CN105618108B - A kind of method of modifying of Y type molecular sieve - Google Patents
A kind of method of modifying of Y type molecular sieve Download PDFInfo
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Abstract
A kind of method of modifying of Y type molecular sieve, comprises the following steps：(1) compound of titaniferous and/or zirconium is dispersed in water, the pH value for adjusting mixture is 3~10；(2) molecular sieve is mixed with mixture obtained by step (1), stirred；Optionally filtering and/or drying；(3) in 300~700 DEG C of roastings.Y type molecular sieve method of modifying provided by the invention, production cost is low, and obtained Modified Zeolite Y has higher heat and hydrothermal stability.
Description
Technical field
The present invention relates to a kind of method of modifying of Y type molecular sieve.
Background technology
In catalytic cracking catalyst, molecular sieve is a kind of very extensive material of application, while is also very important
A kind of component, the performance of molecular sieve have directly influenced the reactivity worth of catalytic cracking catalyst.According to different needs, can be with
The requirement that different modifications is used to reach is carried out to molecular sieve.Divide for example, the rare earth ion of molecular sieve is modified to be conducive to improve
The stability and cracking activity of son sieve, are largely widely applied for a long time.However, rare earth is as important strategic resource
And its it is non-renewable, rare earth price fluctuates in causing in recent years, makes FCC catalyst cost increase.FCC how is reduced to urge
Content of rare earth in agent becomes the problem of current in the urgent need to address.Therefore, it is intended that other metal ions are introduced into molecular sieve
To strengthen the stability of molecular sieve and cracking activity.
CN1350887A discloses one kind while contains noble metal and non-noble metal modified Y molecular sieve and preparation method thereof,
By carrying out noble metal and non-noble metal ion exchange to NaY raw materials, hydro-thermal process and ammonium salt exchange, be finally made
Containing 0.05 weight %~2.0 weight % noble metal, the non-noble metal modified Y molecular sieve of the weight of 0.5 weight %~15.0 %.
CN1765492A discloses a kind of alumina support containing Y molecular sieve and preparation method thereof, and wherein modified Y molecular sieve is using the
One or more in group vib and/or group VIII metal W, Ni, Co, Fe, Mo are modified by way of cation exchange
's.US2007010698A1 discloses a kind of carbon monoxide-olefin polymeric, comprising a kind of with lanthanide series and group VIIIB metal exchange
Y molecular sieve, the group VIIIB metal are mainly selected from platinum and palladium, using ion exchange and dipping method that lanthanide series salt is water-soluble
Liquid and group VIIIB aqueous metal salt processing Y molecular sieve.
The preparation method for the metal-modified Y zeolites that above patent of invention provides, is mainly exchanged and is impregnated using conventional ion
Method handles Y molecular sieve with aqueous metal salt, and the heat and hydrothermal stability of obtained other metal-modified Y molecular sieves are poor,
So as to have impact on its application in catalytic cracking catalyst.
Some very strong metal ions of hydrolysis ability (such as Fe3+、Cr3+、Ti4+、Zr4+), play can occurs in it in aqueous
Strong hydrolysis, it is in highly acid (pH value is less than 1) to make aqueous solution, and the skeleton structure of stronger acid condition meeting saboteur's sieve, is shown
Writing reduces its activity.In order to avoid destruction of the metal ion to skeleton structure of zeolite, Wang Yangdong etc. use metatitanic acid in preparation process
Butyl ester/ethanol solution is impregnated with USY zeolite, titaniferous USY zeolite is prepared for, as the smaller (≤4.8%TiO of Ti contents2) when,
Ti high dispersives are small in zeolite surface, pore passage structure change；When Ti contents are higher, there is TiO2Diffraction maximum, can block zeolite pore
Road structure；Ti mainly combined in the form of monodentate or bidentate with zeolite surface silicone hydroxyl (" preparation and representation of titaniferous USY zeolite ",
Chemical journal, 2000,58 (6)), this method prepares molecular sieve in organic solvent, and the molecular sieve prepared is used for catalytic cracking
Its cracking activity is not high.
The content of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of titaniferous or/and the Y type molecular sieve of zirconium.
