CN104556120B - Preparation method of metal modified Y type molecular sieve - Google Patents
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Abstract
The invention discloses a preparation method of a metal modified Y type molecular sieve. The preparation method comprises the following steps: (1) treating the Y type molecular sieve with an acid solution; (2) dehydrating the treated Y type molecular sieve; (3) then dissolving a compound of modified metal elements in a buffer solution of ethyl alcohol-ammonium acetate-water so as to prepare impregnation liquid, mixing and impregnating the impregnation liquid and the molecular sieve obtained in the step (1), and calcining. Wherein modified metal is one or more of Fe, Cr, Ga, In, Tl, Sn and Co. The metal modified Y type molecular sieve obtained by the method is high in hydrothermal stability, and the productive rate for gasoline by cracking hydrocarbon oil is high.
Description
Technical field
The present invention relates to a kind of preparation method of metal-modified y type molecular sieve, it is furtherly to be related to one kind there is height
The preparation method of the metal-modified y type molecular sieve of hydrothermal stability.
Background technology
Research with regard to metal modified molecular screen is concentrated mainly on the high-silica zeolites such as zsm-, mcm-, ts- series at present
On.The synthesis of these metal modified molecular screens adopts hydrothermal synthesis method mostly, that is, during conventional hydrothermal synthesis of molecular sieve
Corresponding metallic compound is added in synthetic system.Metal current modified molecular screen by hydrothermal synthesis method or can pass through
Then Hydrothermal Synthesiss Si-Al molecular sieve introduces modified metal by the method for post-modification.Such as zsm-5 type Zeolite synthesis system
Ph value relatively low, metal heteroatom can in synthetic system stable existence, therefore, synthesis hetero atom zsm-5 molecular sieve can adopt
Use hydro-thermal method.And the ph value of y type Zeolite synthesis system is too high, metal heteroatom can occur intense hydrolysis to react, and y type divides
The silica alumina ratio of son sieve is relatively low, is difficult to metal heteroatom is incorporated in y type molecular sieve using hydrothermal synthesis method.
A kind of method synthesizing metal-modified y type molecular sieve is by metal heteroatom using liquid-solid phase solid lipid nanoparticles method
It is incorporated in y type molecular sieve.Cn1807243a provides one kind and prepares metal heteroatom modified molecules by solid phase isomorphous substitution
The method of sieve, can prepare the y type molecular sieve of high-crystallinity.Tang Yi etc. uses nh4bf4、(nh4)2tif6、(nh4)2zrf7、
(nh4)2fef6Have studied the liquid-solid phase solid lipid nanoparticles rule to y type molecular sieve for the hetero atoms such as ti, fe, zr for substituting agent, send out
Now in addition to b, other metals all can enter y zeolite (y molecular sieve) skeleton, and (" metallic element is same to the liquid-solid phase class matter of y zeolite
Brilliant replacement " " SCI " 1990,11 (12): 1317-1321).It is suitable that cn101134576a provides a kind of selection
When hetero atom carries out framework modification to y zeolite, improve y zeolite heat and the method for hydrothermal stability, the method is included using directly
Hydrothermal crystallizing synthetic method, adds appropriate hetero atom, the my type zeolite containing cage heteroatom for the preparation, my zeolite is carried out secondary
nh4 +Ion exchange and after baking, add hetero atom of the same race on a small quantity before second calcination process, obtain super steady heteroatom zeolite
Usmy, its heat stability and hydrothermal stability significantly improve than conventional usy zeolite.But its course of reaction is loaded down with trivial details, introduce miscellaneous
The type and quantity of atom are also very limited, and the hydrothermal stability of the y zeolite obtaining is not still high.
The other method preparing metal-modified y type molecular sieve includes liquid-phase ion exchange and infusion process, with respect to water
Thermal synthesis method and liquid-solid phase solid lipid nanoparticles method, the preparation process is simple of liquid-phase ion exchange and infusion process is it is easier to reality
Apply.Cn1350887a discloses one kind and contains noble metal and non-noble metal modification y type molecular sieve and preparation method thereof simultaneously, passes through
Nay Molecular sieve raw material is carried out with the step such as noble metal and non-noble metal ion exchange, hydrothermal treatment consists and ammonium salt exchange, finally makes
Obtain the noble metal containing 0.05 weight %～2.0 weight %, the non-noble metal modification y type molecular sieve of 0.5 weight %～15.0 weight %.
