(0.1～1): sodium form β zeolite, ammonium salt and water are mixed by the weight ratio of (5～15)
Close, stir 0.5～5 hour at room temperature～100 DEG C, then filter, optionally drying, optional roasting；
Said process may be repeated one or many, makes Na in zeolite2O content is not more than 0.2 weight %；
When repeating described exchange process, after described sodium form β zeolite is the exchange that last exchange obtains
β zeolite.
In the preparation method of the modified beta zeolite that the present invention provides, by step (1) described in step (2)
The β zeolite impregnating metal in organic solvent obtained, described metal (also referred to as modified metal) includes Zr
And optional other metal of one or more in Ti, Cr, Fe and Ga (also referred to as other
Modified metal).Described dipping can carry out one or many, and dipping can impregnate described in introducing every time
It is multiple that a kind of in metal can also introduce in described metal；Each metal can be by once soaking
Stain is incorporated in modified beta zeolite and can also be incorporated in modified beta zeolite by repeatedly dipping.Each time
Can also be dried or moist after dipping, if described dipping is carried out once, preferably impregnate laggard
Row is dried；If described dipping is carried out repeatedly, it is dried after at least last dipping, twice leaching
Can be with roasting or not roasting between stain.Impregnate each time, excess infusion process or equivalent impregnation can be used
Method (equi-volume impregnating), it is preferred to use equivalent impregnation method.
The preparation method of the modified beta zeolite that the present invention provides, in step (2), a kind of embodiment,
The described β zeolite impregnating metal in organic solvent that step (1) is obtained, including one or many with
Lower described dipping process, and the modified metal chemical combination that the most described dipping process of at least a part of which is used
Thing includes the compound of zirconium: by the compound of Zr and/or selected from the compound of Ti, the compound of Cr,
Other metallic compound of one or more in the compound of Fe and the compound of Ga and organic molten
The β zeolitic contact that the preferred solution of mixture of agent and described step (1) obtain (wherein, repeatedly impregnates
Time, dipping is directly to be contacted by the β zeolite that described mixture obtains with described step (1) for the first time,
Second time and later dipping are to be connect by the β zeolite that described mixture and last time obtain after dipping process
Touch), stir or stand (not stirring) and the most under agitation protect for 0.5～24 hour such as 0.5～12 hour
Hold 0.5～24 hour such as 0.5～12 hour, then optionally drying and/or roasting；Impregnate the most every time,
The β zeolite (in terms of butt) that step (1) obtains is preferably 1:(0.5～5 with the solid-to-liquid ratio of organic solvent)
Weight ratio.
The preparation method of the modified beta zeolite that the present invention provides, in step (2), a kind of preferably enforcement
Mode, the described β zeolite impregnating metal in organic solvent step (1) obtained is: will be selected from
One or more change of Zr compound, Ti compound, Cr compound, Fe compound or Ga compound
Property metallic compound and organic solvent form solution, the zeolite then this solution and step (1) obtained
Mixing, stirs or stands at least 0.5 hour such as 0.5～24 hour or 0.5～12 hour and impregnate,
Then being dried, this dipping process carries out one or many, and modified described in dipping process at least one times
Metallic compound includes Zr compound.When described metal is Zr and selected from Ti, Cr, Fe and Ga
In other metal of one or more time, Zr and other metal can impregnate simultaneously, it is also possible to respectively
Dipping, such as, can form solution with organic solvent, so by Zr compound and other metallic compound
Obtain β zeolite afterwards to mix impregnate with described step (1), it is also possible to by Zr compound and
Other compound forms zirconium compounds solution and other compound solution with organic solvent respectively, then
The β zeolite that described step (1) is obtained obtained zirconium compounds solution and other compound solution
Impregnate respectively；Other metallic compound described is selected from Ti compound, Cr compound, Fe compound
With in Ga compound one or more.
