CN106925335A - A kind of catalytic cracking catalyst of preventing from heavy metal and preparation method thereof - Google Patents
A kind of catalytic cracking catalyst of preventing from heavy metal and preparation method thereof Download PDFInfo
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- CN106925335A CN106925335A CN201511020504.0A CN201511020504A CN106925335A CN 106925335 A CN106925335 A CN 106925335A CN 201511020504 A CN201511020504 A CN 201511020504A CN 106925335 A CN106925335 A CN 106925335A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/24—After treatment, characterised by the effect to be obtained to stabilize the molecular sieve structure
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Abstract
A kind of catalytic cracking catalyst of preventing from heavy metal and preparation method thereof.The catalyst is calculated with catalyst quality as 100%, contains binding agent of inorganic oxide and 5~20% of clay, 0~40% of other molecular sieves, 10~80% of 10~55% modified molecular screen, 0~45% in terms of butt in terms of butt in terms of butt in terms of oxide in terms of oxide；Described modified molecular screen is obtained by following preparation methods, NaY molecular sieve is first exchanged with ammonium ion, compound of the mixing containing III B element in the periodic table of elements after filtering, it is not scrubbed to be directly spray-dried and hydrothermal calcine, then exchanged with ammonium salt again, and make to contain the anion that III B element can be made to produce precipitation in the exchange slurries, carried out after filtering or do not carry out hydrothermal calcine.Catalyst disclosed by the invention has excellent activity stability, cracking reaction selectivity and preventing from heavy metal pollution performance.
Description
Technical field
It is more particularly to a kind of with excellent activity stability the present invention relates to a kind of catalytic cracking catalyst
With the catalytic cracking catalyst of preventing from heavy metal pollution performance.
Background technology
Crude oil heaviness, in poor quality degree are increasingly sharpened, highly-efficient processing heavy oil, mix refining residual oil turn into oil refining look forward to
Industry improves working ability, obtains the active demand of more high profit.Catalytic cracking is the most important work of processing of heavy oil
Skill, because its heavy oil transformation efficiency is high, good product quality, non-hydrogen and the low significant advantage of operating pressure,
It is occupied very important status in refinery's processing heavy oil technique, be the main source of oil plant profit.
According to statistics, current whole world catalytic cracking unit has 420 sets or so, and single set catalytic cracking unit scale is most
Greatly up to 10,000,000 tons/year, about 7.37 hundred million tons of total working ability occupies the first place of secondary operation.
Due to the macromolecular compound of coke is easily produced in heavy oil and residual oil containing colloid, asphalitine etc., and
And containing heavy metal nickel, vanadium etc., cause on catalytic cracking equilibrium catalyst nickel content of vanadium in 10000 μ g/g
It is relatively common, and the up to serious pollution of 15000 μ g/g is not also rare, vanadium is in catalytic cracking high temperature hydro-thermal ring
The structure of the molecules of active components sieve under border in heavy damage catalyst, causes catalyst activity to reduce, and makes to urge
Change cracked product distribution to be deteriorated.Accordingly, it would be desirable to develop with excellent activity, hydrothermal stability and an anti-huge sum of money
Belong to the catalyst of pollution, to meet the strict demand of heavy oil, slag oil cracking to catalyst performance.
It is general in the prior art to use rare earth or phosphorus to molecular sieve in order to improve the activity and stability of catalyst
Or catalyst is modified treatment, such as Chinese patent CN1169717C discloses a kind of Y zeolites rare earth
Method and product that ion is modified, the method NaY molecular sieve is raw material, is first exchanged through ammonium, so
Laggard water-filling heat treatment, then with containing H+、NH4 +And RE3+Solution treatment after, it is scrubbed, drys, roast
Burn, obtain modified molecular screen product.Chinese patent CN1111136 C disclose the Y of a kind of phosphorous and rare earth
The preparation method of type molecular sieve, is, first with ammonium ion and rare earth ion exchanged, to be roasted NaY molecular sieve
Burn, then the P with 1~10 weight % in phosphorus compound reaction bonded2O5, then be calcined.It is Chinese special
Sharp CN1209288 C disclose the preparation method of the faujasite of a kind of phosphorous and rare earth, are to boil octahedral
After stone first carries out an exchange reaction with ammonium compounds and phosphorus compound, then rare earth is introduced in slurries are exchanged
Solution further reacts, and through filtering, washing, then is calcined.Catalyst activity containing the zeolite is steady
Qualitative good, yield of gasoline is high, and coke yield is low, and heavy oil cracking ability and preventing from heavy metal pollution ability are strong.In
State patent CN1026225 C disclose a kind of preparation method of rare-earth Y molecular sieve, are by NaY molecular sieve
After carrying out ion exchange in aqueous with rare earth ion, filtering, filter cake is roasted in the water vapour of flowing
Burning is obtained.Chinese patent CN1069553 C disclose a kind of method for preparing rare earth Y type molecular sieve, are
After NaY molecular sieve and rare earth ion are carried out into ion exchange, filtering, filter cake is calcined again, after roasting
Product 1~40% be recycled back into continuing operations described above in next group rare earth exchanged slurries, remaining
It is used to prepare catalyst as REY zeolite products, is so carried out continuously, obtains rare earth Y type molecular sieve.
Chinese patent CN103058217 A disclose a kind of preparation method of the Y molecular sieve containing rare earth, the method
It is raw material with NaY molecular sieve, is first exchanged through ammonium, then carries out hydro-thermal process, then with containing H+、NH4 +、
RE3+After the mixed solution treatment of organic solvent, mother liquor is separated, filter cake roasting, obtains modified molecular screen product
Product.Chinese patent CN1159101 C disclose a kind of preparation method of super-stable Y zeolite containing rare-earth elements, the party
Method mixes the overstable gamma zeolite that sodium oxide content is 3~5 weight % with a kind of rare earth compound solution, system
Into a kind of slurries, the slurries that will be obtained are in shear stress at least 10 kilograms per centimeters2Under conditions of grind at least 1
Minute, obtain modified molecular screen product.The method prepare zeolite have hydrothermal stability high, anti-sodium and
The ability of preventing from heavy metal pollution.