The present invention provides a kind of method of modifying of Y type molecular sieve, wherein, this method comprises the following steps：
(1) compound of titaniferous and/or zirconium is dispersed in water, the pH value for adjusting mixture is 3~10；
(2) Y type molecular sieve is mixed with mixture obtained by step (1), stirred at least 10 minutes, optionally filtered and/or dry
It is dry；
(3) roasted at 300~700 DEG C, obtain the Modified Zeolite Y of titaniferous and/or zirconium.
In the method for modifying of molecular sieve of the present invention, step (1) described compound by titaniferous and/or zirconium is dispersed
In water, (titanium is with TiO in terms of the oxide of titanium and/or zirconium for the mass concentration of gained mixture2Meter, zirconium is with ZrO2Meter, when at the same time
Containing titanium and zirconium, with TiO2With ZrO2The sum of meter) for 0.05%~15% be, for example, 0.4~6%.
In the method for modifying of Y type molecular sieve provided by the present invention, the compound of titaniferous and/or zirconium described in step (1)
One or more in the compound or the compound of titaniferous and zirconium of compound, zirconium for titanium.The compound of the titanium can be
Titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride, tetraalkyl titanate (Ti (alkoxy)4) such as butyl titanate, fluorine
One or more in titanium acid ammonium, the tetraalkyl titanate (Ti (alkoxy)4The carbon number of middle alkyl is preferably 1,2,3,
4th, 5 or 6；The compound of the zirconium can be zirconium chloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide
In one or more, the water can be deionized water, distilled water, decationized Y sieve water or its mixture.
In the method for modifying of Y type molecular sieve provided by the present invention, pH value described in step (1) for example can be with for 3~10
For 3.5~7.Can by add alkaline matter for example add alkaline solution adjust mixture pH value, make zirconium ion and/or titanium from
Son forms hydroxide.The alkaline solution can be the aqueous solution of alkaline matter, such as ammonium hydroxide, waterglass can be selected water-soluble
One or more in liquid, sodium metaaluminate aqueous solution or sodium hydrate aqueous solution, are preferably ammonium hydroxide.The quality of the alkaline solution
Concentration can be 2~20% for example, 3~15%.
It is in step (1) that the compound of titaniferous and/or zirconium is equal in the method for modifying of Y type molecular sieve provided by the present invention
Even to be dispersed in water to obtain mixture, the pH value for adjusting mixture is 3~10, is then stirred；It is preferred that in temperature be 0~100 DEG C
Stirring for example stir within least 10 minutes 10 minutes to 24 it is small when for example stir 10~180 minutes and for example stirred at room temperature~950 DEG C
Mix 0.5~2 it is small when.It is further preferred that the temperature (whipping temp) of mixture is room temperature to 100 DEG C during stirring, mixing time for 10~
120 minutes；Such as the temperature of mixture is room temperature to 90 DEG C during stirring, mixing time is 20~90 minutes.Further, it is described to stir
Mix preferred room temperature~60 DEG C of temperature, mixing time preferably 30~90min.The room temperature can be 15~40 DEG C.
In the method for modifying of Y type molecular sieve provided by the present invention, in step (2), (titanium in terms of titanium and/or Zirconium oxide
With TiO2Meter, zirconium is with ZrO2Meter, while titaniferous and zirconium are with TiO2And ZrO2The sum of meter) the step of (1) obtained by mixture with butt
The mass ratio of the Y type molecular sieve of meter is (0.005~0.15):1, it is, for example, 0.01~10:1.Preferably, step (2) institute
Stating the dosage of mixture obtained by Y type molecular sieve and step (1) makes the titanium being introduced into the Y type molecular sieve and/or zirconium (titanium is with TiO2
Meter, zirconium is with ZrO2Meter, while titaniferous and zirconium are with TiO2And ZrO2The sum of meter) with the mass ratio of the Y type molecular sieve for (0.01~
0.15):1.A kind of embodiment, (titanium is with TiO in terms of oxide in mixture obtained by step (1)2Meter, zirconium is with ZrO2Meter, at the same time
Titaniferous and zirconium are with TiO2And ZrO2The sum of meter) titanium and/or zirconium and the mass ratio of the Y type molecular sieve counted using butt as
0.01~0.15:1.In step (2), mixture obtained by step (1) and the Y type molecular sieve and mass ratio can be 1~20:
1, it is, for example, 1.5~10:1 or 1.7~5:1.
