CN106140296A - A kind of method of catalytic cracking spent catalyst recycling - Google Patents
A kind of method of catalytic cracking spent catalyst recycling Download PDFInfo
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- CN106140296A CN106140296A CN201510194951.1A CN201510194951A CN106140296A CN 106140296 A CN106140296 A CN 106140296A CN 201510194951 A CN201510194951 A CN 201510194951A CN 106140296 A CN106140296 A CN 106140296A
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Abstract
The method that the invention discloses a kind of catalytic cracking spent catalyst recycling, the method is with catalytic cracking spent catalyst, roasting kaolin microsphere as primary raw material, supplementary silicon source, without additional aluminum source in the case of, prepare fresh catalyst Cracking catalyst by the method for in-situ crystallization so that catalytic cracking spent catalyst is reused.The method of the catalytic cracking spent catalyst recycling that the present invention provides is compared with the method that existing catalytic cracking spent catalyst recycles, and method is simple, and energy consumption is low, and prepared fresh catalyst Cracking catalyst can carry out commercial Application.
Description
Technical field
The method that the present invention relates to a kind of catalytic cracking spent catalyst recycling.
Background technology
Catalytic cracking unit will discharge substantial amounts of dead catalyst every year, due to catalytic cracking spent catalyst
Content of beary metal is higher, particularly has certain radioactivity, and people and surrounding are harmful to by it,
External as detoxication, it transports, discharges, processes costly；It is catalyzed simultaneously
Agent metal poisoning also makes the cracking performance of catalyst and selectivity decline to a great extent, and makes the yield of light oil drop
Low, directly affects the economic benefit of oil plant.Therefore, exploitation catalytic cracking spent catalyst regeneration
Technology will bring great economic benefit and environmental benefit.
Dead catalyst buries the processing method being to be easier to realize, and is the most still used, but this method spends
Greatly, and not it is the method effected a permanent cure.Some Enterprises is had to use magnetic method to FCC dead catalyst both at home and abroad
Carrying out physical treatment, this method is preferably to be gone out by physical method to pollute gently, better performances, Shang Keji
The continuous poising agent used, and the performance of the catalyst that those have inactivated is not improved, thus nothing
Method fundamentally solves the process problem of dead catalyst.It addition, people attempt to FCC dead catalyst
For producing cement and paving the way, but because the dead catalyst fine powder content of different FCC apparatus is different, solidification
Time Inconsistency, the hardness of cured article is the most different, needs according to different useless catalysis in production process
Agent adjusts formula, but consecutive production can not frequent modulation formula, this just becomes and hinders dead catalyst at this
One factor of field application.
Patent CN101219396A discloses a kind of inorganic and organic coupling method resurrection FCC dead catalyst
Method, i.e. by the reaming effect of mineral acid and the coordination function of organic acid, the two work in coordination with much money
Reparation in the removing belonged to and FCC dead catalyst pore structure.But this chemistry resurrection method pollutes gold in removing
While genus, will also result in activity over catalysts component and lose, and and unresolved framework of molecular sieve destruction
The irreversible inactivation caused, the catalyst activity stability after resurrection is not enough.
Patent CN201010236528 discloses one and utilizes FCC dead catalyst to prepare NaY for raw material
The method of molecular sieve, is mainly characterized by: first activated by FCC dead catalyst alkali fusion, then at additional silicon
Structure directing Hydrothermal Synthesis technology is utilized to prepare Y type molecular sieve under conditions of source.The method is due to must be the most right
Dead catalyst carries out high temperature alkali fuse activation, complex process, and preparation cost is higher.It addition, the NaY obtained
Zeolite crystal is less, only about 200nm.
Patent CN102247880B discloses a kind of side by the useless cracking agent of " in-situ crystallization " recycling
Method, it is characterised in that using catalytic cracking spent catalyst is raw material fabricated in situ catalytic cracking catalyst, system
Preparation Method is that the method initially with pickling removes the heavy metals such as the vanadium in catalytic cracking spent catalyst and nickel
Component, then at high temperature carries out roasting by the mixture of dead catalyst after pickling and alkali and lives it
Change, then by dead catalyst and waterglass after activation, Kaolin, auxiliary agent, dispersant or/and binding agent etc.
The spray-dried microsphere A that is shaped to, then carries out crystalline substance by microsphere A with waterglass, water and directed agents etc.