Cn1765492a discloses a kind of alumina support of the molecular sieve of type containing y and preparation method thereof, and wherein modified y type molecular sieve is to adopt
Carried out by way of cation exchange with vib race and/or viii race metal one or more of w, ni, co, fe, mo
Modified.Us2007010698a1 discloses a kind of carbon monoxide-olefin polymeric, comprises one kind lanthanide series and viiib race metal is handed over
The y type molecular sieve changing, described viiib race metal is mainly selected from platinum and palladium, using ion exchange and dipping method by lanthanide series
Saline solution and viiib race aqueous metal salt process y type molecular sieve.
However, because catalytic cracking reaction condition is harsh, there is high temperature and high water vapor it is desirable to be used as catalytic cracking
The y type molecular sieve of the active component of catalyst has very high heat and hydrothermal stability.But adopt traditional ionic liquid phase at present
Metal (such as one or more of fe, cr, ga, in, tl, sn, co) the modification y type that exchange process or dipping method are prepared divides
Son sieve hydrothermal stability poor, for catalytically cracked gasoline yield not high it is difficult to meet the requirement of catalytic cracking catalyst.
Content of the invention
The technical problem to be solved in the present invention is the problem existing for existing metal-modified y molecular sieve, provides a kind of tool
There is the preparation method of the metal-modified y type molecular sieve of high hydrothermal stability.
A kind of preparation method of metal-modified y type molecular sieve, the method comprises the following steps:
(1) y molecular sieve acid solution is processed；Described acid is organic acid and/or mineral acid；Y after acid treatment is divided
Son sieves makes the water in molecular sieve contain less than 400 DEG C of dehydration roastings for example at 200～400 DEG C to remove absorption water in temperature
Amount is not higher than 5 weight %；
(2) molecular sieve that step (1) is obtained impregnating metal in the buffer solution of ethanol-ammonium acetate-water；
(3) by the y molecular sieve of above-mentioned impregnating metal under 300～800 DEG C, 1～100% water vapour roasting 0.5～5 hour,
Metal-modified y type molecular sieve is obtained.
In the preparation method of metal-modified y type molecular sieve that the present invention provides, by the acid of y Molecular sieve raw material in step (1)
Processed, wherein said y molecular sieve, as raw material, be selected from nay, nanh4y、nh4Y, hy, usy, reusy, a friendship one
One or more of roasting y molecular sieve, two friendship two roasting y molecular sieves, two friendship one roasting y molecular sieve.Molten with acid described in step (1)
It can be to make y molecular sieve (in terms of butt) and acid solution in room temperature～100 DEG C according to the weight ratio of solid-to-liquid ratio 1:5～20 that liquid is processed
Lower contact at least 0.5 hour such as 0.5～3 hour, then filters, washs；In acid solution, the concentration of acid is with h+It is calculated as 0.1～
1mol/l, for example, for 0.2～0.5mol/l or can be 0.5～1mol/l.The available water such as deionized water of described washing,
Distilled water wash, can be for 5～20:1 with the mass ratio washing away the acid in zeolite, such as water and zeolite.Described mineral acid is for example
One or more of hydrochloric acid, sulphuric acid and nitric acid；Described organic acids such as one of formic acid, acetic acid, oxalic acid, citric acid or several
Kind, described acid solution is aqueous acid.
In the preparation method of metal-modified y type molecular sieve that the present invention provides, with the institute after acid solution process in step (1)
State na in molecular sieve2O content is preferably no greater than 4.0 weight %(in terms of butt), na in more preferably described molecular sieve2O content is not higher than
2.0 weight %.
Molecule in the preparation method of metal-modified y type molecular sieve that the present invention provides, after gained acid treatment in step (1)
Sieve can at 200～400 DEG C roasting to remove absorption water, described roasting makes water content in molecular sieve be not higher than 5 weight %,
For example it is not higher than 3 weight %, roasting time can be 2～10 hours;After roasting, the solid content (calcination alkali number) of molecular sieve is not less than
95 weight % are for example not less than 97 weight %, for example, can be 97～99 weight %.
In the preparation method of metal-modified y type molecular sieve that the present invention provides, step (1) being obtained described in step (2)
To molecular sieve impregnate modified metal in the buffer solution of ethanol-ammonium acetate-water, including by containing described modified metal element
Compound dissolution make impregnation liquid in the buffer solution of ethanol-ammonium acetate-water, according still further to the preferred equivalent of conventional impregnation methods
Molecular sieve obtained by step (1) is mixed by infusion process with described impregnation liquid, dip time 0.5～24 hour, then optionally dry
Dry.Can be immersed in by one or many and in y molecular sieve, introduce described modified metal, that is, described dipping can carry out once or
Repeatedly.