Existing Y type molecular sieve technology of preparing, solves deficiency of the molecular sieve in terms of some, meets point
Sub- sieve catalyst demand in some aspects, but prior art is after the rare earth ion exchanged of molecular sieve, typically
By filtering, filter cake carries out calcination process, and so resulting in rare earth all can not exchange on molecular sieve
Go, a part of rare earth enters filtrate and is lost in, and rare earth utilization rate is not high.Prior art or in rare earth exchanged
It is preceding just to carry out hydrothermal calcine, cause molecular sieve structure to destroy more, molecular sieve activity decrease.Repeatedly will roasting
1~40% of molecular sieve product after burning is recycled back into proceeding treatment in next group rare earth exchanged slurries
Operation, the problems such as cause preparation of molecular sieve complicated, energy waste and molecular sieve yield to reduce.Molecular sieve
In preparation process new problem of environmental pollution can be brought using organic solvent.In addition, the Y molecules containing rare earth
Sieve has that filtering is difficult, is restricted the continuity produced in industrial processes, reduces containing dilute
The production capacity of native molecular sieve.Therefore, in order to meet activity, the water of heavy oil and slag oil cracking to molecular sieve catalyst
The requirement of heat endurance and preventing from heavy metal pollution ability, meets cleaning and continuity for molecular sieve preparation process
It is required that, despite recent molecular sieve technology of preparing, but still need III B such as preparation technology environmental protection, rare earth
Element utilization rate is high or does not lose, and process is simple is feasible, at the same have excellent activity, hydrothermal stability and
The molecular sieve new preparation technology and corresponding catalyst preparation technology of preventing from heavy metal pollution.
The content of the invention
The purpose of the present invention is that the deficiency for avoiding above-mentioned technology, there is provided a kind of different from existing method divides
Son sieve and method for preparing catalyst, the Y type molecular sieve preparation process obtained by the inventive method, containing III B element
Molecular sieve pulp easily filter, III B element is not lost substantially, and molecular sieve technology of preparing is more environmentally-friendly；This
The catalytic cracking catalyst for providing, its preparation process is simple, with excellent activity stability, cracking are provided
Reaction selectivity and preventing from heavy metal pollution performance.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, is 100% with catalyst quality
Meter, contains other molecules of 10~55% Modified Zeolite Y, 0~45% in terms of butt in terms of butt
Sieve, inorganic oxide of 10~80% clay, 0~40% in terms of butt in terms of oxide and 5~20% with
The binding agent of oxide meter；Described Modified Zeolite Y is by the preparation side including following preparation processes
Method is obtained：NaY molecular sieve is first exchanged with ammonium ion, and mixing is containing III B element in the periodic table of elements after filtering
Compound, it is not scrubbed to be directly spray-dried and hydrothermal calcine, then exchanged with ammonium salt again, and make this
Containing the anion that III B element can be made to produce precipitation in exchange slurries, carried out after filtering or do not carry out hydro-thermal roasting
Burn.
It is also specific to recommend described modified Y types point in the catalytic cracking catalyst of the preventing from heavy metal of the invention
The preparation method of son sieve at least includes：
3) NaY molecular sieve and ammonium salt are carried out into ion exchange, water with molecular sieve than 2~30,
PH=2.8~6.5,5~100 DEG C of temperature, 0.3~3.5 hour swap time, filtering, Washing of Filter Cake
Mix with water, the compound containing III B element in the periodic table of elements afterwards, in terms of III B element oxide,
In the molecular sieve of butt meter content be 0.5~20 weight %, it is not scrubbed directly carry out spraying do
It is dry, hydrothermal calcine；Molecular sieve sodium oxide content after roasting is 2~6 weight %；
4) molecular sieve obtained by step (1), ammonium salt and water are carried out into ion exchange, and makes this
In molecular sieve pulp after exchanging slurries or exchanging containing can make III B element produce precipitation it is cloudy from
Son, water is with molecular sieve than 2~30, pH=2.8~9.0,5~100 DEG C of temperature, swap time
0.3~3.5 hour, carried out after filtering or be not calcined.III B element content of final molecular sieve
It is 0.5~20 weight %, sodium oxide content is 0.3~2 weight %.
In step (2)：Can make III B element to contain in the molecular sieve pulp after making exchange slurries or exchanging
The anion of precipitation is produced, precipitating reagent is preferably added, such as precipitating reagent can select that the generation of III B element can be provided
The ammonium salt of the anion of precipitation, it is specific such as ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, diammonium hydrogen phosphate, phosphoric acid
One or more in ammonium dihydrogen, ammonium phosphate etc., it is also possible to which selection meets the precipitation of above-mentioned requirements using other
Agent, one or more in specific such as ammoniacal liquor, oxalic acid, carbon dioxide, urea.
The addition of described precipitating reagent meets the material mol ratio in precipitation reaction.Described grass
Acid, ammonium oxalate, ammonium carbonate, ammonium hydrogen carbonate, carbon dioxide, phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate,
The addition of ammonium phosphate, urea etc. depending on the addition of III B element compound, precipitating reagent: oxide meter
III B element compound weight ratio be 0.02~5: 1.When precipitating reagent is ammoniacal liquor, the addition of ammoniacal liquor is regarded
Depending on the pH value of molecular sieve pulp, molecular sieve pulp pH value is set to be maintained in the range of 6.0~9.0.Precipitating reagent
In molecular sieve pulp being added before the exchange of step (2) molecular sieve ammonium salt, can also be in step (2) point
Son sieve ammonium salt is added in molecular sieve pulp after exchanging, and is preferably at least stirred 10 minutes after adding precipitating reagent, with
Ensure that III B element dissociated in molecular sieve pulp precipitates.
In molecular sieve, the distribution of III B element is different in the periodic table of elements, to the shadow of molecular sieve performance
Ring different, wherein, III B element on molecular sieve, the meeting during hydrothermal calcine are exchanged in the form of an ion
Into in the small cage of molecular sieve, molecular sieves stabilized crystal structure, there is provided more acid activity centers.With only
III B element that vertical phase form is present, being capable of trap heavy metals vanadium, the vanadate of formation stabilization, it is to avoid vanadium breaks
The crystal structure of bad element's sieve, reaches the effect of preventing from heavy metal pollution.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, the wherein preparation of modified molecular screen
In method, mixed with the compound containing III B element in the periodic table of elements by filter cake in rate-determining steps (1)
Time, mixed proportion and in rate-determining steps (2) precipitating reagent addition, reach Molecular regulator sieve in III
The purpose of the distribution of B element, can be according to molecular sieve activity, stability and preventing from heavy metal pollution
It is actually needed, the ratio of III B element that regulation exists in the form of an ion and in independent phase form.Filter cake with contain
The compound mixing of III B element in the periodic table of elements, in 5~100 DEG C of stirrings of temperature at least more than half an hour,
Be spray-dried again, hydrothermal calcine, in the molecular sieve of gained, III B element is mainly exchanged to point in the form of an ion
On son sieve, whipping temp is more high more is conducive to III B element to exchange to molecular sieve in the form of an ion up, wherein
III B element that molecular sieve gets on is not exchanged on a small quantity, during follow-up hydrothermal calcine, a part is logical
Cross migration of solid phases and enter molecular sieve, play and acted on III B element identical of ion exchange, another part with
Independent phase form is present, and can be used for trap heavy metals during catalytic cracking reaction.In step (2),
There is anticommuting in the periodic table of elements between III B element and ammonium salt, partly into molecular sieve pulp, add
This B element of part III can be made to precipitate over a molecular sieve containing the anion that can precipitate the generation of III B element, this
Sample, had both caused that the sodium oxide content of molecular sieve is further reduced, and it also avoid the loss of III B element, improved
The utilization rate of III B element, the sediment of this B element of part III can be played in catalytic cracking reaction process
The effect of middle trap heavy metals.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, the wherein preparation of modified molecular screen
In method, the ammonium salt in step (1) and step (2) is selected from ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, chlorine
Change ammonium, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate, ammonium citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate
In one or more, ammonium salt be mainly used in exchange Y type molecular sieve on sodium, make by after exchange point
Sub- sifter device has surface acidity.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, the wherein preparation of modified molecular screen
In method, III described B element is selected from one or more in scandium, yttrium, lanthanide series rare-earth elements.Described
Lanthanide rare is lanthanum rich rare earth, cerium-rich rare earth, pure lanthanum or pure cerium.In step (1) containing III B element
Compound be selected from the halide of water-soluble III B element, nitrate, sulfate, rich III B element
One or more in compound, or the oxide of III water insoluble B element, hydroxide,
One or more in carbonate, it is also possible to selected after acid is molten.