Change reaction, obtain NaY zeolite content be 20%～70%, the crystallization of Zeolite 4.0～6.0 micro-
Ball, then be modified process and obtain Cracking catalyst product.Although the method can be improved by in-situ crystallization
Microsphere Middle molecule sieve content, increases catalyst activity, but needs in preparation process to enter useless cracking agent in advance
Row pickling and high-temperature alkali calcination process, preparation cost is high and operation is complicated.
Prepare " in-situ crystallization " skill of active component NaY molecular sieve and substrate with Kaolin for raw material simultaneously
Art is a kind of important catalytic cracking catalyst preparation method.Engelhard company is in patent
In preparation method disclosed in US4493902, by adding ultrafine kaolin in Kaolin parent microsphere,
NaY molecular sieve content in crystallization microsphere can be brought up to more than 40%, become Engelhard company
Significant patented technology.Due to ultrafine kaolin to be used so that the preparation cost of the method is higher.
In blooming preparation in situ disclosed in patent CN1232862A, kaolin microsphere is existed respectively
Roasting at a temperature of 700～900 DEG C and 900 DEG C～1000 DEG C, carries out crystallization after mixing anti-by a certain percentage
Should, in the crystallization microsphere obtained, NaY molecular sieve content is about 30%.The method is owing to use two
Plant the kaolin microsphere of temperature calcination so that preparation technology is complex, and preparation cost is higher.
Summary of the invention
The method that it is an object of the invention to provide a kind of catalytic cracking spent catalyst recycling.The method is to urge
Change cracking dead catalyst, roasting kaolin microsphere is primary raw material, in supplementary silicon source, without additional aluminum
In the case of source, prepare fresh catalyst Cracking catalyst by the method for in-situ crystallization so that catalytic cracking
Dead catalyst is reused.
To achieve these goals, the present invention provides a kind of method that catalytic cracking spent catalyst recycles,
The method includes: a, according to Na2O:Al2O3: SiO2: H2: (40-400) O=(1-12): 1:(4-20)
Total mol ratio by catalytic cracking spent catalyst, roasting kaolin microsphere, silicon source, alkali source, directed agents
Mix with water, obtain mixed serum；Wherein, with dry basis, described catalytic cracking spent catalyst with
The weight ratio of described roasting kaolin microsphere is (1:99)-(99:1)；And lead described in wherein,
In agent salic weight account in described mixed serum the 1-5 weight % of salic gross weight；
B, by crystallization 5h-40h at 70 DEG C-120 DEG C of the mixed serum of gained in step a, by products therefrom mistake
Filter, wash, be dried, obtain crystallization microsphere；C, the crystallization microsphere of gained in step b is carried out ammonium friendship
Change and/or rare earth exchanged and/or acid modification, obtain fresh catalyst Cracking catalyst.
Preferably, wherein, with dry basis, described catalytic cracking spent catalyst and described roasting kaolinite
The weight ratio of soil microsphere is (20:80)-(80:20).
Preferably, wherein, with dry basis, described catalytic cracking spent catalyst and described roasting kaolinite
The weight ratio of soil microsphere is (30:70)-(70:30).
Preferably, wherein, the preparation method of described roasting kaolin microsphere comprises the steps: kaolinite
Soil, dispersant and water carry out mixing making beating successively, obtain kaolin slurry；Wherein, with SiO2The institute of meter
State the 2-4 weight % that weight is the described Kaolin gross weight in terms of butt of dispersant, described kaolinite soil paste
The solid content of liquid is 35-45 weight %；Described kaolin slurry is spray-dried, obtains Kaolin micro-
Ball；Described kaolin microsphere is carried out roasting 0.5-20 hour at 650-1000 DEG C, obtains roasting kaolin
Microsphere.
Preferably, wherein, the preparation method of described directed agents comprises the steps: according to (15-18)
Na2O:Al2O3:(15-17)SiO2:(280-380)H2The mol ratio of O by alkali source, sodium aluminate, silicon source and
Water mixes, and stands aging 0.5-48 hour at room temperature to 70 DEG C, obtains described directed agents.
Preferably, wherein, described silicon source is selected from waterglass, silica gel, Ludox, white carbon and diatom
At least one in soil, described alkali source is sodium hydroxide.
Preferably, wherein, the dynamic crystallization under crystallization described in step b is stirring.