Preferably, on the basis of the butt weight of titaniferous and/or the modified Y molecular sieve of zirconium, obtained titaniferous and/or zirconium
Modified Y molecular sieve in, the content of IV B races metal is counted as 1~15 weight % using oxide, the IV B races metal for titanium and/or
(titanium is with TiO for zirconium2Meter, zirconium is with ZrO2Meter).
In the method for modifying of Y type molecular sieve provided by the present invention, the Y type molecular sieve (raw material) described in step (2) is for example
For HY, NH4Y, the Y molecular sieve of hydro-thermal ultra-steady Y molecular sieve and different content of rare earth is one kind in the Y type molecular sieve containing rare earth
Or a variety of, the Y molecular sieves containing rare earth such as REY, REHY, RE NH4One in hydro-thermal ultra-steady Y molecular sieves of the Y containing rare earth
Kind or more in.Can be a friendship one roasting Y molecular sieve, two friendships, two roasting Y molecular sieves, two friendships, one roasting Y molecular sieve.The super steady Y of hydro-thermal
Molecular sieve is super-stable Y molecular sieves prepared by hydrothermal dealumination method.The Y molecular sieve is commercially available, such as DASY
(0.0)、DASY(2.0)；It can also be prepared according to existing method, such as according to C.V.Dvid etc. in Zeolite Chemistry
It is prepared by and Catalysis, ACS Monograph 171,285-331, Washington D.C., 1976 methods proposed.
In the method for modifying of Y type molecular sieve provided by the present invention, by Y type molecular sieve (raw material) and step in step (2)
(1) when gained mixture mixing, stirring at least 10 minutes are, for example, 0.5~12 small, temperature (the stirring temperature of mixture during stirring
Degree) it is 0~100 DEG C of for example, room temperature~95 DEG C；Preferably, mixing time for 0.5~12 it is small when, such as 0.5~4 it is small when.One
Kind embodiment, step (2) preferred room temperature~80 DEG C of the whipping temp, such as 1~3 is small when mixing time preferably 0.5~4 is small
When.
In the method for modifying of Y type molecular sieve provided by the present invention, obtained mixture can be straight after step (2) stirring
Roasting is connect, obtained solid product is roasted or will roasted after step (2) drying after can also being filtered,
Or filter and roasted after drying.
In the method for modifying of Y type molecular sieve provided by the present invention, in step (3), the temperature of roasting is 300~700 DEG C,
More than when roasting time preferably 0.5 is small, when being, for example, 0.5~12 small.Preferably, the calcination temperature is 400~650 DEG C, roasting
When the burning time preferably 1~6 is small；Such as calcination temperature is 450~650 DEG C, when roasting time is 2~5 small.The roasting can be
Carry out to carry out under steam-laden atmospheric condition in air atmosphere, 1~100 is contained in the steam-laden atmosphere
Volume % vapor, preferably comprises 20~100 volume % water vapours, more preferably 100% water vapour atmosphere.
The method of modifying of Y type molecular sieve provided by the invention, can obtain the molecular sieve of high activity, high stability.Such as
The modified Y molecular sieve containing 3.8 weight % zirconiums that the prior art is prepared in water environment is in 800 DEG C, 100% vapor burin-in process
17 it is small when after crystallization reservation degree be 45.9%, far below 50%, and close zirconium content prepared by method provided by the invention
Modified Y molecular sieve 800 DEG C, 100% vapor burin-in process 17 it is small when after crystallization reservation degree be 58.4%, be far above
50%, show its hydrothermal stability with higher.Obtained titaniferous and/or the Modified Zeolite Y of zirconium obtains than existing methods
The Modified Zeolite Y containing IV B races metal arrived has the heat and hydrothermal stability of higher.
The modified Y molecular sieve prepared by the present invention, the IV B races metal containing 1~15 weight %, the IV B races metal
For titanium and/or zirconium, rare earth can be used without using rare earth or less, reaches the heat of even more high suitable with rare earth modified Y molecular sieve
And hydrothermal stability.Its production procedure more optimizes, and production cost is lower.Modified Y zeolite provided by the invention can be used for making
Standby catalytic cracking catalyst, and then reacted for hydrocarbon oil catalytic cracking, the yield of gasoline of rare earth modified Y zeolites can be reached and turned
Change activity, or even there is more preferable effect.