The present invention provide the preparation method of metal-modified y type molecular sieve in, the described modified metal of step (2) be selected from fe,
One or more of cr, ga, in, tl, sn, co etc., preferably one or more of fe, cr, ga.Modified metal amount (with
Oxide meter) account for 0.5～15 weight % of described metal-modified y type molecular sieve butt quality, preferably 1～10 weight %.
In the preparation method of metal-modified y type molecular sieve that the present invention provides, the described ethanol-ammonium acetate-water of step (2)
The preparation method of buffer solution can be mixed to get by ethanol, acetic acid, ammonia and water or mix ethanol, ammonium acetate and water
Merging acetic acid adjusts ph and is worth to.A kind of embodiment, ammonium acetate and second in the buffer solution of described ethanol-ammonium acetate-water
Than for 0.09～0.11:1, than for 17～21:1, ph value is 3～5 to the weight of alcohol for the weight of water and ethanol.The gold that the present invention provides
Belong in the preparation method of modified y type molecular sieve, described in step (2), the buffer solution of ethanol-ammonium acetate-water is by ethanol, water, second
Acid solution and ammonia are mixed to get, and wherein water and the volume ratio of ethanol are 12～20:1, the volume ratio of ethanol and acetic acid solution
For 3～5:1, it is 3～5 that the consumption of ammonia makes the ph value of the buffer solution obtaining, and the concentration of acetic acid solution is 4.5～5.5mol/
L, the concentration of ammonia is 8～11mol/l.Described in step (2), the ph value of the buffer solution of ethanol-ammonium acetate and water is 3～5,
Preferably ph value is 3.0～4.5, for example, 3.5～4.5.The buffer solution of described ethanol-ammonium acetate-water can be in accordance with the following methods
Preparation: by 4.5～5.5mol/l aqueous acetic acid 2.7～3.3 parts by volume, ethanol 10.5～13.5 parts by volume and water 160～200
Parts by volume mixes, and adjusting ph value with 9～11mol/l ammonium hydroxide aqueous solution is 3～5.The buffering of described ethanol-ammonium acetate-water
Solution also can be obtained by following methods: the mixing of the water of the ethanol of 12 ± 0.5 parts by volume and 180 ± 5 parts by volume, add 5 ±
Acetic acid aqueous solution 3 parts by volume of 0.2mol/l, the ph value adjusting solution with the ammonia of 10 ± 0.5mol/l is 3～5.
Another preparation method of buffer solution of described ethanol-ammonium acetate-water: by the ethanol of 12 parts by volume and 180 bodies
The water mixing of long-pending part, adds acetic acid solution 3 parts by volume of 5mol/l, and the ph value adjusting solution with the ammonia of 10mol/l is 3～5
Such as 3.5～4.5.
In the method that the present invention provides, in step (2), the salt of described modified metal compound such as modified metal is dissolved
Prepare impregnation liquid in described buffer solution, described modified metal compound can be selected from metal sulfate, nitrate, hydrochloric acid
The compound of one or more of the salts such as salt, such as ferrum can be iron sulfate, ferrous sulfate, ferric nitrate, iron chloride, protochloride
One or more of ferrum；The compound of chromium (cr) can be selected from one or more of chromic nitrate, chromic sulfate, chromium trichloride；
The compound of gallium (ga) can be selected from gallium chloride, Ganite (Fujisawa)., one or more of gallium sulfate；The compound of indium (in) can select
From indium chloride, indium nitrate, one or more of indium sulfate；The compound of thallium (tl) can be selected from thallium chloride, thallium nitrate, sulphuric acid
One or more of thallium；The compound of stannum (sn) can be selected from stannic chloride, nitric acid stannum, one or more of STANNOUS SULPHATE CRYSTALLINE；Cobalt
(co) compound can be selected from cobaltous chloride, cobalt nitrate, one or more of cobaltous sulfate.With or without crystallization in described salt
Water.
In the preparation method of metal-modified y type molecular sieve that the present invention provides, the described sintering temperature 300～800 of step (3)
DEG C, preferably 350～650 DEG C, roasting time 0.5～5 hour, preferably 1～5 hour, calcination atmosphere 1～100% water vapour, preferably
100% water vapour.
The metal-modified y type molecular sieve of the method preparation that the present invention provides, has higher degree of crystallinity, degree of crystallinity can reach
To more than 70%, after 800 DEG C, 100% steam treatment 8 hours, the crystallization reservation degree of molecular sieve is not less than 70%.The present invention carries
For metal-modified y type molecular sieve there is the crystal structure of conventional y type molecular sieve, modified metal is not found by xrd spectral characterization
The characteristic peak of oxide, shows that modified metal is not assembled in molecular sieve surface, metal ion is in molecular sieve surface high degree of dispersion
Or inside entrance molecular sieve.