Preferably, wherein, the acid that described acid modification is used is mineral acid and/or organic acid, institute
Stating mineral acid is at least one in hydrochloric acid, nitric acid and sulphuric acid, described organic acid be selected from oxalic acid,
At least one in citric acid and tartaric acid.
The catalysis useless with existing catalytic cracking of the reuse method of the catalytic cracking spent catalyst that the present invention provides
The reuse method of agent is compared, and method is simple, and energy consumption is low, and prepared fresh catalyst cracking catalysis
In agent, Y type molecular sieve content (degree of crystallinity) at 20%-70%, framework si-al ratio more than 4.8,
The activity of catalytic cracking spent catalyst and residual oil cracking products distribution all be improved significantly, it is possible to carry out work
Industry is applied.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is stereoscan photograph (the i.e. embodiment of the crystallization microsphere prepared by method using the present invention
The stereoscan photograph of the crystallization microsphere KEY-B2 prepared by 2)；
Fig. 2 is the XRD spectra of the catalytic cracking spent catalyst YH-3 that the embodiment of the present invention is used；
Fig. 3 is XRD spectra (the i.e. embodiment 2 of the crystallization microsphere prepared by method using the present invention
The XRD spectra of prepared crystallization microsphere KEY-B2).
Detailed description of the invention
Below in conjunction with accompanying drawing, the detailed description of the invention of the present invention is described in detail.It should be appreciated that
Detailed description of the invention described herein is merely to illustrate and explains the present invention, is not limited to this
Bright.
The present invention provides a kind of method that catalytic cracking spent catalyst recycles, and the method includes: a, press
According to Na2O:Al2O3: SiO2: H2: the total mol ratio of (40-400) O=(1-12): 1:(4-20)
Catalytic cracking spent catalyst, roasting kaolin microsphere, silicon source, alkali source, directed agents and water are mixed,
To mixed serum；Wherein, with dry basis, described catalytic cracking spent catalyst and described roasting kaolinite
The weight ratio of soil microsphere is (1:99)-(99:1), is preferably (20:80)-(80:20),
More preferably (30:70)-(70:30)；And wherein, in described directed agents, institute is salic
Weight account in described mixed serum the 1-5 weight % of salic gross weight；B, by gained in step a
Mixed serum crystallization 5h-40h at 70 DEG C-120 DEG C, products therefrom filtered, wash, be dried,
To crystallization microsphere；C, the crystallization microsphere of gained in step b is carried out ammonium exchange and/or rare earth exchanged and/
Or acid modification, obtain fresh catalyst Cracking catalyst.
According to the present invention, described catalytic cracking spent catalyst is well-known to those skilled in the art, permissible
From catalytic cracking unit, it is also possible to from catalytic cracking catalyst process units, its composition is not had yet
Limit especially.It should be noted that the catalytic cracking spent catalyst of the present invention carry out before crystallization can be without
Process through pulverizing, pickling and alkali cleaning etc., can be raw directly as molecular sieve as roasting kaolin
Long carrier.
According to the present invention, described roasting kaolin microsphere refers to that using in-situ crystallization method to prepare catalytic cracking urges
During agent, carry out the kaolin microsphere through high-temperature roasting before in-situ crystallization, be those skilled in the art
Known, such as, its preparation method may include steps of: Kaolin, dispersant and water is depended on
Secondary carrying out mixes making beating, obtains kaolin slurry；Wherein, with SiO2The weight of the described dispersant of meter is
The 2-4 weight % of the described Kaolin gross weight in terms of butt, the solid content of described kaolin slurry is 35-45
Weight %；Described kaolin slurry is spray-dried, obtains kaolin microsphere；By micro-for described Kaolin
Ball carries out roasting 0.5-20 hour at 650-1000 DEG C, obtains roasting kaolin microsphere.
According to the present invention, described directed agents refers to that the molecular sieve with some Y type molecular sieve nucleus closes
Become raw material, for accelerating the crystallization velocity of Y type molecular sieve, be well-known to those skilled in the art, example
As, the preparation method of described directed agents may include steps of: according to (15-18) Na2O:Al2O3:
(15-17)SiO2:(280-380)H2Alkali source, sodium aluminate, silicon source and water are mixed by the mol ratio of O, and
At room temperature to 70 DEG C, stand aging 0.5-48 hour, obtain described directed agents.Wherein, preparation guides
Silicon source used by agent can be identical with the silicon source in step a and alkali source with alkali source, it is also possible to different, but excellent
Phase selection is same.