Embodiment
The following examples illustrate the present invention further, it is intended to helps reader to more fully understand the reality of the present invention
Where matter and caused beneficial effect, but should not be construed as to the present invention can practical range any restriction.
In each embodiment and comparative example, the lattice constant (cell parameter) and crystallinity of zeolite use PHILIPS X '
Pert types x-ray powder diffraction instrument measures, Cu K alpha rays, tube voltage 40kV, tube current 40mA, 2 °/min of sweep speed, scanning
2 θ=5~70 ° of scope；Wherein crystallize the ratio that reservation degree is crystallinity and crystallinity before aging after zeolite aging, specific surface area
Reservation degree be zeolite aging before with the ratio after aging.Constituent content is by x-ray fluorescence spectrometry.Crystal structure avalanche temperature
Degree is measured by differential thermal analysis (DTA).
Chemical reagent used does not indicate especially in comparative example and embodiment, its specification is pure for chemistry.Embodiment and contrast
NaY molecular sieve (also referred to as NaY zeolite) used, asphalt in Shenli Refinery of sinopec catalyst Co., Ltd (also referred to as Shandong catalyst in example
Factory) product, Si/Al molar ratios are 2.5, Na2O content is 12.8 heavy %, cell parameter α0=2.466nm, 75 weight % of butt.
DASY (0.0) molecular sieve used, is asphalt in Shenli Refinery of sinopec catalyst Co., Ltd product, and Si/Al molar ratios are 6.1,
Na2O content is 1.2 heavy %, cell parameter α0=2.448nm, 86 weight % of butt.Dilute hydrochloric acid concentration used is 15 weight %, institute
With weak aqua ammonia concentration (with NH3Meter) it is 5 weight %.
Comparative example 1
This comparative example illustrates that conventional aqueous exchange process prepares modified zirconia Y molecular sieve.
200g (dry basis) NaY molecular sieve is taken, after being beaten with 2000g deionized waters, 60g ammonium sulfate is added, uses dilute hydrochloric acid
Adjust pH=3.8, be warming up to 85 DEG C exchange 1 it is small when, filter and be washed with deionized, then by filter cake 650 DEG C, 100%
When roasting 2 is small in vapor, the hydro-thermal ultra-steady Y molecular sieve of a friendship one roasting is obtained, is denoted as DY1-1.
Above-mentioned molecular sieve is placed in 2000g deionized waters and is stirred evenly, 27.9g zirconium nitrates Zr is added into above-mentioned slurries
(NO3)4·5H2O, be warming up to 90 DEG C continue stirring 3 it is small when, after filtering by filter cake be placed in 100 DEG C of baking ovens dry 12 it is small when, so
When roasting 2 is small in 650 DEG C, 100% vapor afterwards, the Y molecular sieve of modified zirconia is obtained, is denoted as DY1, its property is shown in Table 1.
Comparative example 2
This comparative example illustrates that conventional aqueous infusion process prepares titanium modified Y molecular sieve.
51.2g butyl titanates are dissolved in 200g deionized waters maceration extract is made, gained maceration extract and 200g (butts
DY1-1 molecular sieves are uniformly mixed again), are stood 12h at room temperature when drying 8 is small in 100 DEG C of baking ovens, are then roasted at 500 DEG C
Burn 3 it is small when, obtain titanium modification Y molecular sieve, be denoted as DY2, its property is shown in Table 1.
Embodiment 1
By 27.9g zirconium nitrate Zr (NO3)4·5H2O is dissolved in 500g deionized waters, is stirred evenly, and weak aqua ammonia is used at 26 DEG C
The pH value for adjusting mixture is 4.5, is then warming up to 40 DEG C, stirs 60min；The DY1-1 molecular sieves provided in comparative example 1 are provided
200g (dry basis) is added in said mixture, be sufficiently stirred at 40 DEG C 2 it is small when；After filtering, by gained filter cake 650
DEG C, when roasting 2 is small in 100% vapor, obtains the Y molecular sieve of modified zirconia, be denoted as Y1, its property is shown in Table 1.