The metal-modified y type molecular sieve preparation method that the present invention provides, the obtained more existing side of metal-modified y type molecule
The described metal-modified y type molecular sieve of method preparation has higher hydrothermal stability, and it is used for RFCC, catalysis activity
Significantly improve with residual oil cracking performance, liquid is received and improved, and gasoline yield improves, and liquefied gas yield improves.
Brief description
The xrd spectrogram of the metal-modified y type molecular sieve that Fig. 1 is prepared for the present invention.
Specific embodiment
The following examples illustrate the present invention further it is intended to help reader to more fully understand the reality of the present invention
Matter is located and the beneficial effect brought, but should not be construed as to the present invention can practical range any restriction.
In each embodiment and comparative example, the lattice constant (cell parameter) of molecular sieve and degree of crystallinity adopt philips x '
Pert type x-ray powder diffractometer measures, cu k alpha ray, tube voltage 40kv, tube current 40ma, 2 °/min of scanning speed, scanning
Scope 2 θ=5～70 °, wherein crystallization reservation degree are the ratio of the aging rear degree of crystallinity of molecular sieve and aging front degree of crystallinity, specific surface area
Reservation degree be molecular sieve aging after with aging front ratio.Constituent content is by x-ray fluorescence spectrum method for measuring.Crystal structure avalanche
Temperature is measured by differential thermal analysises (dta).Described room temperature can be 15-40 DEG C.
Raw materials used in embodiment and comparative example: nay molecular sieve, hydro-thermal super stable molecular sieve dasy (0.0) and one hand over one
Roasting y molecular sieve, is provided by Sinopec catalyst asphalt in Shenli Refinery, and property is shown in Table 1.
Embodiment 1
Under room temperature, take 150g (butt) dasy(0.0) molecular sieve, with the hydrochloric acid solution for 1.0mol/l for the molar concentration
1500ml mixes, and stirs 30 minutes, filters, uses 1500ml deionized water wash, obtain the y molecular sieve after acid treatment, its oxidation
Sodium content is 0.6 weight %；By the y molecular sieve after gained acid treatment at 300 DEG C roasting 3 hours, obtain solid content be 97 weight %
Molecular sieve, be designated as fz-1；
Take 12ml ethanol to add in 180ml deionized water, add 5mol/l aqueous acetic acid 3ml, use 10mol/l hydroxide
Aqueous ammonium adjusts solution ph to 3.7, then by 30.4g fe (no3)3·9h2O is dissolved in above-mentioned buffer solution, is soaked
Stain liquid, above-mentioned fz-1 molecular sieve is mixed homogeneously with impregnation liquid, stands 12h, dries roasting 2 under 650 DEG C, 100% water vapour
Hour, obtain final product ferrum modification y type molecular sieve (being designated as fe-y) of present invention offer, its physicochemical data is listed in table 2.
Embodiment 2
Under room temperature, take 200gnay molecular sieve (butt 75 weight %), with the hydrochloric acid solution for 0.5mol/l for the molar concentration
1500ml mixes, and stirs 30 minutes, filters, uses 1500ml deionized water wash, obtain the nay molecular sieve after acid treatment, its oxygen
Change sodium content is 1.5 weight %；By the nay molecular sieve after gained acid treatment at 300 DEG C roasting 3 hours, obtain solid content be 96
The molecular sieve (water content 4 weight %) of weight %, is designated as fz-2；
Take 12ml ethanol to add in 180ml deionized water, add 5mol/l aqueous acetic acid 3ml, adjusted with 10mol/l ammonia
Section solution ph, to 4.5, obtains buffer solution, by 37.6g cr (no3)3·9h2O is dissolved in above-mentioned buffer solution, is impregnated
Liquid, above-mentioned molecular sieve fz-2 is mixed homogeneously with this impregnation liquid, stands 12h, dries roasting 5 under 500 DEG C, 100% water vapour
Hour, obtain final product chromium modification y type molecular sieve (cr-y) of present invention offer, its physicochemical data is listed in table 2.