According to the present invention, described silicon source and alkali source are well-known to those skilled in the art, such as, described
Silicon source can be at least one in waterglass, silica gel, Ludox, white carbon and kieselguhr, institute
Stating alkali source can be sodium hydroxide.
According to the present invention, crystallization described in step b is well-known to those skilled in the art, and the present invention is not
Repeat again.It should be noted that owing to mixed serum prepared in step a of the present invention containing molding
Catalytic cracking spent catalyst and roasting kaolin microsphere, easily deposit during crystallization, therefore the present invention mixing
The crystallization state of serosity is preferably dynamic crystallization, and described dynamic crystallization is well known to those skilled in the art
, the present invention repeats no more.
According to the present invention, it is well-known to those skilled in the art for being dried described in step b, and its condition can
Thinking: the temperature being dried is 80-150 DEG C, the time being dried is 8-24 hour.
According to the present invention, modification described in step c is well-known to those skilled in the art, permissible
For ammonium exchange and/or rare earth exchanged and/or acid modification.The ammonium salt that the exchange modification of described ammonium is used can
Think selected from ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate, ammonium hydrogen carbonate, ammonium hydrogen sulfate, ammonium phosphate,
At least one in ammonium dihydrogen phosphate and diammonium phosphate；The rare earth that the modification of described rare earth exchanged is used
Compound can be at least one in rare earth chloride, nitric acid rare earth and sulfuric acid rare earth；Described acid exchange
The modified acid used can be mineral acid and/or organic acid, and described mineral acid can be selected from hydrochloric acid, nitre
At least one in acid and sulphuric acid, described organic acid can be in oxalic acid, citric acid and tartaric acid
At least one.
To be further detailed the present invention by embodiment below, instrument and equipment used is as without special
Not mentionleting alone bright, be routine instrument device in prior art, the present invention repeats no more, but the most therefore
And limit the present invention.
In fresh catalyst Cracking catalyst prepared by the embodiment of the present invention, the degree of crystallinity of Y type molecular sieve is adopted
Measure with RIPP 146-90 standard method.
Framework si-al ratio uses following equation to measure:
SiO2/Al2O3=2 × (25.8575-a0)/(a0-24.191)；
Wherein, a0It is the cell parameter of molecular sieve, uses RIPP 145-90 standard method to measure.
The Na of fresh catalyst Cracking catalyst2O content uses RIPP 129-90 method to measure, RE2O3
Content uses RIPP 131-90 method to measure.
Micro-reactivity uses RIPP 92-90 standard method to measure.
RIPP standard method mentioned herein specifically can be found in " Petrochemical Engineering Analysis method ", Yang Cuiding
Deng volume, nineteen ninety version.
The preparation process of the used directed agents of the embodiment of the present invention is as follows:
According to 16Na2O:Al2O3:15SiO2:320H2The mol ratio of O by sodium hydroxide, sodium aluminate,
(Shandong catalyst Co. provides waterglass, SiO2262g/L, modulus 3.43, density 1260g/L) and
Chemical water mixes, and stands aging 24 hours at 30 DEG C, has obtained directed agents.
Embodiment 1
This example demonstrates that the preparation of roasting kaolin microsphere.
(Shandong catalyst Co. provides, SiO to add 300g waterglass in 15Kg chemical water2262g/L,
Modulus 3.43, density 1260g/L) as dispersant, under stirring, add 10Kg butt Kaolin
(Kaolin of Suzhou Products, SiO250.8%, Al2O344.3%, K2O 0.59%, Fe2O30.83%)
Making beating, spray-dried obtains kaolin microsphere.By kaolin microsphere 900 DEG C of roasting 3h in Muffle furnace,
Obtain roasting kaolin microsphere.