Embodiment 2
51.2g butyl titanates are dissolved in 800g deionized waters, are stirred evenly, the pH value of mixture is adjusted with weak aqua ammonia
For 6.0,30min is then stirred at room temperature；The DY1-1 molecular sieves 200g (dry basis) provided in comparative example 1 is taken to be added to
State in mixture, be warming up to 60 DEG C, continue stirring 1 it is small when；After filtering, gained filter cake is roasted in 500 DEG C, 100% vapor
Burn 3 it is small when, obtain titanium modification Y molecular sieve, be denoted as Y2, its property is shown in Table 1.
Embodiment 3
By 10.5g zirconium oxychlorides ZrOCl2·8H2O is dissolved in 1800g deionized waters, is stirred evenly, and is adjusted with weak aqua ammonia mixed
The pH value of compound is 7.0, is warming up to 80 DEG C, stirs 20min；200g (dry basis) DASY (0.0) molecular sieve is taken to be added to above-mentioned
In mixture, continue at 80 DEG C stirring 2 it is small when；After filtering, it is small that gained filter cake is roasted in 450 DEG C, 100% vapor to 5
When, the Y molecular sieve of modified zirconia is obtained, is denoted as Y3, its property is shown in Table 1.
Embodiment 4
47.5g titanium tetrachlorides are dissolved in 300g deionized waters, are stirred evenly, the pH value that mixture is adjusted with weak aqua ammonia is
3.5,90min is stirred at room temperature；Take 200g (dry basis) DASY (0.0) molecular sieve to be added in said mixture, be warming up to 60
DEG C, continue stirring 3 it is small when；After filtering, gained filter cake is roasted in 600 DEG C, 100% vapor 2 it is small when, obtain titanium modification
Y molecular sieve, is denoted as Y4, its property is shown in Table 1.
Embodiment 5
200g (dry basis) NaY molecular sieve is taken, after being beaten with 2000g deionized waters, adds 270g/lRECl3The milli of solution 15
Rise, be warming up to 90 DEG C, when stirring 1 is small after add 50g ammonium sulfate, and adjust slurries pH=3.8 with dilute hydrochloric acid, 1 exchanged at 90 DEG C
Hour, filter and be washed with deionized, then filter cake is roasted in 600 DEG C, 100% vapor 2 it is small when, obtain a friendship one
The rare earth modified Y molecular sieve of roasting, is denoted as Y5-1.
By 17.1g butyl titanates and 13.9g zirconium nitrate Zr (NO3)4·5H2O is dissolved in 600g deionized waters, and stirring is equal
Even, the pH value that mixture is adjusted with weak aqua ammonia is 5.0, then stirs 30min at room temperature；By 200g (dry basis) Y5-1 point
Son sieve be added in said mixture, continue at room temperature stirring 1.5 it is small when；After filtering, by gained filter cake in 500 DEG C, 100% water
When roasting 3 is small in steam, the Y molecular sieve of titanium and modified zirconia is obtained, is denoted as Y5, its property is shown in Table 1.
Table 1
As can be seen from Table 1, compared with comparative example, modified Y molecular sieve prepared by 1~embodiment of embodiment 5,13 has
There is the lattice damage temperature of the specific surface area of bigger, the crystallinity of higher and higher, show prepared by method provided by the invention
Modified Y molecular sieve has higher heat endurance.
Embodiment 6~10
Embodiment 6~10 illustrates the hydrothermal stability of modified Y molecular sieve prepared by the present invention.
After when by the modified Y molecular sieve of the preparation of embodiment 1~5, aging 17 is small under 800 DEG C, 100% water vapor conditions, survey
Fixed its crystallinity and specific surface area, and crystallization reservation degree and specific surface area reservation degree are calculated, the results are shown in table 2.
And carry out light oil microactivity evaluation, using RIPP92-90 standard method (see《Petrochemical Engineering Analysis method》
(RIPP test methods) Yang Cui surely wait compile, Science Press, nineteen ninety publish) evaluation sample light oil microactivity, catalyst
Loading amount is 5.0g, and 460 DEG C of reaction temperature, feedstock oil is 235~337 DEG C of straight distillation light diesel oils of boiling range, and product is formed by gas-chromatography
Analysis, calculates light oil microactivity, the results are shown in table 2 according to product composition.