Embodiment 3
Take 200gnay molecular sieve (ibid), after the making beating of 1500 grams of deionized waters, add 45g ammonium chloride and 33.5ml
recl3Solution (its concentration is calculated as 270g/l with re2o3), rare-earth salts is (with re2o3Meter): ammonium salt: nay molecular sieve: deionized water
For 0.06:0.3:1:10, the ph value adjusting serosity is 3.8 to weight ratio, is warmed up to 80 DEG C and exchanges 2 hours, filters and use water wash,
Then by filter cake under 600 DEG C, 100% water vapour roasting 2 hours.Molecular sieve after roasting and molar concentration are 0.2mol/l
Sulfuric acid solution 1500ml mixing, stir 30 minutes, filter, use 1500ml deionized water wash, obtain the y molecule after acid treatment
Sieve, its sodium oxide content is 1.2 weight %；By the y molecular sieve after gained acid treatment at 350 DEG C roasting 3 hours, admittedly being contained
Measure the molecular sieve for 97 weight %, be designated as fz-3；
Take 12ml ethanol to add in 180ml deionized water, be subsequently adding 5mol/l aqueous acetic acid 3ml, use 10mol/l hydrogen
Oxidation aqueous ammonium adjusts solution ph to 5.0, obtains buffer solution, by 5.3gco (no3)2·6h2It is molten that o is dissolved in above-mentioned buffering
In liquid, obtain impregnation liquid, above-mentioned molecular sieve fz-3 mixed homogeneously with impregnation liquid, stand 0.5h, dry after 550 DEG C, 100%
Roasting 4 hours under water vapour, obtain final product cobalt improved y type molecular sieve (co-y) of present invention offer, and its physicochemical data is listed in table 2.
Embodiment 4
Under room temperature, 150g (butt) is taken to hand over a roasting y molecular sieve, with the oxalic acid solution for 0.1mol/l for the molar concentration
1500ml mixes, and stirs 30 minutes, filters, uses 1500ml deionized water wash, obtain the y molecular sieve after acid treatment, its oxidation
Sodium content is 1.1 weight %；By the y molecular sieve after gained acid treatment at 350 DEG C roasting 3 hours, obtain solid content be 98.5
The molecular sieve of weight %, is designated as fz-4；
Take 12ml ethanol to add in 180ml deionized water, be subsequently adding the aqueous acetic acid that molar concentration is 5mol/l
3ml, adjusts solution ph to 4.0 with 10mol/l ammonium hydroxide aqueous solution, by 33.4gga (no3)3·9h2O is dissolved in above-mentioned buffering
In solution, obtain impregnation liquid, above-mentioned molecular sieve fz-4 mixed homogeneously with this impregnation liquid, stand 6h, dry after 700 DEG C,
Roasting 1 hour under 100% water vapour, obtains final product gallium modification y type molecular sieve (ga-y) of present invention offer, and its physicochemical data is listed in table
2.
Embodiment 5
Take 200gnay molecular sieve (ibid), after 3000 grams of deionized water making beating, add 60g ammonium chloride, ammonium salt: nay divides
Son sieve: for 0.4:1:20, the ph value adjusting serosity is 3.8 to the weight of deionized water ratio, is warmed up to 80 DEG C and exchanges 2 hours, filters
And use water wash, then by filter cake under 600 DEG C, 100% water vapour roasting 2 hours.Molecular sieve after roasting is continued to use 3000
The making beating of gram deionized water, adds 60g ammonium chloride, proceeds second ion exchange, reaction temperature and time with hand over for the first time
That changes is essentially identical, is then filtered, washed and dried, the molecular sieve after being exchanged.Then by above-mentioned y molecular sieve with mole dense
Spend the citric acid solution 2000ml mixing for 0.6mol/l, stir 40 minutes, filter, use 2000ml deionized water wash, obtain
Y molecular sieve after acid treatment, its sodium oxide content is 0.5 weight %；By the y molecular sieve roasting at 350 DEG C after gained acid treatment
3 hours, obtain the molecular sieve that solid content is 98 weight %, be designated as fz-5；
Take 12ml ethanol to add in 180ml deionized water, be subsequently adding 5mol/l aqueous acetic acid 3ml, use 10mol/l hydrogen
Oxidation aqueous ammonium adjusts solution ph to 3.5, is subsequently adding 17.5g tlno3, dissolving obtain impregnation liquid, by this impregnation liquid with
Above-mentioned molecular sieve fz-5 mix homogeneously, stands 12h, dries roasting 3 hours under 500 DEG C, 100% water vapour, obtains final product the present invention
Thallium modification y type molecular sieve (tl-y) providing, its physicochemical data is listed in table 2.
Comparative example 1
This comparative example illustrates the metal-modified y molecular sieve of conventional aqueous infusion process preparation.