Embodiment 2
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 75g roasting kaolin microsphere and 75g catalytic cracking spent catalyst (Yanshan Petrochemical company catalysis car
Between provide, be designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%, Ni
1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 371g waterglass2262g/L, mould
Several 3.43, density 1260g/L), 214g directed agents and 90g water mix homogeneously in synthesis reactor, stirring
It is warming up to 98 DEG C under state, and keeps dynamic crystallization 26h.Then crystallization product is drawn off, through filtering,
Washing, in baking oven, 120 DEG C are dried overnight, and obtain the crystallization microsphere that the present invention provides, are designated as KEY-B2,
Its degree of crystallinity is 33.7%, and framework si-al ratio is 5.4.The XRD spectrum of catalytic cracking spent catalyst YH-3
Figure is as in figure 2 it is shown, the scanning electron microscope (SEM) photograph (SEM) of crystallization microsphere KEY-B2 and XRD spectra are distinguished
(scanning electron microscope (SEM) photograph of the crystallization microsphere prepared by Examples hereinafter and XRD as shown in figures 1 and 3
Spectrogram is similar to KEY-B2, no longer lists).From scanning electron microscope (SEM) photograph it can be seen that crystallization microsphere KEY-B2
Surface there is the crystal grain of a large amount of Y type molecular sieve, and from XRD figure it can also be seen that crystallization microsphere
The characteristic peak of Y type molecular sieve is greatly enhanced.This all illustrates the process by this method, and catalytic cracking is useless urges
In agent, molecular sieve content increases.
Embodiment 3
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 120g roasting kaolin microsphere and (the Yanshan Petrochemical company catalysis of 30g catalytic cracking spent catalyst
Workshop provides, and is designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%,
Ni 1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 397g waterglass2262g/L,
Modulus 3.43, density 1260g/L), 222g directed agents and 101g water mix homogeneously in synthesis reactor, stir
Mix and under state, be warming up to 95 DEG C, and keep dynamic crystallization 33h.Then crystallization product is drawn off, through filtering,
Washing, in baking oven, 120 DEG C are dried overnight, and obtain the crystallization microsphere that the present invention provides, are designated as KEY-B3,
Its degree of crystallinity is 44.0%, and framework si-al ratio is 5.2.
Embodiment 4
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 48g roasting kaolin microsphere and 72g catalytic cracking spent catalyst (Yanshan Petrochemical company catalysis car
Between provide, be designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%, Ni
1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 480g waterglass2262g/L, mould
Several 3.43, density 1260g/L), 10.2g NaOH (Beijing Chemical Plant's reagent, analytical pure), 171g
Directed agents and 61g water mix homogeneously in synthesis reactor, be warming up to 93 DEG C under stirring, and keeps dynamically
Crystallization 20h.Then being drawn off by crystallization product, through filtering, washing, in baking oven, 120 DEG C are dried overnight,
Obtaining the crystallization microsphere that the present invention provides, be designated as KEY-B4, its degree of crystallinity is 51.2%, framework silicon-aluminum
Ratio is 5.3.
Embodiment 5
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 36g roasting kaolin microsphere and 84g catalytic cracking spent catalyst (Yanshan Petrochemical company catalysis car
Between provide, be designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%, Ni
1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 465g waterglass2262g/L, mould
Several 3.43, density 1260g/L), 14.5g NaOH (Beijing Chemical Plant's reagent, analytical pure), 240g
Directed agents and 89g water mix homogeneously in synthesis reactor, be warming up to 90 DEG C under stirring, and keeps dynamically
Crystallization 29h.Then being drawn off by crystallization product, through filtering, washing, in baking oven, 120 DEG C are dried overnight,
Obtaining the crystallization microsphere that the present invention provides, be designated as KEY-B5, its degree of crystallinity is 65.2%, framework silicon-aluminum
Ratio is 5.1.
Embodiment 6
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 70g roasting kaolin microsphere and 30g catalytic cracking spent catalyst (Yanshan Petrochemical company catalysis car
Between provide, be designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%, Ni
1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 517g waterglass2262g/L, mould
Several 3.43, density 1260g/L), 12.5g NaOH (Beijing Chemical Plant's reagent, analytical pure), 142g
Directed agents and 105g water mix homogeneously in synthesis reactor, be warming up to 88 DEG C under stirring, and keeps dynamic
State crystallization 37h.Then being drawn off by crystallization product, through filtering, washing, in baking oven, 120 DEG C are dried overnight,
Obtaining the crystallization microsphere that the present invention provides, be designated as KEY-B6, its degree of crystallinity is 58.6%, framework silicon-aluminum
Ratio is 5.1.