Can be actually needed according to molecular sieve activity, stability and preventing from heavy metal pollution, III B of regulation units
The ratio of plain compound.In catalyst preparation process, molecular sieve used preferably in catalyst preparation process,
Spray drying is preceding by reducing grain graininess treatment, at one or more in shearing, sand milling, ball milling
Reason, makes molecular sieve median D (v, 0.5) less than 5 μm.
In the preparation method of modified molecular screen of the present invention, the roasting described in step (1) and step (2)
Journey, is that the molecular sieve containing III B element in the periodic table of elements is entered into water-filling under 10%~100% water vapour atmosphere
Thermal bake-out, 450~700 DEG C of sintering temperature, roasting time 0.5~4 hour.In roasting process, there is dealuminzation
And silicon migration so that the Si-O-Al on framework of molecular sieve is replaced by Si-O-Si, because Si atoms are (straight
Footpath is 0.082nm) it is smaller than Al atom (a diameter of 0.1nm), bond distance shorten (Si-O bond distance 0.161nm,
Al-O bond distance 0.174nm), structure cell is shunk, and molecular sieve structure stability is improved.In roasting process, also together
When along with Ion transfer, wherein, the Ion transfer of III B element is to molecular sieve sodalite in the periodic table of elements
S I and the positions of S II in cage, play a part of molecular sieves stabilized crystal structure and provide acid activity center,
Na in sodalite cage+Ion is then moved in supercage, and molecular sieve is departed from follow-up ion exchange process.
Compared with simple high-temperature roasting, hydrothermal calcine is carried out under 100% water vapour atmosphere, be more beneficial for above-mentioned
III B element ion and Na+The migration of ion, is more favorable to keep the crystal structure and structure cell of molecular sieve
Shrink.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, the wherein preparation of modified molecular screen
In method, filter aid, filter aid can be also added to be selected from PAMC, the moon in step (2)
One or more in cationic polyacrylamide, polyethyleneimine, aluminium polychloride.Its addition relative to
Molecular sieve butt is 0.01%~5%.Before the exchange of step (2) molecular sieve ammonium salt, in exchange or can hand over
Added after changing in molecular sieve pulp, be stirred after adding filter aid, preferably stirred more than 2 minutes.Due to
The Y molecular sieve of III B element ion modification has that filtering is difficult, makes the company produced in industrial processes
Continuous property is restricted, and reduces the production capacity of the molecular sieve containing III B element, adds filter aid to effectively improve point
The rate of filtration of son sieve, so as to ensure that the raising of the continuity and production capacity of production.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, the wherein preparation of modified molecular screen
In method, III B element (being counted with the oxide) content of Modified Zeolite Y is 0.5~20 weight %,
Sodium oxide content is 0.3~2 weight %.
In catalytic cracking catalyst of the present invention, to other molecular sieves, clay, inorganic oxide, bonding
Agent is the material used in existing catalytic cracking catalyst, and the present invention is not limited, and can be used.
Preferred scheme of the invention is as follows：Counted with catalyst quality as 100%, containing 15~45% in terms of butt
Clay of other molecular sieves, 20~65% of Modified Zeolite Y, 0~30% in terms of butt in terms of butt,
5~30% inorganic oxide and 5~15% binding agent in terms of oxide in terms of oxide.
Other molecular sieves be selected from Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, ZSM molecular sieve,
One or more in HTS；Wherein Y type molecular sieve, selected from USY, REUSY, REHY,
HY、NH4Y, REY, phosphorous Y molecular sieve.
Clay be selected from halloysite, metakaolin, acid extracting kaolin, alkali density kaolin, montmorillonite,
In diatomite, rectorite, galapectite, saponite, sepiolite, attapulgite, hydrotalcite, bentonite one
Plant or various, these clays are known to those of ordinary skill in the art.
Inorganic oxide is aluminum oxide, silica, amorphous silicon aluminium, titanium oxide, zirconium oxide or its mixture
In one or more.The aluminum oxide is selected from the aluminum oxide and/or hydrated alumina of various forms, for example
Gama-alumina, η-aluminum oxide, θ-aluminum oxide, a diaspore (Boehmite, boehmite), three
Diaspore (Gibbsite), one or more in bayerite (Bayreite).
Binding agent is selected from one or more in the binding agent commonly used in Cracking catalyst, such as Ludox, aluminium
One or more in colloidal sol, modified silicasol, modified Alumina gel, amorphous silicon alumina gel, aluminum oxide,
Except boehmite.
Invention additionally discloses the preventing from heavy metal catalytic cracking catalyst preparation method, including：Will be modified
Y type molecular sieve or Modified Zeolite Y and other molecular sieves, clay, inorganic oxide, binding agent
Mixing mashing, then by slurries spray drying, roasting, washing, prepares catalyst.
A kind of catalytic cracking catalyst of preventing from heavy metal disclosed in this invention, wherein method for preparing catalyst
In, the addition sequence of described modified molecular screen, other molecular sieves, clay, inorganic oxide and binding agent
It is not particularly limited, as long as above-mentioned each component is mixed into mashing, spray drying, roasting, washing, you can meet
Requirement of the invention.For example, after molecular sieve pulp can mix with clay, then with inorganic oxide and bonding
Agent mixing mashing；After two or more in clay, inorganic oxide and binding agent can also being mixed into mashing,
Add the mixing mashing such as molecular sieve.