Light oil microactivity (MA)=(gasoline production+gas yield+coke output for being less than 216 DEG C in product)/charging
Total amount × 100%
Comparative example 3~4
After when by 1~2 modified Y molecular sieve of comparative example, aging 17 is small under 800 DEG C, 100% water vapor conditions respectively, measure
Its crystallinity and specific surface area, and crystallization reservation degree and specific surface area reservation degree are calculated, the results are shown in table 2.And according to embodiment 6
Method evaluation sample light oil microactivity, the results are shown in Table 2.
Table 2
From table 2 it can be seen that molecular sieve by 800 DEG C, 100% vapor aging 17 it is small when after, prepared by the present invention changes
Property Y molecular sieve have higher crystallization reservations degree and specific surface area reservation degree, with higher micro-activity.Show that the present invention carries
Modified Y molecular sieve prepared by the method for confession has the hydrothermal stability and activity of higher.
Embodiment 11
Method according to embodiment 1 prepares zirconium content (with ZrO2Meter) it is 1 weight %, 5 weight %, 10 weight %, 15 weights
The modified zirconia Y molecular sieve of % is measured, its physico-chemical property is shown in Table 3.After when aging 17 is small under 800 DEG C, 100% water vapor conditions, survey
Fixed its crystallinity and specific surface area, and crystallization reservation degree and specific surface area reservation degree are calculated, and evaluated according to the method for embodiment 6
The light oil microactivity of sample, the results are shown in Table 3.
Comparative example 5
200gNaY zeolites are taken, after being beaten with 2000g deionized waters, add 270g/l RECl328.2 milliliters of solution, use is dilute
Hydrochloric acid adjusts pH=4.5, be warming up to 80 DEG C exchange 1 it is small when, after filtration washing by filter cake when 500 DEG C of roastings 3 are small.Then by institute
Y zeolites are obtained with after the mashing of 2000g deionized waters, 45g ammonium sulfate is added, adjusts pH=3.6 with dilute hydrochloric acid, be warming up to 80 DEG C of exchanges
1 it is small when, then filter, wash, filter cake is roasted in 650 DEG C, 100% water vapour 2 it is small when.Obtain 5 weight % of content of rare earth
Rare earth modified Y zeolites.
According to above-mentioned existing method (adjustment content of rare earth) prepare content of rare earth for 1 weight %, 5 weight %, 10 weight %,
The rare earth modified Y molecular sieve of 15 weight %, its physico-chemical property are shown in Table 3.When aging 17 is small under 800 DEG C, 100% water vapor conditions
Afterwards, its crystallinity and specific surface area are measured, and calculates crystallization reservation degree and specific surface area reservation degree, and according to the side of embodiment 6
Method evaluates the light oil microactivity of sample, and the results are shown in Table 3.
Comparative example 6
According to the method for above-mentioned comparative example 5, re chloride is replaced with zirconium nitrate solution, obtains 1 weight % of zirconium content
Modified Y molecular sieve, its physico-chemical property is shown in Table 3.
Table 3
By table 3 as it can be seen that compared with rare earth modified Y molecular sieve, modified zirconia Y molecular sieve prepared by the method for the present invention has quite
Even preferable heat and hydrothermal stability, there is suitable even preferable micro-activity.
Embodiment 12
Modified Y molecular sieve Y1, the Y2 prepared respectively using the method provided by the present invention is split as active component according to conventional catalysis
Change catalyst method and prepare catalyst.Preparation method is as follows：According to molecular sieve (in terms of butt)：Kaolin (in terms of butt)：Intend
Boehmite is (with Al2O3Meter)：Aluminum sol is (with Al2O3Meter) it is 38：34：20：8 ratio, kaolin and decationized Y sieve water are beaten
Slurry is uniformly rear to add Aluminum sol, boehmite is separately added into the case where being stirred continuously, stir about is after 30 minutes, by containing molecular sieve
Slurries are added in colloid, and after remixing uniformly, spray drying forming, obtains catalyst, is denoted as C1, C2.