Embodiment 7
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 16g roasting kaolin microsphere and 64g catalytic cracking spent catalyst (Yanshan Petrochemical company catalysis car
Between provide, be designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%, Ni
1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 635g waterglass2262g/L, mould
Several 3.43, density 1260g/L), 17.9g NaOH (Beijing Chemical Plant's reagent, analytical pure), 113g
Directed agents and 115g water mix homogeneously in synthesis reactor, be warming up to 95 DEG C under stirring, and keeps dynamic
State crystallization 32h.Then being drawn off by crystallization product, through filtering, washing, in baking oven, 120 DEG C are dried overnight,
Obtaining the crystallization microsphere that the present invention provides, be designated as KEY-B7, its degree of crystallinity is 48.5%, framework silicon-aluminum
Ratio is 5.6.
Embodiment 8
This example demonstrates that the preparation of the crystallization microsphere that the present invention provides.
By 9g roasting kaolin microsphere and 81g catalytic cracking spent catalyst (Yanshan Petrochemical company catalysis car
Between provide, be designated as YH-3:SiO237.4%, Al2O352.8%, RE2O33.2%, Fe 0.84%, Ni
1.19%, V 0.39%) (Shandong catalyst Co. provides, SiO with 590g waterglass2262g/L, mould
Several 3.43, density 1260g/L), 15.4g NaOH (Beijing Chemical Plant's reagent, analytical pure), 127g
Directed agents and 113g water mix homogeneously in synthesis reactor, be warming up to 98 DEG C under stirring, and keeps dynamic
State crystallization 27h.Then being drawn off by crystallization product, through filtering, washing, in baking oven, 120 DEG C are dried overnight,
Obtaining the crystallization microsphere that the present invention provides, be designated as KEY-B8, its degree of crystallinity is 52.3%, framework silicon-aluminum
Ratio is 5.5.
Embodiment 9
This example demonstrates that the crystallization microsphere that the present invention provides is modified the cracking performance being prepared as catalyst.
Crystallization microsphere KEY-B8 embodiment 8 prepared, by conventional " two hand over two roastings ", technique is respectively
Modification is swapped with earth solution and ammonium chloride solution.The proportioning (weight) of rare earth exchanged is:
Crystallization microsphere: RE2O3: H2O=1:0.08:8；
The temperature of roasting for the first time is 550 DEG C, and the time is 2 hours；
The proportioning of ammonium exchange is:
Crystallization microsphere: NH4Cl:H2O=1:0.35:8；
The temperature of roasting for the second time is 550 DEG C, and the time is 2 hours；
In exchange process, exchange liquid respectively with 10 weight % hydrochloric acid solutions adjustment pH value between 3.0-3.5,
To ensure removing sodium effect.
The catalyst obtained is designated as KEY-CB8, Na2O content is 0.30%, RE2O3Content is 7.4%,
Measuring micro-activity after 800 DEG C/17h hydrothermal aging is 70%, and the micro-anti-work of catalytic cracking spent catalyst
Property is directly determined as 55%.On ACE device, comparative evaluation catalyst KEY-CB8 and catalysis are split
Change the heavy oil (decompression residuum of Daqing vacuum gas oil interpolation 30wt%, raw oil character is shown in Table 1) of dead catalyst
Cracking performance, the results are shown in Table 2.
As seen from Table 2, the catalytic cracking spent catalyst reuse method provided by the present invention is obtained
Catalyst, can make the cracking activity of catalytic cracking spent catalyst significantly improve, and crackate distribution significantly changes
Kind.