Roasting process when catalyst is prepared in the present invention is solidification process commonly employed in the art, this hair
Bright to be not specially limited its condition, general conditions generally control 350~600 DEG C of temperature, time
0.15~1 hour.
Main advantages of the present invention and effect：
Catalyst disclosed in this invention, in the preparation of modified molecular screen therein, is first exchanged with ammonium ion
NaY molecular sieve, makes the sodium oxide content of NaY molecular sieve in the range of 2~6 weight %, after filtering, filters
Cake compound of the mixing containing III B element in the periodic table of elements, it is not scrubbed to be directly spray-dried and hydro-thermal
Roasting, is then exchanged with ammonium salt again, exchanges addition precipitating reagent or precipitating reagent and filter aid, filtering in slurries
After carry out or do not carry out hydrothermal calcine.This preparation of molecular sieve, the molecular sieve pulp containing III B element holds
Easily filtering, III B element is not lost substantially, and molecular sieve preparation process is more environmentally-friendly, the III B units in molecular sieve
Element exists in two kinds of forms of ion exchange and independent phase, each serves as raising molecular sieve activity, stability and resists
The purpose of heavy metal energy.Catalyst containing modified molecular screen of the present invention has excellent activity, water simultaneously
Heat endurance and preventing from heavy metal pollution performance.
Catalyst disclosed in this invention, it is adaptable to RFCC, is particularly suited for heavy metal content of vanadium
RFCC high.The heavy oil include but is not limited to reduced crude, decompression residuum, vacuum gas oil (VGO),
One or more in AGO (atmospheric gas oil), deasphalted oil and coker gas oil.
Specific embodiment
The present invention is illustrated with embodiment further below, but the present invention is not limited in these examples.
(1) analysis test method used in embodiment.
1. sodium oxide molybdena, rare earth oxide, yttria levels：Analyzed using X-fluorescence method.
2. the crystallinity of molecular sieve, lattice constant：Analyzed using X-ray diffraction method.
3. the determination of activity of catalyst：It is enterprising in the CSA-B type catalyst evaluation devices of Huayang company production
OK.Catalyst is advance after aging 4h or 17h under 800 DEG C, 100% water vapor conditions, light using huge port
Diesel oil carries out determination of activity for raw material, 460 DEG C of reaction temperature, reaction time 70s, catalyst loading amount 5.0g,
Oil ratio 3.2.
(2) raw materials used specification in embodiment
1.NaY molecular sieves, REUSY molecular sieves (RE2O3Content 4.02%, Na2O content 1.24%),
Kaolin (igloss 18.6%), diatomite (igloss 15.4%), boehmite (igloss 36.4%),
Alumina gel (salic 21.2 heavy %), rare earth chloride (RE2O3 288.7g/L), ammoniacal liquor (concentration 16%),
Boehmite (igloss 17.0%), silica (white carbon, igloss 9.91%)：Industrial goods are, are adopted
From Catalyst Factory of Lanzhou Petrochemical Company.Alkaline silica sol：PH value 8.5-10.5, the heavy % of silicon oxide-containing 25,
Qingdao Marine Chemical Co., Ltd. produces.
2. ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium oxalate, ammonium carbonate, yttrium nitrate, lanthanum nitrate, sun from
Sub- polyacrylamide, polyethyleneimine, PAMA, aluminium polychloride：It is chemical reagent.
3. hydrochloric acid：Concentration 36%, chemical reagent.
Embodiment 1
(1) by 1000g NaY molecular sieves (butt) addition 7L deionized waters, under stirring, add
350g ammonium chlorides, 1h is stirred at adjusting 3.50,85 DEG C of slurry pH value with hydrochloric acid, is filtered afterwards, is washed,
Gained filter cake mixes with 250mL rare earth chlorides, 2.2L deionized waters, stirs 0.5h, is spray-dried, so
Carry out hydrothermal calcine, 600 DEG C of sintering temperature, during roasting under 100% water vapour atmosphere in roaster afterwards
Between 2 hours.
(2) by the molecular sieve obtained by step (1), ammonium chloride and water according to molecular sieve (butt)：Ammonium salt：
Water=1：0.3：7 weight forms slurries than mixing, is stirred 1 hour under the conditions of 80 DEG C, pH=3.5,
1% (relative to molecular sieve butt) PAMC is added, is stirred 5 minutes, add carbonic acid
Ammonium, ammonium carbonate addition meets ammonium carbonate：Weight ratio=0.4 of III B element (oxide meter), stirring 10
Minute, filtering, washing, filter cake are calcined 2 hours under 600 DEG C, 100% water vapour atmosphere.
Obtain molecular sieve Z-1 of the present invention.
(3) by 600g (butt) molecular sieves Z-1 add 1.2L deionized waters in, by sanded treatment,
Make molecular sieve median D (v, 0.5) less than 5 μm, obtain molecular sieve pulp Z-1J.By 425g aluminium
Colloidal sol, 1972g kaolin, 943g boehmites, the mixing mashing of 5L water, add 50mL hydrochloric acid,
50 DEG C are warmed up to, are stirred 1 hour, then cool to 25 DEG C, addition 420mL alkaline silica sols, stirring 15
Minute, it is subsequently adding molecular sieve pulp Z-1J, continue to stir 30 minutes, spray drying forming after homogeneous,
(400 DEG C of temperature, 0.6 hour time) is calcined, is washed, dried, obtain catalyst C-1 of the present invention.
Embodiment 2
(1) except the molecular sieve pulp after ammonium salt in the step of embodiment 1 (2) is exchanged is added without filter aid
Outside PAMC, other conditions are obtained molecular sieve Z-2 of the present invention with embodiment 1.
(2) by 600g (butt) molecular sieves Z-2 add 1.2L deionized waters in, by sanded treatment,
Make molecular sieve median D (v, 0.5) less than 5 μm, obtain molecular sieve pulp Z-2J.By 425g aluminium
Colloidal sol, 1972g kaolin, 943g boehmites, the mixing mashing of 5L water, add 50mL hydrochloric acid,
50 DEG C are warmed up to, are stirred 1 hour, then cool to 25 DEG C, addition 420mL alkaline silica sols, stirring 15
Minute, it is subsequently adding molecular sieve pulp Z-2J, continue to stir 30 minutes, spray drying forming after homogeneous,
Roasting (400 DEG C of temperature, 0.6 hour time), washing, dry, prepared catalyst C-2 of the present invention.
Comparative example 1
The contrast molecular sieve DZ-1 containing rare earth is obtained by ion-exchange process.