Catalyst first passes through 800 DEG C in advance, when 100% steam treatment 17 is small, then in small-sized fluidized bed evaluating catalyst
Evaluated on device (ACE), evaluate raw materials used oil and mix three to be military, its property is shown in Table 4.Reaction temperature, oil ratio (weight ratio) and
Evaluation result is listed in table 5.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Coke selectivity=100/ conversion ratios of coke yield *
Table 4
Comparative example 7
Cracking catalyst is prepared according to the method for embodiment 12, the difference is that replacing Y1 therein with equivalent DY1 molecular sieves
Molecular sieve, obtains catalyst, is denoted as DC1, and then DC1 is evaluated according to the method for embodiment 12.Evaluation result is shown in Table 5.
Comparative example 8
Prepare Cracking catalyst according to the method for embodiment 12, unlike with the rare earth modified Y molecular sieve of equivalent (according to
RE prepared by 5 method of comparative example2O3Content is the molecular sieve of 4.0 weight %) Y1 molecular sieves therein are replaced, catalyst is obtained, is remembered
For DC2, then DC2 is evaluated according to the method for embodiment 12.Evaluation result is shown in Table 5.
Table 5
| Numbering | Embodiment 12 | Comparative example 6 | Comparative example 7 |
| Catalyst | C1 | DC1 | DC2 |
| Reaction temperature, DEG C | 500 | 500 | 500 |
| Oil ratio | 8.04 | 8.04 | 8.04 |
| Product is distributed, % | |||
| Dry gas | 1.39 | 1.42 | 1.18 |
| Liquefied gas | 12.02 | 12.03 | 12.03 |
| Coke | 5.27 | 5.37 | 5.47 |
| Gasoline | 43.91 | 38.58 | 42.07 |
| Diesel oil | 19.48 | 19.33 | 18.35 |
| Heavy oil | 17.93 | 23.27 | 20.9 |
| Conversion ratio, % | 62.59 | 57.4 | 60.75 |
5 data of table can be seen that with using 6 phase of comparative example of molecular sieve prepared by aqueous solution exchange process for active component
Than the conversion ratio of catalyst provided by the invention, gasoline yield dramatically increase, and heavy oil cracking ability significantly improves.Change with rare earth
Property Y molecular sieve compared for the comparative example 7 of active component, catalyst provided by the invention has cracking capability and the gasoline production of higher
Rate.
Embodiment 13
Method according to embodiment 3 prepares molecular sieve, unlike, it is 9.5 that zirconium salt solution ammonium hydroxide, which adjusts pH value,.
By 10.5g zirconium oxychlorides ZrOCl2·8H2O is dissolved in 1800g deionized waters, is stirred evenly, and is adjusted with weak aqua ammonia mixed
The pH value of compound is 9.5, is warming up to 80 DEG C, continues to stir 20min；200g (dry basis) DASY (0.0) molecular sieve is taken to be added to
In said mixture, continue at 80 DEG C stirring 2 it is small when；After filtering, gained filter cake is roasted in 450 DEG C, 100% vapor
5 it is small when, obtain the Y molecular sieve of modified zirconia, be denoted as Y13, its property is shown in Table 1.
Claims (21)
1. a kind of method of modifying of Y type molecular sieve, wherein, this method comprises the following steps：
（1）The compound of titaniferous and/or zirconium is dispersed in water, the pH value for adding alkaline solution adjusting mixture is 4.5 ~ 10,
Zirconium ion and/or titanium ion is set to form hydroxide；
（2）Y type molecular sieve is mixed with mixture obtained by step (1), is stirred at least 10 minutes, optionally filtering and/or drying；
（3）Step（2）Obtained product is roasted at 300 ~ 700 DEG C, obtains the modified Y molecular sieve of titaniferous and/or zirconium.
2. in accordance with the method for claim 1, it is characterised in that step（1）The compound by titaniferous and/or zirconium is disperseed
In water, with TiO2And/or ZrO2The mass concentration of meter gained titaniferous and/or zirconium compounds mixture is 0.05% ~ 15%.
3. in accordance with the method for claim 1, it is characterised in that the compound of the titaniferous and/or zirconium for titanium compound,
One or more in the compound or titaniferous of zirconium and the compound of zirconium, the compound of the titanium is titanium sulfate, titanyl sulfate, four
One or more in titanium chloride, titanium trichloride, butyl titanate, tetraalkyl titanate, ammonium titanium fluoride, the compound of the zirconium
For the one or more in zirconium chloride, zirconium sulfate, zirconium nitrate, zirconium oxychloride, acetic acid zirconium, zirconium iso-propoxide.