Method according to embodiment 1 prepares molecular sieve, except for the difference that: dasy(0.0) molecular sieve is without peracid treatment；Will
30.4g fe(no3)3·9h2O is dissolved in deionized water and obtains impregnation liquid, by above-mentioned dasy(0.0) molecular sieve mixed with impregnation liquid
Uniformly, stand 12h, dry under 650 DEG C, 100% water vapour roasting 2 hours, obtain final product contrast molecular sieve, be labeled as fe (w)-
Y, its physicochemical data is listed in table 2.
Comparative example 2
According to the method for embodiment 4, except for the difference that: take 150g (butt) to hand over a roasting y molecular sieve, without peracid treatment；
By 33.4g ga (no3)3·9h2O is dissolved in described buffer solution and obtains impregnation liquid, and above-mentioned molecular sieve is mixed with impregnation liquid
Uniformly, stand 6h, dry roasting 1 hour under 700 DEG C, 100% water vapour, the contrast molecular sieve of present invention offer, mark are provided
It is designated as ga (w)-y, its physicochemical data is listed in table 2.
Table 1
| Raw material | nay | dasy(0.0) | One hands over a roasting |
| Elementary composition, weight % | |||
| na2o | 12.8 | 1.2 | 3.7 |
| al2o3 | 21.9 | 23.6 | 23.4 |
| sio2 | 64.4 | 71.7 | 72.0 |
| Lattice constant, nm | 2.466 | 2.448 | 2.453 |
| Degree of crystallinity, % | 81.6 | 65.6 | 78.0 |
| Total specific surface area, m2/g | 762 | 620 | 644 |
| Total pore volume, ml/g | 0.377 | 0.353 | 0.352 |
The physicochemical data of the modified y type molecular sieve of table 2
In table 2, w% refers to weight percentage.
As can be seen from Table 2, compared with comparative example modified molecular screen, the metal of the method preparation that the present invention provides changes
Property y type molecular sieve has higher degree of crystallinity (being not less than 70%), and has higher molecular sieve lattice damage temperature, shows
The metal-modified y type molecular sieve of present invention preparation has higher heat stability.
Embodiment 6～10
Embodiment 6～10 illustrates the hydrothermal stability of the modified y type molecular sieve of present invention preparation.
By the modified y type molecular sieve of embodiment 1～5 preparation respectively aging 8 hours under the conditions of 800 DEG C, 100% water vapour
Afterwards, measure its degree of crystallinity and specific surface area, calculate crystallization reservation degree and specific surface area reservation degree, and to described modification y type molecule
Sieve carries out light oil microactivity evaluation.Using ripp92-90 standard method (see " Petrochemical Engineering Analysis method " (ripp test
Method) Yang Cui surely waits and compiles, Science Press, nineteen ninety publishes) and evaluate the light oil microactivity of sample, catalyst loading amount is
5.0g, 460 DEG C of reaction temperature, raw oil is 235～337 DEG C of straight distillation light diesel oils of boiling range, and product forms by gas chromatographic analysiss, root
Calculate light oil microactivity according to product composition, result is listed in table 3.
Light oil microactivity (ma)=(being less than 216 DEG C of gasoline production+gas yield+coke output in product)/enter
Material total amount × 100%.
Comparative example 3～4
By modified for comparative example 1～2 y type molecular sieve respectively aging 8 hours under the conditions of 800 DEG C, 100% water vapour after, survey
Its degree of crystallinity fixed and specific surface area, and calculate crystallization reservation degree and specific surface area reservation degree, result is listed in table 3.
And the light oil microactivity of the method evaluation sample according to embodiment 6, the results are shown in Table 3.
From table 3 it can be seen that compared with comparative example, 800 DEG C, 100% steam aging is after 8 hours, the present invention provides
Modified y type crystallization of molecular sieves reservation degree improves 10～15 percentage points, and specific surface area reservation degree improves 10～15 percentages
Point, micro-activity improves 5～12 percentage points.Show the metal-modified y type molecular sieve of method preparation provided by the present invention
There is more preferable hydrothermal stability and light oil microactivity.
The hydrothermal stability of the modified y type molecular sieve of table 3
Embodiment 11～15
The metal-modified y type molecular sieve that embodiment 11～15 explanation is prepared with the inventive method is prepared for active component
The performance of catalytic cracking catalyst.
According to molecular sieve (in terms of butt): Kaolin (in terms of butt): boehmite is (with al2o3Meter): Alumina gel (with
al2o3Meter) for 38:34:20:8 ratio, by Kaolin and decationized Y sieve water making beating uniformly afterwards add Alumina gel, be stirred continuously
Under be separately added into boehmite, stir about, after 30 minutes, the serosity containing molecular sieve is added in colloid, remixes uniformly
Afterwards, spray drying forming, obtains catalyst.