(1) according to existing patented technology, by 1000g NaY molecular sieves (butt) add 7L deionized waters in,
Under stirring, 350g ammonium chlorides, 250mL rare earth chlorides are added, slurry pH value 3.50 are adjusted with hydrochloric acid,
1h is stirred at 85 DEG C, filtered afterwards, washed, gained filter cake is in roaster under 100% water vapour atmosphere
Carry out hydrothermal calcine, 600 DEG C of sintering temperature, roasting time 2 hours.
(2) the molecular sieve preparation condition in step (2) is with embodiment 1.
Contrast molecular sieve DZ-1 is obtained.
(3) by 600g (butt) molecular sieves DZ-1 add 1.2L deionized waters in, by sanded treatment,
Obtain molecular sieve pulp DZ-1J.By 425g Alumina gels, 1972g kaolin, 943g boehmites,
The mixing mashing of 5L water, adds 50mL hydrochloric acid, is warmed up to 50 DEG C, stirs 1 hour, then cools to 25 DEG C,
420mL alkaline silica sols are added, is stirred 15 minutes, be subsequently adding molecular sieve pulp DZ-1J, continue to stir
Mix 30 minutes, spray drying forming after homogeneous, roasting (400 DEG C of temperature, 0.6 hour time), washing,
Dry, obtain comparative catalyst DC-1.
Comparative example 2
(1) except the molecular sieve pulp after ammonium salt in the step of embodiment 1 (2) is exchanged is added without precipitating reagent
Outside ammonium carbonate, other conditions are obtained contrast molecular sieve DZ-2 with embodiment 1.
(2) by 600g (butt) molecular sieves DZ-2 add 1.2L deionized waters in, by sanded treatment,
Obtain molecular sieve pulp DZ-2J.By 425g Alumina gels, 1972g kaolin, 943g boehmites,
The mixing mashing of 5L water, adds 50mL hydrochloric acid, is warmed up to 50 DEG C, stirs 1 hour, then cools to 25 DEG C,
420mL alkaline silica sols are added, is stirred 15 minutes, be subsequently adding molecular sieve pulp DZ-2J, continue to stir
Mix 30 minutes, spray drying forming after homogeneous, roasting (400 DEG C of temperature, 0.6 hour time), washing,
Dry, obtain comparative catalyst DC-2.
Embodiment 3
(1) by 1000g NaY molecular sieves (butt) add 10L deionized waters in, under stirring, plus
Enter 300g ammonium sulfate, 1h is stirred at adjusting 3.45,90 DEG C of slurry pH value with hydrochloric acid, filter afterwards, wash
Wash, gained filter cake mixes with 271g yttrium nitrates, 2.4L deionized waters, make NaY molecular sieve (butt)：Yttrium
Compound (being counted with yittrium oxide) weight ratio be 1：0.08, stir 0.5h, spray drying, in roaster
In hydrothermal calcine, 620 DEG C of sintering temperature, roasting time 1.5 hours are carried out under 100% water vapour atmosphere.
(2) by the molecular sieve obtained by step (1), ammonium sulfate and water according to molecular sieve (butt)：Ammonium salt：
Water=1：0.3：5 weight forms slurries than mixing, is stirred 1 hour under the conditions of 90 DEG C, pH=3.5,
Add 0.02% (relative to molecular sieve butt) PAMC and ammonium oxalate, ammonium oxalate addition
Meet ammonium oxalate：Weight ratio=1.2 of III B element (oxide meter), stir 10 minutes, filter, wash
Wash, filter cake is calcined 1.5 hours under 620 DEG C, 100% water vapour atmosphere.
Obtain molecular sieve Z-3 of the present invention.
(3) by 870g (butt) molecular sieves Z-3 add 1.7L deionized waters in, by sanded treatment,
Make molecular sieve median D (v, 0.5) less than 5 μm, obtain molecular sieve pulp Z-3J.By 1622g
Kaolin, 943g boehmites, the mixing mashing of 3.3L water, add 25mL hydrochloric acid, are warmed up to 60 DEG C,
Stirring 1 hour, then cool to 25 DEG C, 708g Alumina gels, 66g silica, molecular sieve pulp Z-3J are added,
Continue to stir 1 hour, spray drying forming after homogeneous, roasting (500 DEG C of temperature, 0.4 hour time),
Wash, dry, obtain catalyst C-3 of the present invention.
Comparative example 3
According to existing patented technology, the contrast molecular sieve DZ-3 containing yttrium is obtained by ion-exchange process.
(1) by 1000g NaY molecular sieves (butt) add 10L deionized waters in, under stirring, plus
Enter 300g ammonium sulfate, 271g yttrium nitrates, make NaY molecular sieve (butt)：The compound of yttrium is (with yittrium oxide
Meter) weight ratio be 1：0.08,1h is stirred at adjusting 3.45,90 DEG C of slurry pH value with hydrochloric acid, afterwards mistake
Filter, washing, gained filter cake carry out hydrothermal calcine, roasting temperature in roaster under 100% water vapour atmosphere
620 DEG C of degree, roasting time 1.5 hours.
(2) by the molecular sieve obtained by step (1), ammonium sulfate and water according to molecular sieve (butt)：Ammonium salt：
Water=1：0.3：5 weight forms slurries than mixing, is stirred 1 hour under the conditions of 90 DEG C, pH=3.5,
Filtering, washing, filter cake are calcined 1.5 hours under 620 DEG C, 100% water vapour atmosphere.
Contrast molecular sieve DZ-3 is obtained.
(3) by 870g (butt) molecular sieves DZ-3 add 1.7L deionized waters in, by sanded treatment,
Obtain molecular sieve pulp DZ-3J.1622g kaolin, 943g boehmites, 3.3L water are mixed and is beaten
Slurry, adds 25mL hydrochloric acid, is warmed up to 60 DEG C, stirs 1 hour, then cools to 25 DEG C, addition 708g
Alumina gel, 66g silica, molecular sieve pulp DZ-3J, continue to stir 1 hour, are spray-dried after homogeneous
It is molded, is calcined (500 DEG C of temperature, 0.4 hour time), washes, dry, obtains comparative catalyst DC-3.
Embodiment 4
(1) by 1000g NaY molecular sieves (butt) addition 8L deionized waters, under stirring, add
350g ammonium chlorides, 1h is stirred at adjusting 4.20,80 DEG C of slurry pH value with hydrochloric acid, is filtered afterwards, is washed,
Gained filter cake mixes with 425g lanthanum nitrates, 3.0L deionized waters, makes NaY molecular sieve (butt)：The change of lanthanum
Compound (being counted with lanthana) weight ratio is 1：1h is stirred at 0.16,80 DEG C, is spray-dried, then in roasting
Burn and carry out hydrothermal calcine under 60% water vapour atmosphere in stove, 580 DEG C of sintering temperature, roasting time 2.5 is small
When.