The preparation method of the modified beta zeolite that the present invention provides, described Zr compound can be the organic of zirconium
Metallic compound or the inorganic compound of zirconium, described zirconium compounds such as Zirconium tetrachloride., Disulfatozirconic acid.,
One or more in zirconium nitrate, zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide.Described Ti, Cr, Fe
Or the compound of Ga can be selected from their inorganic salt and/or their organic compound, described inorganic
The compound of the one in salt such as sulfate, nitrate, chlorate, such as titanium can be selected from metatitanic acid four
One or more in butyl ester, titanyl sulfate, Titanium Nitrate, titanium tetrachloride, the compound of described chromium can
With one or more in chromic nitrate, Chlorizate chromium, chromic sulfate, chromic anhydride；The compound of described ferrum
One or more in iron sulfate, ferric nitrate, iron chloride, ferrous sulfate, ferrous chloride can be selected from,
The compound of described gallium can be selected from one or more in Ganite (Fujisawa)., gallium chloride, potassium sulfate；Institute
The compound of Zr, Ti, Cr, Fe or Ga of stating can contain or not contain water of crystallization.Described have
Machine solvent can be the one in alkane, aromatic hydrocarbon, alcohol, ketone, ether, ester, halogenated alkane or many
Kind, the normal boiling point of described organic solvent preferably 40～100 DEG C, the preferred normal hexane of described organic solvent,
Hexamethylene, heptane, benzene, toluene, methanol, ethanol, isopropanol, acetone, butanone, chloroform
One or more in Deng.The water content of described organic solvent be less than 5 weight %, preferably more than 3
Weight % is such as less than 1 weight %.
The preparation method of the modified beta zeolite that the present invention provides, to step (2) gained in step (3)
To the zeolite of impregnating metal carry out roasting, described sintering temperature is 350～800 DEG C, and roasting time is
More than 0.5 hour, roasting time was 0.5～5 hour, and such as sintering temperature is 450～650 DEG C, roasting
Time is 1～4 hour.The β zeolite roasting that in step (3), step (2) obtained or roast after drying
Burn；Sintering temperature is 350～800 DEG C, and roasting time is more than 0.5 hour, for example, 0.5～5 hour.
Described calcination atmosphere is dry air, noble gas, preferably noble gas.Described noble gas is 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, preferably include to do before described roasting
Dry step, to reduce the content of organic solvent in zeolite, described being dried can be step (2) to be obtained
To zeolite be room temperature～100 DEG C of drying times are 4～48 hours in temperature.
In the preparation method of modified beta zeolite provided by the present invention, step uses phosphorus-containing compound in (4)
With aqueous acid (abbreviation acid solution) and step (3) gained β zeolitic contact, including by described
Step (3) gained β zeolite contacts with phosphorus compound and acid solution, and the temperature of contact is room temperature～100 DEG C,
It is preferably not less than 0.2 hour time of contact, preferably 0.5～5 hour, β zeolite (in terms of butt): phosphorus
(with P2O5Meter): the mass ratio of acid solution is 1:(0.01～0.1): the weight of (5～20), phosphorus and β zeolite
Amount ratio 0.01～0.1, preferably 0.02～0.07, 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.Room temperature for example, 15～40 DEG C.Institute
State washing can by with contact after zeolite wash with water to wash away free acid, then dry or moist,
It is dried and can use drying or be spray-dried, to reduce the water content in zeolite.
In the preparation method of modified beta zeolite of the present invention, acid described in step (4) be selected from hydrochloric acid,
One or more in sulphuric acid, nitric acid, oxalic acid, acetic acid, formic acid, citric acid, preferably hydrochloric acid, grass
One or more in acid, formic acid, citric acid.
In the preparation method of modified beta zeolite of the present invention, described in step (4), phosphorus compound is permissible
It is orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, aluminum phosphate and pyrophosphoric acid
In one or more.
In the preparation method of modified beta zeolite of the present invention, described in step (5), 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 such as roasting time be 0.5～5 hour.
In the modified beta zeolite that the present invention provides, on the basis of butt weight, zirconic content is
0.5～15 weight %, the content of described other metal (M) oxide is 0～10 weight %, with P2O5
The content of meter phosphorous oxide is 1～10 weight %, and the content of aluminium oxide is 0.5～15 weight %, silicon oxide
Content is 60～98 weight % such as 65～98 weight %, and the content of sodium oxide is 0～0.2 weight %.Enter
One step, described zirconic content is 1～10 weight %, the content of described other modified metal (M)
Being 0～8 weight % such as 0.5～8 weight %, the content of phosphorous oxide is 2～7 weight %, containing of aluminium oxide
Amount is 1～10 weight %, and the content of silicon oxide is 70～95 weight % such as 75～95 weight %, oxidation
The content of sodium is 0～0.2 weight %.
In the preparation method of the modified beta zeolite that the present invention provides, to treated β zeolite, first adopt
With the metal described in the introducing of organic solvent dipping method, then carried out P Modification, and carried out suitably
Post processing, the β zeolite with high hydrothermal stability can be obtained.
The modified beta zeolite that the present invention provides, in phosphorus, Zr and optional Ti, Cr, Fe, Ga
One or more are modified, and compared with prior art, the modified beta zeolite that the present invention provides has more
High hydrothermal stability, higher specific surface area and pore volume, its cracking hydrocarbon ability significantly improves,
Selectivity improves, and improves the productivity of propylene of crackate.Can apply in catalytic cracking of hydrocarbon,
As catalyst or the active component of auxiliary agent.