Respectively with molecular sieve fe-y, cr-y, co-y, ga-y, tl-y as active component, prepare catalyst c1, c2, c3, c4,
c5.
Respectively in the upper evaluation of small-sized fluidized bed catalyst test apparatus (ace) through 800 DEG C, 100% steam aging 8 hours
Catalyst c1～c5 afterwards, evaluates raw materials used oil for military mixed three, its property is shown in Table 4.Reaction temperature, oil ratio (weight ratio),
Weight space velocity (weight (hourly) space velocity (WHSV)) and evaluation result are listed in table 5.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield.
Comparative example 5～6
The catalysis that the metal-modified y type molecular sieve that comparative example 1～2 is obtained is prepared by comparative example 5～6 explanation for active component
The performance of Cracking catalyst.
According to the method for embodiment 11, respectively with molecular sieve fe (w)-y, ga (w)-y as active component, prepare catalyst
Dc1～dc2.
Method according to embodiment 11 evaluates comparative catalyst dc1～dc2, and reaction result is listed in table 5.
Comparative example 7
According to the method for embodiment 2, except for the difference that by 30.4g fe (no3)3·9h2O is dissolved in deionized water and being impregnated
The dasy(0.0 through peracid treatment described in immersion stain) molecular sieve.Molecular sieve must be contrasted, be labeled as fe (w2)-y, its materialization number
According to being listed in table 2.
Comparative example 8
According to the method for embodiment 11, with molecular sieve fe (w2)-y as active component, prepare catalyst dc3.
Method according to embodiment 11 evaluates comparative catalyst dc3, and reaction result is listed in table 5.
Table 4
Table 5
As can be seen from Table 5, the catalyst that the present invention provides has a relatively low heavy oil yield, higher total liquid yield, illustrate by
The molecular sieve of present invention preparation is that the catalyst of active component has higher heavy oil conversion performance.It can be seen that, by the inventive method
The metal-modified y type molecular sieve of preparation can significantly improve the product slates of catalyst, improves the cracking activity of catalyst, gasoline
Yield increases substantially.
Claims (12)
1. a kind of preparation method of metal-modified y type molecular sieve, the method comprises the following steps:
(1) y type molecular sieve is processed with acid solution, described acid is organic acid and/or mineral acid；By the y molecule after acid treatment
Sieve and be less than 400 DEG C of dehydrations in temperature, make the water content in molecular sieve be not higher than 5 weight %；
(2) molecular sieve that step (1) is obtained impregnating metal in the buffer solution of ethanol-ammonium acetate-water；
(3) by the y molecular sieve of above-mentioned impregnating metal under 300～800 DEG C, 1～100% water vapour roasting 0.5～5 hour, system
Obtain metal-modified y type molecular sieve.
2. in accordance with the method for claim 1 it is characterised in that the y molecular sieve described in step (1) is selected from nay, nanh4y、
nh4Y, hy, usy, reusy, a friendship one roasting y molecular sieve, two friendship two roasting y molecular sieves, two friendships one roast one of y molecular sieve or many
Kind.
3. in accordance with the method for claim 1 it is characterised in that the process described in step (1) be according to solid-to-liquid ratio 1:5～
The weight ratio of 1:20 make y molecular sieve and acid solution contact at room temperature～100 DEG C 0.5～3 little when, then filter, washing, acid is molten
In liquid, the concentration of acid is with h+It is calculated as 0.1～1mol/l.
4. in accordance with the method for claim 1 it is characterised in that described in step (1) in temperature be less than 400 DEG C dehydration
It is by the y molecular sieve roasting at 200～400 DEG C after described acid treatment, roasting time is 2～10 hours.
5. in accordance with the method for claim 1 it is characterised in that metal described in step (2) be fe, cr, ga, in, tl,
One or more of sn, co, in terms of oxide, the content of described modified metal accounts for 0.5～15 weight of this molecular sieve butt weight
Amount %.
6. according to the metal-modified y type molecular sieve described in claim 1 or 5 preparation method it is characterised in that in step (2)
The molecular sieve that step (1) is obtained impregnating metal in the buffer solution of ethanol-ammonium acetate-water is: with described modified metal
The molecular sieve dipping that the solution that the buffer solution of compound and described ethanol-ammonium acetate-water is formed and step (1) obtain, institute
The modified metal compound stated is the sulfate of described modified metal, one or more of nitrate, hydrochlorate, described salt
In with or without water of crystallization.