(2) by the molecular sieve obtained by step (1), ammonium nitrate and water according to molecular sieve (butt)：Ammonium salt：
Water=1：0.4：5 weight forms slurries than mixing, is stirred 2 hours under the conditions of 70 DEG C, pH=3.5,
0.8% (relative to molecular sieve butt) PAMA is added, with ammoniacal liquor Molecular regulator screening the pulp liquid
PH value in the range of 6.5~7.0, stir 25 minutes, filtering, washing, filter cake is in 200 DEG C of dryings.
Obtain molecular sieve Z-4 of the present invention.
(3) 900g (butt) molecular sieve Z-4,60g (butt) REUSY molecular sieves are added into 1.9L
In deionized water, by sanded treatment, molecular sieve median D (v, 0.5) is set less than 5 μm, to obtain
To molecular sieve pulp Z-4J.By 1290g kaolin, 177g diatomite, 708g boehmites, 3.5L
Water mixing mashing, adds 38mL hydrochloric acid, stirs 1 hour, adds the thin water of 1132g Alumina gels, 181g
Aluminium stone, molecular sieve pulp Z-4J, continue to stir 1 hour, spray drying forming, roasting (temperature after homogeneous
600 DEG C, 0.2 hour time), washing, dry, obtain catalyst C-4 of the present invention.
Comparative example 4
According to existing patented technology, the contrast molecular sieve DZ-4 containing lanthanum is obtained by ion-exchange process.
(1) by 1000g NaY molecular sieves (butt) addition 8L deionized waters, under stirring, add
350g ammonium chlorides, 425g lanthanum nitrates, make NaY molecular sieve (butt)：The compound (in terms of lanthana) of lanthanum
Weight ratio is 1：0.16,1h is stirred at adjusting 4.20,80 DEG C of slurry pH value with hydrochloric acid, filtering afterwards,
Washing, gained filter cake carries out hydrothermal calcine, sintering temperature 580 in roaster under 60% water vapour atmosphere
DEG C, roasting time 2.5 hours.
(2) by the molecular sieve obtained by step (1), ammonium nitrate and water according to molecular sieve (butt)：Ammonium salt：
Water=1：0.4：5 weight forms slurries than mixing, is stirred 2 hours under the conditions of 70 DEG C, pH=3.5,
Filtering, washing, filter cake is in 200 DEG C of dryings.
(3) 900g (butt) molecular sieve DZ-4,60g (butt) REUSY molecular sieves are added into 1.9L
In deionized water, by sanded treatment, molecular sieve pulp DZ-4J is obtained.By 1290g kaolin, 177g
Diatomite, 708g boehmites, the mixing mashing of 3.5L water, add 38mL hydrochloric acid, stir 1 hour,
1132g Alumina gels, 181g boehmites, molecular sieve pulp DZ-4J are added, continue to stir 1 hour,
Spray drying forming, roasting (600 DEG C of temperature, 0.2 hour time), washing, drying, obtain after homogeneous
To comparative catalyst DC-4.
Embodiment 5
(1) except the molecular sieve pulp after ammonium salt in the step of embodiment 1 (2) is exchanged is added without filter aid
PAMC, but add outside 0.5% (relative to molecular sieve butt) polyethyleneimine,
Other conditions are obtained molecular sieve Z-5 of the present invention with embodiment 1.
(2) by 600g (butt) molecular sieves Z-5 addition 1.2L deionized waters, molecular sieve pulp is obtained
Z-5J.425g Alumina gels, 1972g kaolin, 943g boehmites, 5L water are mixed into mashing, plus
Enter 50mL hydrochloric acid, be warmed up to 50 DEG C, stir 1 hour, then cool to 25 DEG C, addition 420mL alkalescence
Ludox, stirs 15 minutes, is subsequently adding molecular sieve pulp Z-5J, continues to stir 30 minutes, after homogeneous
Spray drying forming, roasting (400 DEG C of temperature, 0.6 hour time), washing, drying, obtain this hair
Bright catalyst C-5.
Embodiment 6
(1) except the molecular sieve pulp after ammonium salt in the step of embodiment 1 (2) is exchanged is added without filter aid
PAMC, but add outside 0.3% (relative to molecular sieve butt) aluminium polychloride,
Other conditions are obtained molecular sieve Z-6 of the present invention with embodiment 1.
(2) by 600g (butt) molecular sieves Z-6 add 1.2L deionized waters in, by sanded treatment,
Make molecular sieve median D (v, 0.5) less than 5 μm, obtain molecular sieve pulp Z-6J.By 425g aluminium
Colloidal sol, 1972g kaolin, 943g boehmites, the mixing mashing of 5L water, add 50mL hydrochloric acid,
50 DEG C are warmed up to, are stirred 1 hour, then cool to 25 DEG C, addition 420mL alkaline silica sols, stirring 15
Minute, it is subsequently adding molecular sieve pulp Z-6J, continue to stir 30 minutes, spray drying forming after homogeneous,
(400 DEG C of temperature, 0.6 hour time) is calcined, is washed, dried, obtain catalyst C-6 of the present invention.
Molecular sieve Z-1~the Z-6 prepared using embodiment 1~6 and the molecular sieve prepared using comparative example 1~4
DZ-1~DZ-4, its physico-chemical property analysis test result is listed in Table 1 below.
The property of the Y type molecular sieve of table 1
The result of table 1 shows, with the molecular sieve DZ-1 prepared using the comparative example 1 of existing ion exchange technique
Compare, using embodiment 1 prepare molecular sieve Z-1, sodium oxide content, crystallinity, lattice constant with it is right
Than molecular sieve DZ-1 quite, but during system with molecular sieve for preparing is standby, the basic free of losses of rare earth, and use contrast
Molecular sieve DZ-1 prepared by example 1, content of rare earth is less than Z-1 molecular sieves 22.8%, and substantial amounts of rare earth is being handed over
Molecular sieve is not exchanged to during changing up, be lost in filtrate in filter process, cause the utilization of rare earth
Rate is low, if do not process can also bring environmental pollution into the rare earth in filtrate.
Compared with the molecular sieve DZ-2 prepared using comparative example 2, the molecular sieve Z-1 prepared using embodiment 1,
Its content of rare earth is 7.81%, higher than contrast molecular sieve (content of rare earth is 6.90%), illustrates to use rare earth
Precipitating reagent is conducive to making molecular sieve exchange the rare earth deposition dissociated in slurries over a molecular sieve, it is to avoid rare earth is with filter
Liquid is lost in, so as to improve rare earth utilization rate of the system with molecular sieve for preparing for during.