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
The essence place of the present invention and the beneficial effect brought, but should not be construed as implementing the present invention
Any restriction of scope.
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 %), mix with 3000g deionized water and 45g ammonium chloride and beat
Slurry, stirs 2 hours at 80 DEG C, then filters, and repeats said process 3 times, the Na in zeolite2O
Content is less than 0.2 weight %, in 600 DEG C, roasting 2 hours under 100% water vapour, after obtaining ammonium exchange
β zeolite, be designated as A-1, its water content 3 weight %；
By 52.3g zirconium nitrate Zr (NO3)4·5H2O is dissolved in 150g ethanol (analytical pure) and being impregnated
Liquid, the β Wessalith CS-1 after then being exchanged with ammonium by above-mentioned impregnation liquid is mixed homogeneously, and 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), it is subsequently adding 4.87g (NH4)H2PO4, mix homogeneously, rise
Temperature to 80 DEG C stirs 3 hours, then filters, is washed with deionized that (the washing water yield is zeolite butt
15 times of weight), filter, filter cake is placed in 600 DEG C, roasting 1 hour in 100% water vapour, obtains
The modified beta zeolite that the present invention provides, is designated as B1.Element chemistry consists of
0.1Na2O·9.9ZrO2·2.0P2O5·5.5Al2O3·82.5SiO2(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), mix with 2000g deionized water and 45g ammonium chloride and beat
Slurry, stirs 1 hour at 80 DEG C, then filters, repeat above-mentioned exchange process 3 times, at 650 DEG C
Roasting 2 hours, obtains the β Wessalith CS-2 after ammonium exchange；Na in Wessalith CS-22O content is less than 0.2
Weight %, water content 1 weight %；
18.9g zirconium iso-propoxide is dissolved in 450g ethanol, the β after then gained solution being exchanged with ammonium
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 subsequently adding 13.96g (NH4)2HPO4, it is warmed up to 90 DEG C, stirs 1 hour, then mistake
Filter, it is washed with deionized (the washing water yield is 15 times of molecular sieve butt weight), takes out filter cake and put
In 500 DEG C, roasting 2 hours in 100% water vapour, obtain the modified beta zeolite that the present invention provides, note
For B2.Element chemistry consists of 0.05Na2O·3.8ZrO2·4.9P2O5·7.2Al2O3·84.05SiO2Weight
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, mix making beating with 2000g deionized water and 60g ammonium chloride,
90 DEG C are stirred 3 hours, then filter, and repeat said process 2 times, Na in zeolite2O content is less than
0.2 weight %, in 500 DEG C of air roastings 5 hours, obtains β Wessalith CS-3 after ammonium exchange, and its water contains
Measure 1.5 weight %；
By 10.5g zirconium nitrate Zr (NO3)4·5H2O is dissolved in 200g ethanol, then by gained solution with
Obtained β Wessalith CS-3 mix homogeneously after ammonium exchange, stands 12 hours post-dryings；After drying
Zeolite mixes with the impregnation liquid being made up of 25.6g butyl titanate and 200g ethanol, stands 12 hours,
Then dry 24 hours in 100 DEG C, in nitrogen atmosphere, roasting 2 hours at 600 DEG C, after obtaining roasting
β zeolite, 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, it is subsequently adding 14.5g (NH4)3PO4, stir 3 hours at 80 DEG C, then filter, spend
Ionized water washing (the washing water yield is 20 times of molecular sieve butt weight), take out filter cake be placed in 500 DEG C,
Roasting 3 hours in 100% water vapour, obtain the modified beta zeolite B3 that the present invention provides, element chemistry
Consist of 0.1Na2O·1.9ZrO2·4.1TiO2·6.8P2O5·4.2Al2O3·82.9SiO2(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 hydro-thermal is forward and backward, and calculate crystallization reservation degree, crystallization reservation degree is hydro-thermal
Relative crystallinity after 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 (ibid), mix with 2000g deionized water and 45g ammonium sulfate and beat
Slurry, is warmed up to 85 DEG C and stirs 3 hours, then filter, repeat said process 3 times, the Na in zeolite2O
Content, less than 0.2 weight %, in 600 DEG C of roastings 2 hours, obtains β Wessalith CS-4 after ammonium exchange, its
Water content is 1.5 weight %；
By 15.7g zirconium oxychloride ZrOCl2·8H2O is dissolved in 250g ethanol, then by gained solution with
β Wessalith CS-4 mixing after the exchange of above-mentioned ammonium, stands 12 hours, dries；Zeolite after drying with by
15.2g ferric nitrate Fe (NO3)3·9H2The impregnation liquid mixing of O and 250g ethanol composition, stands 12 hours
Soak, then dry 24 hours in 100 DEG C, in nitrogen atmosphere, roasting 3 hours at 450 DEG C；?