7. according to the metal-modified y type molecular sieve described in claim 6 preparation method it is characterised in that described modified gold
Belong to compound be the compound of ferrum, the compound of chromium, the compound of gallium, the compound of indium, the compound of thallium, the compound of stannum,
One or more of compound of cobalt；The compound of described ferrum is iron sulfate, ferrous sulfate, ferric nitrate, iron chloride, protochloride
One or more of ferrum；The compound of chromium is selected from one or more of chromic nitrate, chromic sulfate, chromium trichloride；The chemical combination of gallium
Thing is selected from gallium chloride, Ganite (Fujisawa)., one or more of gallium sulfate；The compound of indium is selected from indium chloride, and indium nitrate, in indium sulfate
One or more；The compound of thallium is selected from thallium chloride, thallium nitrate, one or more of thallium sulfate；The compound of stannum is selected from
Stannic chloride, nitric acid stannum, one or more of STANNOUS SULPHATE CRYSTALLINE；The compound of cobalt is selected from cobaltous chloride, cobalt nitrate, one of cobaltous sulfate
Or it is multiple, with or without water of crystallization in described salt.
8. according to the metal-modified y type molecular sieve described in claim 1 preparation method it is characterised in that being changed with described metal
On the basis of the butt weight of property y type molecular sieve, in terms of oxide, modified metal described in described metal-modified y type molecular sieve contains
Measure as 1～10 weight %.
9. in accordance with the method for claim 1 it is characterised in that buffer solution is by ethanol, water, acetic acid described in step (2)
Solution and ammonia are mixed to get, and wherein water and the volume ratio of ethanol are 12～20:1, and ethanol is 3 with the volume ratio of acetic acid solution
～5:1, it is 3～5 that the consumption of ammonia makes the ph value of the buffer solution obtaining, and the concentration of acetic acid solution is 4.5～5.5mol/l, ammonia
The concentration of water is 8～11mol/l.
10. in accordance with the method for claim 1 it is characterised in that the buffer solution of described ethanol-ammonium acetate-water according to
Lower section method preparation: by 4.5～5.5mol/l aqueous acetic acid 2.7～3.3 parts by volume, ethanol 10.5～13.5 parts by volume and water
160～200 parts by volume mixing, adjusting ph value with 9～11mol/l ammonium hydroxide aqueous solution is 3～5.
11. in accordance with the method for claim 1 it is characterised in that the buffer solution of described ethanol-ammonium acetate-water is by following
Method obtains: the water mixing of the ethanol of 12 ± 0.5 parts by volume and 180 ± 5 parts by volume, adds the acetic acid solution 3 of 5 ± 0.2mol/l
Parts by volume, the ph value adjusting solution with the ammonia of 10 ± 0.5mol/l is 3～5.
12. according to the method described in claim 1,10 or 11 it is characterised in that the buffer solution of described ethanol-ammonium acetate-water
Than for 0.09～0.11:1, than for 17～21:1, ph value is 3～5 to the weight of middle ammonium acetate and ethanol for the weight of water and ethanol.
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| CN110833849B (en) * | 2018-08-17 | 2021-03-12 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method and application thereof |
| CN110835113B (en) * | 2018-08-17 | 2021-08-06 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN110833853B (en) * | 2018-08-17 | 2021-04-06 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN110833857B (en) * | 2018-08-17 | 2021-04-06 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833854B (en) * | 2018-08-17 | 2021-03-12 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833856B (en) * | 2018-08-17 | 2022-05-03 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN110833863B (en) * | 2018-08-17 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| US11691132B2 (en) * | 2018-08-17 | 2023-07-04 | China Petroleum & Chemical Corporation | Modified Y-type molecular sieve, catalytic cracking catalyst comprising the same, their preparation and application thereof |
| CN110833855B (en) * | 2018-08-17 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833851B (en) * | 2018-08-17 | 2021-04-06 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833861B (en) * | 2018-08-17 | 2022-05-03 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN110833850B (en) * | 2018-08-17 | 2021-03-12 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833860B (en) * | 2018-08-17 | 2022-05-03 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833852B (en) * | 2018-08-17 | 2021-04-06 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation method and application thereof |
| CN110833859B (en) * | 2018-08-17 | 2021-03-12 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method and application thereof |
| CN110833858B (en) * | 2018-08-17 | 2021-04-06 | 中国石油化工股份有限公司 | Modified Y-type molecular sieve and preparation method thereof |
| CN112209402B (en) * | 2019-07-12 | 2022-08-12 | 中国石油化工股份有限公司 | Ion exchange method for alkali metal-containing molecular sieve |
| CN115106120B (en) * | 2022-06-14 | 2024-01-19 | 天津大学 | Dehydrogenation catalyst, preparation method and application thereof |
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