Compared with the molecular sieve Z-2 prepared using embodiment 2, the embodiment of the present invention 1,5,6 is respectively adopted
Molecular sieve Z-1, Z-5, Z-6 of preparation, its property are suitable with molecular sieve Z-2, illustrate using filter aid not
The performance of molecular sieve can be significantly affected.Find in an experiment, add filter aid to significantly improve the mistake of molecular sieve
Filtering velocity degree, the molecular sieve filtration time reduces by more than 20%, may promote the solidifying of sieve particle with filter aid
Gather and settle relevant.
Compared with the molecular sieve DZ-3 prepared using comparative example 3, the molecular sieve Z-3 prepared using embodiment 3,
Its yttrium content is 8.85%, higher than contrast molecular sieve (yttrium content is 6.05%), is illustrated using present invention side
Method is more beneficial for making molecular sieve exchange the yttrium load dissociated in slurries over a molecular sieve, it is to avoid yttrium flows with filtrate
Lose, so as to improve the utilization rate of system with molecular sieve for preparing yttrium for during.
Compared with the molecular sieve DZ-4 prepared using comparative example 4, the molecular sieve Z-4 prepared using embodiment 4,
Its content of rare earth is 16.50%, higher than contrast molecular sieve (content of rare earth is 8.64%), even if illustrating
In the case that content of rare earth is high, still it is more beneficial for making molecular sieve dissociate in exchanging slurries using the inventive method
It is rare earth loaded over a molecular sieve, improve system with molecular sieve for preparing for process middle rare earth utilization rate.
Catalyst C-1~the C-6 prepared using embodiment 1~6 and the contrast prepared using comparative example 1~4 are catalyzed
Agent DC-1~DC-4, tests catalyst by the activity after 4h, 17h steam aging, test knot respectively
Fruit is listed in table 2.
In order to investigate the preventing from heavy metal pollution ability of catalyst, above-mentioned catalyst is used into equi-volume impregnating,
3000 μ g/g Ni, 5000 μ g/g V (relative to catalyst) are impregnated respectively, through nickel, the catalyst of pollution of vanadium
4h, the work after test pollution catalyst 4h steam agings are processed under the conditions of 800 DEG C, 100% water vapour
Property, test result is listed in table 2.
In table 2, the hydrothermally stable of catalyst is characterized respectively with activity preservation rate R1 and activity preservation rate R2
Property and preventing from heavy metal pollution ability.Define respectively:Activity preservation rate R1=17h steam agings activity/4h water
Steam ageing activity × 100%；Activity preservation rate R2=pollution 4h steam agings activity/4h water vapours
Aging activity × 100%
The activity of the catalyst of table 2, hydrothermal stability and preventing from heavy metal performance
The result of table 2 shows, compared with the catalyst DC-1 prepared using comparative example 1, is implemented with the present invention
Catalyst C-1 prepared by example 1, its 4h, 17h activity has been respectively increased 4 and 4 percentage points, and activity is protected
Stay rate R1 to improve 1 percentage point, illustrate that catalyst of the present invention has activity and hydrothermal stability higher；
Its activity preservation rate R2 is higher than 5 percentage points of comparative catalyst (DC-1), illustrates catalyst tool of the present invention
There is more preferable preventing from heavy metal pollution performance.
Compared with the catalyst DC-2 prepared using comparative example 2, with molecule prepared by the embodiment of the present invention 1
Sieve Z-1 is catalyst C-1 prepared by active component, and its 4h, 17h activity has been respectively increased 2 and 3 hundred
Branch, activity preservation rate R1 improves 2 percentage points, and activity preservation rate R2 improves 6 percentage points, says
The catalyst of bright rare-earth-containing molecular sieve of the present invention has activity and hydrothermal stability higher, with preferably anti-
Heavy metal energy.
Compared with the catalyst C-2 prepared using embodiment 2, made with the embodiment of the present invention 1,5,6 respectively
Catalyst C-1, C-5, C-6 that standby molecular sieve Z-1, Z-5, Z-6 is prepared for active component, its 4h,
17h activity, and activity preservation rate R1, activity preservation rate R2 and the molecular sieve prepared containing embodiment 2
(Z-2) catalyst C-2 quite, illustrates that using filter aid molecular sieve and catalyst will not be significantly affected
Performance.
Compared with the catalyst DC-3 prepared using comparative example 3, with catalysis prepared by the embodiment of the present invention 3
Agent C-3, its 4h, 17h activity has been respectively increased 4 and 5 percentage points, and activity preservation rate R1 improves 2
Percentage point, activity preservation rate R2 improves 11 percentage points, illustrates molecular sieve catalyst containing yttrium of the invention
With activity higher and hydrothermal stability, with more preferable preventing from heavy metal performance.
Compared with the catalyst DC-4 prepared using comparative example 4, with catalysis prepared by the embodiment of the present invention 4
Agent C-4, its 4h, 17h activity has been respectively increased 8 and 7 percentage points, and activity preservation rate R1 improves 2
Percentage point, activity preservation rate R2 improves 14 percentage points, illustrates rare-earth-containing molecular sieve catalysis of the present invention
Agent has activity and hydrothermal stability higher, with more preferable preventing from heavy metal performance.
The preventing from heavy metal performance improvement of catalyst of the present invention, this preparation method special with molecular sieve of the present invention with
And III B element content of independent phase in molecular sieve is increased relevant, the precipitation of this independent phase using precipitating reagent
Thing is conducive to trap heavy metals vanadium, reduces vanadium during hydrothermal aging to the destruction of molecular sieve structure.
Claims (17)
1. a kind of catalytic cracking catalyst of preventing from heavy metal, it is characterised in that with catalyst quality be 100%
Calculate, contain 10~55% Modified Zeolite Y, 0~45% other in terms of butt point in terms of butt
Son sieve, inorganic oxide and 5~20% of 10~80% clay, 0~40% in terms of butt in terms of oxide
Binding agent in terms of oxide；Described Modified Zeolite Y is obtained by following preparation methods：NaY
Molecular sieve is first exchanged with ammonium ion, compound of the mixing containing III B element in the periodic table of elements after filtering, without
Washing is directly spray-dried and hydrothermal calcine, is then exchanged with ammonium salt again, and make to contain in the exchange slurries
There is the anion that III B element can be made to produce precipitation, carried out after filtering or do not carry out hydrothermal calcine.
2. catalytic cracking catalyst according to claim 1, it is characterised in that be with catalyst quality
100% meter, contains 15~45% Modified Zeolite Y, 0~30% other in terms of butt in terms of butt
Inorganic oxide and 5~15% of clay, 5~30% of molecular sieve, 20~65% in terms of butt in terms of oxide
Binding agent in terms of oxide.