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, it is subsequently adding 8.38g (NH4)2HPO4, mix homogeneously, 80 DEG C of stirrings 2 hours, so
Rear filtration, it is washed with deionized (the washing water yield is 10 times of molecular sieve butt weight), takes out filter
Cake is placed in 550 DEG C, roasting 2 hours in 100% water vapour, obtains the modified beta zeolite that the present invention provides
B4, its anhydrous chemical consists of 0.06Na2O·4.0ZrO2·1.9Fe2O3·2.8P2O5
·3.9Al2O3·87.34SiO2(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), mix with 3000g deionized water and 50g ammonium chloride and beat
Slurry, is warmed up to 75 DEG C and stirs 3 hours, then filter, repeat said process 3 times, Na in zeolite2O
Content is less than 0.2 weight %, in 650 DEG C, roasting 1 hour under 100% water vapour.Obtain the β of ammonium exchange
Wessalith CS-5, water content 2.0 weight %；
By 28.3g zirconium iso-propoxide and 9.4g chromic nitrate Cr (NO3)3·9H2O is dissolved in 500g hexamethylene
To solution, β Wessalith CS-5 after then this solution homogeneous impregnation ammonium being exchanged, stir 6 hours, in
Dry 24 hours for 100 DEG C, in nitrogen atmosphere, roasting 1 hour at 650 DEG C, obtain the boiling of the β after roasting
Stone AC-5；
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, it is subsequently adding 2.79g (NH4)H2PO4, mix homogeneously, it is warmed up to 90 DEG C and continues stirring
1 hour, then filter, be washed with deionized 20 times of molecular sieve butt weight (the washing water yield be),
Take out filter cake and be placed in 600 DEG C, roasting 2 hours in 100% water vapour.Obtain the modification that the present invention provides
β zeolite B5；Element chemistry consists of 0.1Na2O·5.8ZrO2·1.9Cr2O3·1.0P2O5
·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), 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 500 DEG C, roasting 3 hours under 100% water vapour, after obtaining ammonium exchange
β Wessalith CS-6, water content 1.0 weight %；
By 41.8g zirconium nitrate Zr (NO3)4·5H2O and 6.7g Ganite (Fujisawa). Ga (NO3)3·9H2O is dissolved in 250g
In ethanol, β Wessalith CS-6 after then above-mentioned solution homogeneous impregnation ammonium being exchanged, stand 24 hours,
Dry 24 hours in 100 DEG C, in nitrogen atmosphere, roasting 2 hours at 500 DEG C, obtain the boiling of the β after roasting
Stone；
β zeolite after gained roasting is joined the citric acid that 3000g acid concentration is 1.0mol/L water-soluble
In liquid, it is subsequently adding 8.82g (NH4)3PO4, mix homogeneously, it is warmed up to 85 DEG C and continues stirring 2 hours,
Then filter, be washed with deionized 20 times of molecular sieve butt weight (the washing water yield be), take out
Filter cake is placed in 550 DEG C, roasting 3 hours in 100% water vapour.Obtain the modified β boiling that the present invention provides
Stone B6.Element chemistry consists of 0.1Na2O·8.0ZrO2·0.9Ga2O3·3.7P2O5
·7.9Al2O3·79.4SiO2(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
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 modified beta zeolite.
Element chemistry consists of 0.05Na2O·5.8Al2O3·94.2SiO2(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 hydro-thermal 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 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
In 150g deionized water.Finally obtaining modified beta zeolite, element chemistry consists of
0.1Na2O·9.7ZrO2·2.0P2O5·5.2Al2O3·83.0SiO2(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 hydro-thermal 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
According to the method for embodiment 1, except for the difference that, the β zeolite after roasting is without the acid of final step
Process with P Modification.Element chemistry consists of 0.3Na2O·9.9ZrO2·5.9Al2O3·83.9SiO2(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 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
Butyl titanate is dissolved in 200g deionized water, with filter cake hybrid infusion 12 hours after in 600 DEG C,
Under 100% water vapour, roasting 2 hours, obtain modified beta zeolite.