Table 1 raw material oil properties
| Project | Analytical data | Project | Analytical data |
| Density (20 DEG C)/g/cm3 | 0.8731 | Viscosity (80 DEG C)/mm2/s | 17.56 |
| Vacuum distillation range/DEG C | Refractive power (70 DEG C) | 1.4682 | |
| Initial boiling point | 189 | Acid number/mgKOH/g | 0.07 |
| 5% | 398 | Carbon residue/% | 0.7 |
| 10% | 418 | Ash/% | 0.05 |
| 30% | 457 | C/% | 86.43 |
| 50% | 497 | H/% | 13.53 |
| 70% | 549 | S/% | 0.12 |
| 90% | 73.5%, 560 DEG C | N/% | 0.11 |
The fresh catalyst Cracking catalyst that table 2 catalytic cracking spent catalyst YH-3 and the present invention provide
The residual oil cracking performance of KEY-CB8
| Sample ID | YH-3 | KEY-CB8 |
| Reaction temperature/DEG C | 500 | 500 |
| Oil ratio | 5.92 | 5.92 |
| Raw oil | WH-3 | WH-3 |
| Products distribution/% | ||
| Dry gas | 1.42 | 1.39 |
| Liquefied gas | 16.33 | 15.44 |
| Gasoline | 44.10 | 54.05 |
| Diesel oil | 16.64 | 15.08 |
| Heavy oil | 11.41 | 8.75 |
| Coke | 10.10 | 8.28 |
| Add up to | 100.00 | 100.00 |
| Conversion ratio | 71.94 | 79.17 |
Claims (8)
1. a method for catalytic cracking spent catalyst recycling, the method includes:
A, according to Na2O:Al2O3: SiO2: H2: (40-400) O=(1-12): 1:(4-20)
Total mol ratio by catalytic cracking spent catalyst, roasting kaolin microsphere, silicon source, alkali source, directed agents and
Water mixes, and obtains mixed serum；Wherein, with dry basis, described catalytic cracking spent catalyst and institute
The weight ratio stating roasting kaolin microsphere is (1:99)-(99:1)；And wherein, described guiding
In agent salic weight account in described mixed serum the 1-5 weight % of salic gross weight；
B, by crystallization 5h-40h at 70 DEG C-120 DEG C of the mixed serum of gained in step a, gained is produced
Thing filters, washs, is dried, and obtains crystallization microsphere；
C, the crystallization microsphere of gained in step b is carried out ammonium exchange and/or rare earth exchanged and/or acid modified at
Reason, obtains fresh catalyst Cracking catalyst.
Method the most according to claim 1, wherein, with dry basis, described catalytic cracking is useless urges
Agent is (20:80)-(80:20) with the weight ratio of described roasting kaolin microsphere.
Method the most according to claim 1, wherein, with dry basis, described catalytic cracking is useless urges
Agent is (30:70)-(70:30) with the weight ratio of described roasting kaolin microsphere.
Method the most according to claim 1, wherein, the preparation method bag of described roasting kaolin microsphere
Include following steps:
Kaolin, dispersant and water are carried out successively mixing making beating, obtains kaolin slurry；Wherein, with
SiO2The weight of the described dispersant of meter is the 2-4 weight % of the described Kaolin gross weight in terms of butt, institute
The solid content stating kaolin slurry is 35-45 weight %；
Described kaolin slurry is spray-dried, obtains kaolin microsphere；
Described kaolin microsphere is carried out roasting 0.5-20 hour at 650-1000 DEG C, obtains roasting kaolin
Microsphere.
Method the most according to claim 1, wherein, the preparation method of described directed agents includes walking as follows
Rapid: according to (15-18) Na2O:Al2O3:(15-17)SiO2:(280-380)H2The mol ratio of O is by alkali
Source, sodium aluminate, silicon source and water mixing, and at room temperature to 70 DEG C, stand aging 0.5-48 hour,
To described directed agents.
Method the most according to claim 1, wherein, described silicon source is selected from waterglass, silica gel, silicon
At least one in colloidal sol, white carbon and kieselguhr, described alkali source is sodium hydroxide.
Method the most according to claim 1, wherein, crystallization described in step b is under stirring
Dynamic crystallization.
Method the most according to claim 1, wherein, the acid that described acid modification is used is inorganic
Acid and/or organic acid, described mineral acid is at least one in hydrochloric acid, nitric acid and sulphuric acid, described in have
Machine acid is at least one in oxalic acid, citric acid and tartaric acid.
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| CN106938849A (en) * | 2016-12-13 | 2017-07-11 | 江苏天诺新材料科技股份有限公司 | The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst |
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| CN109305767A (en) * | 2017-11-16 | 2019-02-05 | 中国石油化工股份有限公司 | A kind of method that harmlessness disposing FCC dead catalyst prepares geo-polymer |
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| CN110523427A (en) * | 2018-05-24 | 2019-12-03 | 中国石油天然气股份有限公司 | A kind of preparation method of in-situ crystallization type catalytic cracking catalyst |
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| CN115057453B (en) * | 2022-06-07 | 2023-10-20 | 福州大学 | Method for preparing SSZ-13 molecular sieve by using FCC spent catalyst and application thereof |
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