3. catalyst according to claim 1, it is characterised in that described Modified Zeolite Y
Preparation method at least includes：
1) NaY molecular sieve and ammonium salt are carried out into ion exchange, water with molecular sieve than 2~30,
PH=2.8~6.5,5~100 DEG C of temperature, 0.3~3.5 hour swap time, filtering, Washing of Filter Cake
Mix with water, the compound containing III B element in the periodic table of elements afterwards, in terms of III B element oxide,
In the molecular sieve of butt meter content be 0.5~20 weight %, it is not scrubbed directly carry out spraying do
It is dry, hydrothermal calcine；Molecular sieve sodium oxide content after roasting is 2~6 weight %；
2) molecular sieve obtained by step (1), ammonium salt and water are carried out into ion exchange, and makes this
In molecular sieve pulp after exchanging slurries or exchanging containing can make III B element produce precipitation it is cloudy from
Son, water is with molecular sieve than 2~30, pH=2.8~9.0,5~100 DEG C of temperature, swap time
0.3~3.5 hour, carried out after filtering or be not calcined.
4. catalyst according to claim 3, it is characterised in that in step (1) and step (2)
Ammonium salt be selected from ammonium sulfate, ammonium hydrogen sulfate, ammonium nitrate, ammonium chloride, ammonium carbonate, ammonium hydrogen carbonate, ammonium oxalate,
One or more in ammonium citrate, ammonium dihydrogen citrate, diammonium hydrogen citrate.
5. the catalyst according to claim 1 or 3, it is characterised in that III described B element is selected from
One or more in scandium, yttrium, lanthanide series rare-earth elements；Clay is selected from halloysite, metakaolin, acid
Extracting kaolin, alkali density kaolin, montmorillonite, diatomite, rectorite, galapectite, saponite, Hai Pao
One or more in stone, attapulgite, hydrotalcite, bentonite；Inorganic oxide is aluminum oxide, oxidation
One or more in silicon, amorphous silicon aluminium, titanium oxide, zirconium oxide or its mixture；Binding agent is selected from silicon
One or more in colloidal sol, Alumina gel, modified silicasol, modified Alumina gel, amorphous silicon alumina gel；
Other molecular sieves are selected from Y type molecular sieve, beta-molecular sieve, SAPO molecular sieve, ZSM molecular sieve, titanium silicon
One or more in molecular sieve, wherein Y type molecular sieve be selected from USY, REUSY, REHY, HY,
NH4Y, REY, phosphorous Y molecular sieve.
6. catalyst according to claim 5, it is characterised in that described lanthanide rare is that rich lanthanum is dilute
Soil, cerium-rich rare earth, pure lanthanum or pure cerium.
7. the catalyst according to claim 1 or 3, it is characterised in that in step (2)：To make
Containing the anion that III B element can be made to produce precipitation in molecular sieve pulp after exchanging slurries or exchanging, add
Precipitating reagent；Precipitating reagent is ammonium salt, ammoniacal liquor, oxalic acid, the phosphorus that can provide the anion that III B element produces precipitation
One or more in acid, carbon dioxide, urea.
8. catalyst according to claim 7, it is characterised in that ammonium salt be ammonium carbonate, ammonium hydrogen carbonate,
One or more in ammonium oxalate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate etc..
9. catalyst according to claim 3, it is characterised in that in step (1) containing III B units
The compound of element is selected from halide, nitrate, sulfate, rich III B element of water-soluble III B element
Compound, oxide, hydroxide, the carbonate of water insoluble III B element, are one kind therein
Or it is various.
10. catalyst according to claim 3, it is characterised in that step (1) and step (2)
Described in roasting carried out under 10%~100% water vapour atmosphere, 450~700 DEG C of sintering temperature, roasting
0.5~4 hour burning time.
11. catalyst according to claim 3, it is characterised in that exchanging slurries in step (2)
Or add filter aid, filter aid to be selected from PAMC, anion in the molecular sieve pulp after exchanging
One or more in polyacrylamide, polyethyleneimine, aluminium polychloride；Its addition is relative to molecule
Sieve butt is 0.01%~5%.
12. catalyst according to claim 7, it is characterised in that precipitating reagent removes ammonia in step (2)
Outside water, precipitating reagent: the weight ratio of III B element compound of oxide meter is 0.02~5: 1.
13. catalyst according to claim 7, it is characterised in that ammoniacal liquor is used as precipitating reagent, ammoniacal liquor
Addition makes molecular sieve pulp pH value be maintained in the range of 6.0~9.0 depending on the pH value of molecular sieve pulp.
14. catalyst according to claim 1 or 3, it is characterised in that in terms of III B element oxide,
III B element content of described Modified Zeolite Y is 0.5~20 weight %, and sodium oxide content is 0.3~2
Weight %.
15. catalyst according to claim 1 or 3, it is characterised in that in the spray of catalyst preparation
Before mist is dried, slurries containing molecular sieve by shearing, be sanded, one or more treatment in ball milling, make point
Son sieve median D (v, 0.5) is less than 5 μm.
The preparation method of the catalyst described in a kind of 16. claims 1, it is characterised in that catalyst preparation
Method includes：It is Modified Zeolite Y or Modified Zeolite Y and other molecular sieves, clay, inorganic
Oxide, binding agent mixing mashing, are then spray-dried, are calcined, wash, and prepare catalyst.
17. preparation methods according to claim 16, it is characterised in that sintering temperature is 350~600
DEG C, 0.15~1 hour time.
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| CN112108171A (en) * | 2019-06-21 | 2020-12-22 | 中国石油天然气股份有限公司 | Preparation method of anti-heavy metal catalytic cracking catalyst |
| CN112717985A (en) * | 2019-10-28 | 2021-04-30 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof |
| WO2024109549A1 (en) * | 2022-11-25 | 2024-05-30 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst, preparation method therefor and use thereof, and method for processing wax oil |
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| CN103449471A (en) * | 2012-06-01 | 2013-12-18 | 中国石油天然气股份有限公司 | Phosphorus-containing super stable rare earth Y-type molecular sieve and preparation method thereof |
| CN103657700A (en) * | 2012-09-14 | 2014-03-26 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| US20150111722A1 (en) * | 2013-10-22 | 2015-04-23 | China Petroleum & Chemical Corporation | Metal modified y zeolite, its preparation and use |
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| CN112717985B (en) * | 2019-10-28 | 2023-04-07 | 中国石油化工股份有限公司 | Filter residue and preparation method thereof, catalytic cracking catalyst and preparation method thereof |
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