β zeolite after above-mentioned roasting is joined the aqueous hydrochloric acid solution that 1000g acid concentration is 0.5mol/L
In, it is added without the compound of phosphorus, stirs 3 hours at 80 DEG C, then filter, be washed with deionized
(the washing water yield is 20 times of molecular sieve butt weight), takes out that filter cake is placed in 500 DEG C, 100% water steams
Roasting 3 hours in vapour, obtain contrasting modified beta zeolite, and element chemistry consists of
0.1Na2O·1.8ZrO2·4.0TiO2·6.8Al2O3·87.3SiO2(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 hydro-thermal 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.
The physicochemical data of table 1 modified beta zeolite
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 5～8
The modified beta zeolite that comparative example 1～4 is prepared by comparative example 5～8 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.
Catalytic cracking fixed bed micro-anti-on evaluate catalyst, appreciation condition is reaction temperature 500 DEG C, agent
Weight of 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·5.2ZrO2·2.5P2O5·7.8Al2O3·84.4SiO2(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 (6.0) 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 3 changes proportioning and prepares the modified beta zeolite B22 that the present invention provides.B22
Element chemistry consist of 0.05Na2O·3.8ZrO2·3.5TiO2·1.5P2O5·5.2Al2O3·85.95SiO2
(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 4 changes proportioning and prepares the modified beta zeolite B23 that the present invention provides.B23
Element chemistry consist of 0.1Na2O·6.1ZrO2·1.9Fe2O3·3.3P2O5·7.8Al2O3·80.8SiO2
(weight composition).
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 prepares the modified beta zeolite B24 that the present invention provides, except for the difference that, leaching
During stain metal-oxide, by 10.5g zirconium nitrate Zr (NO3)4·5H2O is dissolved in 150g ethylene glycol, so
After by above-mentioned solution homogeneous impregnation ammonium exchange after β zeolite, stand 12 hours post-dryings；After drying
Zeolite is again with 9.4g chromic nitrate Cr (NO3)3·9H2The impregnation liquid of O and 150g ethylene glycol composition is carried out uniformly
Dipping, in 550 DEG C, roasting 2 hours under 100% water vapour after standing 12 hours.The element of B24
Consist of 0.08Na2O·2.0ZrO2·1.9Cr2O3·1.0P2O5·5.5Al2O3·89.52SiO2(weight composition).
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.
Embodiment 17
The method of reference example 6 changes proportioning and prepares the modified beta zeolite B25 that the present invention provides.B25
Element chemistry consist of 0.1Na2O·4.2ZrO2·2.0Ga2O3·1.2P2O5·6.5Al2O3·86.0SiO2
(weight composition).
Then according to the method for embodiment 13 prepares catalyst, except for the difference that with modified beta zeolite B25 generation
For B21.Obtain Cracking catalyst C25 that the present invention provides.The composition of C25 is shown in Table 4.
Comparative example 9
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·5.5Al2O3·94.5SiO2。
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 10
Modified beta zeolite is prepared, except for the difference that by 26.2g zirconium nitrate 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·5.0ZrO2·2.5P2O5·7.0Al2O3·85.4SiO2。
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 18～22
The catalytic performance of the Cracking catalyst that this embodiment explanation present invention provides.
Catalyst C21～C25 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 11～12
The catalytic performance of this comparative example explanation comparative catalyst.
According to the method for embodiment 18, 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 %.
Embodiment 23
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, homogenous disperse 30 minutes, the serosity spray drying forming that will obtain is little in 550 DEG C of roastings 2
Time, obtain Cracking catalyst C26 that the present invention provides.The composition of C26 is shown in Table 6.
Embodiment 24
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 C27 that the present invention provides.The composition of C27 is shown in Table 6.
Embodiment 25
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 C28 that the present invention provides.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 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,
Homogenous disperse 30 minutes, the serosity spray drying forming that will obtain, in 550 DEG C of roastings 1 hour,
Cracking catalyst C29 provided to the present invention.The composition of C29 is shown in Table 6.
Comparative example 13
Catalyst is prepared, except for the difference that with modified beta zeolite DB21 generation according to method described in embodiment 23
For modified beta zeolite B21.Finally obtain comparative catalyst DC23.The composition of DC23 is shown in Table 6.
Comparative example 14
Catalyst is prepared, except for the difference that with modified beta zeolite DB21 generation according to method described in embodiment 23
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 27～30
The catalytic performance of the Cracking catalyst that this embodiment explanation present invention provides.
Catalyst C26～C29 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 15～16
The catalytic performance of this comparative example explanation comparative catalyst.