4. in accordance with the method for claim 1, it is characterised in that step（1）The pH value is 4.5 ~ 7.
5. according to the method described in claim 1 or 4, it is characterised in that step（1）Mixture is adjusted by adding alkaline solution
PH value, the mass concentration of the alkaline solution is 2 ~ 20 %.
6. in accordance with the method for claim 5, it is characterised in that the mass concentration of the alkaline solution is 3 ~ 15 %.
7. in accordance with the method for claim 5, it is characterised in that the alkaline solution is selected from ammonium hydroxide, water glass solution, inclined aluminium
One or more in acid sodium solution or sodium hydroxide solution.
8. in accordance with the method for claim 1, it is characterised in that step（1）In, the pH value for adjusting mixture is 4.5 ~ 10
Afterwards, stirred more than 10 minutes at being 0 ~ 100 DEG C in temperature.
9. in accordance with the method for claim 8, it is characterised in that step（1）In, the temperature of mixture is room during the stirring
Temperature ~ 90 DEG C, mixing time are 10 ~ 120 minutes.
10. according to the method described in claim 1 or 2, it is characterised in that step（2）In, in terms of titanium and/or Zirconium oxide
The mass ratio of mixture and the Y type molecular sieve in terms of butt is obtained by the step (1)（0.005~0.15）:1.
11. in accordance with the method for claim 1, it is characterised in that step（2）Described in Y type molecular sieve be HY, NH4Y, water
One or more in hot ultra-steady Y molecular sieve and Y type molecular sieve containing rare earth.
12. in accordance with the method for claim 1, it is characterised in that step（2）Described in stir and carried out at 0 ~ 100 DEG C.
13. in accordance with the method for claim 12, it is characterised in that step（2）When middle mixing time is 0.5 ~ 4 small.
14. in accordance with the method for claim 1, it is characterised in that step（3）Described in roast, 1 ~ 100 body is contained in atmosphere
Product % vapor.
15. in accordance with the method for claim 1, it is characterised in that step（3）Described in roasting time 0.5 ~ 6 it is small when.
16. in accordance with the method for claim 1, it is characterised in that step（3）The calcination temperature is 400 ~ 650 DEG C, roasting
When time is 1 ~ 5 small.
17. in accordance with the method for claim 1, it is characterised in that step（1）It is described to divide the compound of titaniferous and/or zirconium
Dissipate in water, with TiO2And/or ZrO2The mass concentration of meter gained titaniferous and/or zirconium compounds mixture is 0.4 ~ 6%.
18. in accordance with the method for claim 9, it is characterised in that step（1）In, the mixing time is 20 ~ 90 minutes.
19. in accordance with the method for claim 12, it is characterised in that step（2）Described in stirring at room temperature ~ 95 DEG C into
OK.
20. in accordance with the method for claim 13, it is characterised in that step（2）When middle mixing time is 1 ~ 3 small.
21. a kind of Modified Zeolite Y, the IV B races metal containing in terms of oxide 1 ~ 15 weight %, the IV B races metal is titanium
And/or zirconium, it is characterised in that the Modified Zeolite Y is prepared by any one of claim 1 ~ 20 the method.
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| CN106853973B (en) * | 2015-12-08 | 2019-08-06 | 中国石油天然气股份有限公司 | A kind of method for preparing strongly acidic Y-type molecular sieve |
| CN106669775B (en) * | 2016-11-28 | 2019-08-06 | 中国石油天然气股份有限公司 | A kind of Y/ZrO2 composite material synthesized by seed crystal method and preparation method thereof |
| CN107055567B (en) * | 2016-12-27 | 2021-10-08 | 常州大学 | A kind of preparation method of nano Y zeolite aggregate |
| CN107115886B (en) * | 2017-03-24 | 2019-10-11 | 中国石油天然气集团公司 | A kind of Y/ZrO2 composite material synthesized by two-stage crystallization method and its preparation method |
| CN112657549B (en) * | 2019-10-15 | 2023-08-08 | 中国石油化工股份有限公司 | Regenerated catalyst and preparation method and application thereof |
| CN114854092A (en) * | 2021-06-25 | 2022-08-05 | 安徽星贝达新材料科技有限公司 | High-efficiency deodorant as well as preparation method and application thereof |
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