According to the method for embodiment 27, 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 5,7, the heavy oil conversion performance of the Cracking catalyst that the present invention provides strengthens, gasoline
Productivity improves, and total liquid yield increases, liquefied gas yield increases, and in liquefied gas, density of propylene significantly improves,
Coke yield reduces.The modified beta zeolite that the visible present invention obtains have stronger heavy oil conversion performance and
Product selectivity.
Claims (16)
1. a modified beta zeolite, its anhydrous chemical consists of and is calculated as with oxide mass: (0～0.2)
Na2O (0.5～15) ZrO2(0～10) MxOy(1～10) P2O5(0.5～15) Al2O3(60～98)
SiO2, wherein one or more in Ti, Cr, Fe, Ga of M, x represents the atomic number of M, y
Represent and meet the number needed for oxidation state of M.
2. according to the modified beta zeolite described in claim 1, it is characterised in that described modified beta zeolite
Anhydrous chemical consist of and be calculated as with oxide mass: (0～0.2) Na2O (1～10) ZrO2(0～8)
MxOy(2～7) P2O5(1～10) Al2O3(70～95) SiO2。
3. a preparation method for modified beta zeolite, 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 β zeolite impregnating metal in organic solvent that step (1) is obtained, optionally drying；
(3) β zeolite roasting step (2) obtained or dry roasting, the roasting of described roasting
Temperature is 350～800 DEG C, and roasting time is more than 0.5 hour；
(4) with containing phosphorus compound and aqueous acid contact procedure (3) gained β zeolite, phosphorus (with
P2O5Meter) it is 0.01～0.1 with the weight ratio of step (3) gained β zeolite (in terms of butt), acid
Concentration of aqueous solution is with H+It is calculated as 0.1～2.0mol/L；
(5) β zeolite step (4) obtained roasts under water vapour at 350～800 DEG C, 1～100%
Burn more than 0.5 hour, obtain modified beta zeolite.
The most in accordance with the method for claim 3, it is characterised in that by step described in step (2)
(1) the β zeolite impregnating metal in organic solvent obtained, including following dipping process: with modified gold
The β zeolitic contact that the compound belonged to and the solution of organic solvent or mixture obtain with described step (1),
Stir or stand 0.5～24 hour, optionally drying and/or roasting, the compound of wherein said modified metal
For Zr compound and/or selected from Ti compound, Cr compound, Fe compound and one in Ga compound
Or other multiple modified metal compound；Described dipping process carries out one or many, and at least
Described in the most described dipping process, the compound of modified metal includes Zr compound, when impregnating every time
The solid-to-liquid ratio of the β zeolite that the step (1) in terms of butt obtains and organic solvent as 1:(0.5～5) weight
Ratio.
The most in accordance with the method for claim 3, 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 5, it is characterised in that described organic solvent is the most 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 5, it is characterised in that the standard boiling of described organic solvent
Point is 40～100 DEG C.
The most in accordance with the method for claim 3, it is characterised in that the water content of described organic solvent
It is preferably more than 3 weight % such as less than 1 weight % less than 5 weight %.
The most in accordance with the method for claim 3, it is characterised in that ammonium ion described in step (1)
Exchange includes: according to β zeolite: ammonium salt: water=1:(0.1～1): the weight ratio of (5～15) by β zeolite,
Ammonium salt and water mixing, stir 0.5～5 hour at room temperature～100 DEG C, then filters, is dried；Institute
State ammonium ion exchange process to carry out once arriving repeatedly, Na to zeolite2O content is not more than 0.2 weight %,
When wherein carrying out repeatedly, optionally by zeolite roasting before once exchanging on carrying out.
10. according to the method described in claim 3 or 4, it is characterised in that described in step (2)
Dipping is incipient impregnation or excess dipping.
11. in accordance with the method for claim 3, it is characterised in that in step (3), described roasting
Burning in dry air 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 containing phosphatization in step (4)
Compound and aqueous acid and step (3) gained β zeolitic contact, including by described β zeolite and phosphatization
Compound contacts with acid solution, and the temperature of contact is room temperature～100 DEG C, and it is little that time of contact is preferably not less than 0.2
Time, β zeolite (butt): phosphorus is (with P2O5Meter): the mass ratio of acid solution is 1:(0.01～0.1): (5～20).
13. in accordance with the method for claim 3, 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.
14. in accordance with the method for claim 3, it is characterised in that phosphatization described in step (4)
Compound is orthophosphoric acid, phosphorous acid, ammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, aluminum phosphate or Jiao
One in phosphoric acid or how in.
15. according to the method described in claim 3 or 9, it is characterised in that described in step (1)
The sintering temperature of roasting is 350～800 DEG C, 1～100 under volume % water vapour atmosphere at least 0.5 hour.
16. in accordance with the method for claim 15, it is characterised in that roasts described in step (1)
The sintering temperature burnt is 450～650 DEG C, and roasting time is 1～6 hour, and calcination atmosphere is 1～100 volumes
% water vapour atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181520.1A CN106145136B (en) | 2015-04-16 | 2015-04-16 | A kind of modified beta zeolite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510181520.1A CN106145136B (en) | 2015-04-16 | 2015-04-16 | A kind of modified beta zeolite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106145136A true CN106145136A (en) | 2016-11-23 |
| CN106145136B CN106145136B (en) | 2018-07-31 |
Family
ID=58057725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510181520.1A Active CN106145136B (en) | 2015-04-16 | 2015-04-16 | A kind of modified beta zeolite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106145136B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190083965A1 (en) * | 2017-01-13 | 2019-03-21 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas-purifying composition |
| CN110290871A (en) * | 2017-01-18 | 2019-09-27 | 巴斯夫欧洲公司 | The method of mechanograph of the preparation comprising zinc and titanium-containing zeolite |
| EP3456412A4 (en) * | 2017-01-13 | 2020-01-15 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas-purifying composition |
| US10941354B1 (en) | 2019-10-01 | 2021-03-09 | Saudi Arabian Oil Company | Hydrocracking catalyst comprising a beta zeolite (*BEA) framework substituted with Ti and Zr and methods for its preparation and use |
| US11142703B1 (en) | 2020-08-05 | 2021-10-12 | Saudi Arabian Oil Company | Fluid catalytic cracking with catalyst system containing modified beta zeolite additive |
| US11154845B1 (en) | 2020-07-28 | 2021-10-26 | Saudi Arabian Oil Company | Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts |
| US11274068B2 (en) | 2020-07-23 | 2022-03-15 | Saudi Arabian Oil Company | Process for interconversion of olefins with modified beta zeolite |
| CN114477210A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method thereof |
| US11332678B2 (en) | 2020-07-23 | 2022-05-17 | Saudi Arabian Oil Company | Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst |
| US11420192B2 (en) | 2020-07-28 | 2022-08-23 | Saudi Arabian Oil Company | Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts |
| US11618858B1 (en) | 2021-12-06 | 2023-04-04 | Saudi Arabian Oil Company | Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152476A (en) * | 1995-12-19 | 1997-06-25 | 南开大学 | Catalyst for preparing methyl tert-butyl ether |
| CN101209845A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Method for preparing molecular sieve material |
| CN101450318A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Modification method of beta-molecular sieve |
| CN103787357A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Modified beta molecular sieve |
| CN103787358A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Phosphorus and metal-containing beta molecular sieve |
| CN103787359A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Phosphorus-containing silicon-enriched beta molecular sieve |
-
2015
- 2015-04-16 CN CN201510181520.1A patent/CN106145136B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1152476A (en) * | 1995-12-19 | 1997-06-25 | 南开大学 | Catalyst for preparing methyl tert-butyl ether |
| CN101209845A (en) * | 2006-12-27 | 2008-07-02 | 中国石油化工股份有限公司 | Method for preparing molecular sieve material |
| CN101450318A (en) * | 2007-11-28 | 2009-06-10 | 中国石油化工股份有限公司 | Modification method of beta-molecular sieve |
| CN103787357A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Modified beta molecular sieve |
| CN103787358A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Phosphorus and metal-containing beta molecular sieve |
| CN103787359A (en) * | 2012-10-26 | 2014-05-14 | 中国石油化工股份有限公司 | Phosphorus-containing silicon-enriched beta molecular sieve |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190083965A1 (en) * | 2017-01-13 | 2019-03-21 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas-purifying composition |
| EP3406338A4 (en) * | 2017-01-13 | 2019-12-11 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas-purifying composition |
| EP3456412A4 (en) * | 2017-01-13 | 2020-01-15 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas-purifying composition |
| US10688480B2 (en) * | 2017-01-13 | 2020-06-23 | Mitsui Mining & Smelting Co., Ltd. | Exhaust gas-purifying composition |
| CN110290871A (en) * | 2017-01-18 | 2019-09-27 | 巴斯夫欧洲公司 | The method of mechanograph of the preparation comprising zinc and titanium-containing zeolite |
| CN114599450A (en) * | 2019-10-01 | 2022-06-07 | 沙特***石油公司 | Hydrocracking catalyst comprising a Ti and Zr substituted beta zeolite (BEA) framework, method for preparing same and use thereof |
| WO2021067119A1 (en) | 2019-10-01 | 2021-04-08 | Saudi Arabian Oil Company | Hydrocracking catalyst comprising a beta zeolite (*bea) framework substituted with ti and zr and methods for its preparation and use |
| US10941354B1 (en) | 2019-10-01 | 2021-03-09 | Saudi Arabian Oil Company | Hydrocracking catalyst comprising a beta zeolite (*BEA) framework substituted with Ti and Zr and methods for its preparation and use |
| US11274068B2 (en) | 2020-07-23 | 2022-03-15 | Saudi Arabian Oil Company | Process for interconversion of olefins with modified beta zeolite |
| US11332678B2 (en) | 2020-07-23 | 2022-05-17 | Saudi Arabian Oil Company | Processing of paraffinic naphtha with modified USY zeolite dehydrogenation catalyst |
| US11154845B1 (en) | 2020-07-28 | 2021-10-26 | Saudi Arabian Oil Company | Hydrocracking catalysts containing USY and beta zeolites for hydrocarbon oil and method for hydrocracking hydrocarbon oil with hydrocracking catalysts |
| US11420192B2 (en) | 2020-07-28 | 2022-08-23 | Saudi Arabian Oil Company | Hydrocracking catalysts containing rare earth containing post-modified USY zeolite, method for preparing hydrocracking catalysts, and methods for hydrocracking hydrocarbon oil with hydrocracking catalysts |
| US11142703B1 (en) | 2020-08-05 | 2021-10-12 | Saudi Arabian Oil Company | Fluid catalytic cracking with catalyst system containing modified beta zeolite additive |
| CN114477210A (en) * | 2020-10-26 | 2022-05-13 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method thereof |
| CN114477210B (en) * | 2020-10-26 | 2023-09-05 | 中国石油化工股份有限公司 | Beta molecular sieve and preparation method thereof |
| US11618858B1 (en) | 2021-12-06 | 2023-04-04 | Saudi Arabian Oil Company | Hydrodearylation catalysts for aromatic bottoms oil, method for producing hydrodearylation catalysts, and method for hydrodearylating aromatic bottoms oil with hydrodearylation catalysts |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106145136B (en) | 2018-07-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106145136A (en) | A kind of modified beta zeolite and preparation method thereof | |
| CN104549453B (en) | Zirconium-containing beta zeolite and preparation method thereof | |
| CN106140289A (en) | A kind of Cracking catalyst containing modified beta zeolite | |
| CN103447063B (en) | Heavy oil Efficient Conversion catalytic cracking catalyst and preparation method thereof | |
| CN104549422B (en) | Metal modified Y zeolite and preparation method and application thereof | |
| CN101134172B (en) | Hydrocarbons conversion catalyzer | |
| CN100425534C (en) | Modified beta zeolite | |
| CN103157506B (en) | A kind of high light receipts catalyst for heavy oil catalytic cracking and preparation method thereof | |
| CN104549423B (en) | Metal modified Y zeolite and preparation method and application thereof | |
| JP4771955B2 (en) | MFI molecular molecular sieve containing phosphorus and metal components, and production method and use thereof | |
| BRPI0509507B1 (en) | hydrocarbon conversion catalyst containing zeolite, the process for preparing them, and a process for converting hydrocarbon oils with the catalyst | |
| CN103785458B (en) | A kind of cracking additive improving low-carbon olefin concentration | |
| CN101450318B (en) | Modification method of beta-molecular sieve | |
| CN106140277B (en) | A kind of modified beta zeolite and preparation method thereof | |
| CN103785456B (en) | A kind of cracking additive improving low-carbon olefin concentration | |
| CN102134082B (en) | Preparation method of ZSM-5 molecular sieve | |
| CN103787357B (en) | A kind of modified beta molecular sieve | |
| CN104549463B (en) | Cracking catalyst containing metallic oxide modified beta zeolite | |
| CN102452669A (en) | MFI structure molecular sieve containing phosphorus and transition metal as well as its preparation method | |
| CN105013525A (en) | Catalytic cracking additive for increasing low carbon olefin concentration and preparation method thereof | |
| CN107185586A (en) | Assistant for calalytic cracking of producing more propylene and iso-amylene and its preparation method and application | |
| CN104946301A (en) | Catalytic conversion method for increasing concentration of low-carbon olefin | |
| CN106140290B (en) | A kind of Cracking catalyst containing modified beta zeolite | |
| CN107971013A (en) | A kind of catalytic cracking catalyst and preparation method thereof | |
| CN103785457A (en) | Cracking assistant for improving low-carbon olefin concentration |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |