CN102764670A - In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst - Google Patents
In-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and preparation method of in-situ crystallization cracking catalyst Download PDFInfo
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Abstract
The invention discloses an in-situ crystallization cracking catalyst prepared by polymorph kaolin microspheres and a preparation method of the in-situ crystallization cracking catalyst. The preparation method includes preparing ultrafine raw kaolin and spinel kaolin slurry as basic raw materials for preparing the catalyst at first; mixing and slurrying the raw kaolin, spinel kaolin and a small quantity of water glass, and molding spray microspheres with the sizes ranging from 20 micrometers to 150 micrometers in a spraying manner; calcining the spray microspheres at the proper temperature for a plurality of hours to obtain calcined microspheres containing the spinel kaolin, metakaolin and little mullite; and mixing the calcine microspheres, water glass, NaY guiding agent, sodium hydroxide and the like, then performing hydrothermal crystallization for the mixture to obtain crystallized microspheres containing NaY molecular sieves, and performing treatments including conventional ion exchange, hydrothermal calcination, washing, drying and the like for the crystallized microspheres to obtain the FCC (fluidic catalytic cracking) catalyst containing Y-type molecular sieves. The catalyst contains large quantities of molecular sieves, is of a thriving mesoporous structure, is good in heavy oil cracking reaction activity and high in light weight yield and has few coke and dry gas byproducts.
Description
Technical field
The present invention relates to the in-situ crystallization type Cracking catalyst and preparation method thereof of a kind of polycrystalline phase kaolin microsphere preparation of petrochemical industry.
Background technology
Along with the oil product demand is increased day by day with petroleum resources day by day the shortage; Can obtain more light-end products (gasoline, diesel oil etc.) with heavy charge; So require the FCC catalyst when having greater activity; Increase the middle pore size distribution of catalyst, the mass transfer that helps mink cell focus reacts with the secondary cracking that separates fast, reduces of product, reduces coke and hydrogen accessory substance.
From the sixties in 20th century, molecular sieve is as active component in most of commercial Cracking catalyst (being called for short the FCC catalyst).These catalyst have all taked to be called the granule of microballoon, and granularity is at the 20-150 micrometer range, and the microballoon of 40-110 micron generally is greater than 50% in the commercial catalyst, and microballoon has comprised the matrix components of zeolite activity component and nonzeolite simultaneously.At present; The preparation technology of this Cracking catalyst mainly contains narrow two types on moulding and in-situ crystallization type; The moulding FCC catalyst that narrows is with after binding agent mixes with artificial synthesis of molecular sieve and natural kaolin; Be shaped to microballoon through spray granulation, the one type of FCC catalyst for preparing through a series of post processings again; In-situ crystallization type FCC catalyst is to be raw material with pulp kaolin; Elder generation's mist projection granulating becomes only to contain kaolinic microballoon; Through calcining, crystallization, in-situ crystallization goes out molecular sieve on microballoon, the one type of FCC catalyst for preparing through a series of post processings more again; The carrier of this type of catalyst and active component are all from natural kaolin, so also claim kaolin type or full white-clay type FCC catalyst.
People have recognized that for a long time Cracking catalyst will obtain business success; Except commercial acceptable activity, selectivity and stability etc. being arranged the characteristics; Enough flexibilities also must be arranged so that attractive economically income to be provided; This has needed selectivity increases target product output, reduces the accessory substance of non-target, also will have enough hydrothermal stabilities and wear resistence to guarantee product service life simultaneously.
Hope least in the Industrial Catalysis cracking process that two kinds of accessory substances that produce are coke and hydrogen.These two kinds of accessory substances are except reducing target product (gasoline, diesel oil, liquefied gas) the total recovery, and also can cause catalyst when regenerating, to produce in the process does not too much need heat and increase the PETROLEUM PROCESSING cost; The increase meeting of amounts of hydrogen increases expensive compressor operation expense greatly and increases production cost.
Improving active component in the catalyst (zeolite molecular sieve) content on the one hand is the most important means of improving catalytic selectivity; But people are in Continual Improvement FCC activity of such catalysts, selectivity and stability; A kind of so unfavorable circumstances usually appears; Promptly when improving a kind of performance, or need to sacrifice other a kind of performance, or increased manufacturing cost and make it lack economic attractiveness.The actual result that this circumstances causes is, people must make compromise in the conflicting of the catalytic performance of catalyst and physical property.For example with Ludox, aluminium colloidal sol be the semi-synthetic catalyst of binding agent synthetic in, when the molecular sieve content as active component surpasses after 35%, its mechanical strength can variation and be not suitable for commercial Application.
On the other hand, in the catalytic cracking process, the heavy metal in the raw material (especially nickel and vanadium) can make catalyst poisoning and make outside the catalyst rapid deactivation, also can increase hydrogen transfer reaction, and by-product coke and hydrogen yield are increased.
Summary of the invention
The object of the present invention is to provide a kind of very high molecular sieve content that has, have flourishing central hole structure, the better polycrystalline in-situ crystallization type Cracking catalyst for preparing of kaolin microsphere mutually of residual oil cracking reactivity, higher light oil productive rate, coke still less and dry gas accessory substance.
To achieve these goals, technical scheme of the present invention is: the in-situ crystallization type Cracking catalyst of a kind of polycrystalline phase kaolin microsphere preparation is provided, and the scope of its middle rare earth weight content is 0.0～11.0%, Na
2O content range 0.25～0.80%; Wherein active component comprises the non-sodium type Y molecular sieve of ultra steady and non-super stabilizing, and non-sodium type Y molecular sieve comprises REHY, HUSY type, the REUSY type of rare-earth type REY, Hydrogen HY, rare earth Hydrogen, the compound of one or more in the non-sodium type of the REHUSY type molecular sieve.
Another object of the present invention is to provide a kind of preparation method of in-situ crystallization type Cracking catalyst of polycrystalline phase kaolin microsphere preparation, may further comprise the steps:
(1), living kaolin of ultra-fineization of preparation and spinelle kaolin slurry are as the base stock of preparation catalyst; Wherein: the kaolinic preparation temperature of spinelle is 850～1100 ℃; Ultra-fineization given birth to kaolinic granularity less than 2.5 μ m, and the kaolinic particle of spinelle is less than 2.0 μ m;
The kaolinic concrete preparation method of ultra-fine life adopts stirring mill method commonly used in the preparation inorganic powder material: average meso-position radius is dropped in the universal stirring mill by the 1:1 weight ratio greater than soft natural kaolin of 80% graininess and deionized water less than 10 μ m, crystalline phase kaolinite content, and (as follows) calculated in the calcination that kaolinic here weight is pressed after 800 ℃ of roastings.Stir in the mill and put into the zirconia ball that is equivalent to 30～50% kaolin weight, diameter 1～5mm again, add appropriate amount of fluid waterglass at last as dispersant, agitation grinding 1～8 hour obtains meso-position radius less than the ultra-fine living kaolin slurry of 3.0 μ m.These slurries are the required living kaolin of preparation microballoon.
Ultra-fine spinelle kleit preparation method adopts stirring mill method commonly used in the preparation inorganic powder material: average meso-position radius is put into sapphire discs less than 10 μ m, crystalline phase kaolinite content greater than the soft natural kaolin of 80% graininess; Thickness of feed layer 20～40mm; Sapphire discs is placed the van-type resistance furnace; 900～1300 ℃ of roasting temperatures 2～24 hours; Obtain the spinelle kaolin (have on the kaolinic X-ray diffraction analysis chart of this spinelle spinelle characteristic peak with a small amount of mullite characteristic peak) of loose caking characteristics, break the granule below the written treaty 5mm gently into pieces, this particle and 1.2 times deionized water, 0.5 times corundum bead are mixed put into during stirring grinds with the mortar pestle; Agitation grinding 2～24 hours obtains the slurries of kaolin particle meso-position radius less than 3.5 μ m.These slurries are the required spinelle kaolin of preparation microballoon.
(2), will give birth to kaolin slurry, spinelle kaolin slurry by measuring mixing (in the bright base of kaolin; Its weight ratio is: give birth to kaolin: spinelle kaolin=20～90:10～80); Add an amount of waterglass and NaOH (function additive that is used as microballoon is to improve the intensity of microballoon) again; In the pulp jar, stir pulp and obtained mixed serum in 1～4 hour; These slurries precipitate easily, need acidifying to become stable colloid, and method is to wear out 0.5～2 hour after slowly adding acidifyings such as dilute sulfuric acid or nitric acid.Aging slurries are shaped to the atomized microball that particle size range is 20～150 μ m (PW) on small-sized and stream spray tower.The adding method is used slow spraying; Alr mode and speed are wanted suitably, are advisable with slurries appropriateness back-mixing, and the pulp jar is provided with the back-mixing baffle plate, and stirrer paddle has 30 ° of angles of inclination with respect to horizontal level.Preparation is during atomized microball, adds slurries pH after the acid neutralization greater than 9.5; The acid that neutralization is used is sulfuric acid or hydrochloric acid or formic acid.
(3), above-mentioned PW microballoon is put into sapphire discs; Thickness of feed layer 30～50mm; 500～900 ℃ of following roastings 1～6 hour; Make the living kaolin in the PW microballoon be converted into metakaolin, the roasting microballoon of preparation is called polycrystalline phase kaolin microsphere (being designated as BW) like this, the SiO that contains the mullite of metakaolin, spinelle kaolin, minute quantity among the BW and introduced by making beating waterglass on a small quantity
2And Na
2O, wherein metakaolin and spinelle kaolin content account for more than 90% of DW microballoon (in the calcination base).The kaolinic weight proportion of composing of different crystalline phases is a metakaolin in the roasting microballoon: spinelle kaolin=20～90:10～80; Sintering temperature is controlled at living kaolin in the scope that metakaolin transforms, so that the living kaolin in the roasting process among the PM is converted into metakaolin.Because the temperature of roasting PM is lower than the kaolinic formation temperature of spinelle; So in the roasting process; Spinelle kaolin thing phase and content among the PM can not change; The BW microballoon of preparation contains the kaolin of multiple crystalline phase like this, promptly contains the mullite of spinelle kaolin, metakaolin and minute quantity thereof simultaneously.
SiO in the spinelle
2And Al
2O
3Can react with hydrochloric acid, hydrofluoric acid, NaOH etc., mullite then can not.This is the basis of the present invention with polycrystalline phase kaolin microsphere synthetic catalyst.In the roasting process, changeing brilliant degree and roasting time has substantial connection simultaneously, and the short time more helps the generation of excessive attitude crystal.
(4), the BW microballoon is the important presoma microballoon of the high-quality catalyst of preparation macromolecule sieve content.The roasting microballoon is mixed the back hydrothermal crystallizing with waterglass, NaY directed agents, NaOH etc.; Make the crystallization microballoon (JW) that contains the NaY molecular sieve: concrete steps are following: polycrystalline phase kaolin microsphere DW is with after metering waterglass, NaY directed agents, NaOH, deionized water mix; 90 ℃ of hydrothermal crystallizings 12～32 hours; Can obtain to contain the crystallization microballoon (being designated as JW) of NaY molecular sieve, the proportion of composing of wherein used NaY directed agents (mole is formed) can be Na
2O:Al
2O
3: SiO
2: H
2O=9.5:1:10:720 also can be Na
2O:Al
2O
3: SiO
2: H
2O=15:1:16:320.Through the X-ray diffraction analysis, contain NaY molecular sieve 20～70% among the JW, lattice constant (is equivalent to SiO between 2.464nm～2.472nm
2/ Al
2O
3Than being 5.2～4.1).
(5), the crystallization microballoon is carried out processing such as conventional ion-exchange, hydrothermal calcine, washing, drying, obtain containing the FCC catalyst of Y zeolite, concrete steps are following: JW is carried out ion-exchange earlier to remove a large amount of sodium ions.Ion-exchange has several different methods, generally under pH value 3～4 situation, exchanges 1～2 time with ammonium sulfate earlier, then is used under pH3～4 conditions with rare-earth salts exchange 1～2 time.Rare-earth salts can be the single rare earth lanthanum chloride, also can be to be main mixed rare earth chlorides with the lanthanum chloride.Microballoon after the rare earth exchanged again in 100% steam or air atmosphere in 450～650 ℃ of following roastings 1～4 hour.Above process repeats twice and promptly obtains catalyst of the present invention.Above-mentioned rare earth ion exchanged can replace rare earth exchanged with ammonium sulfate, and the weak point of this replacement is that catalyst activity and stability are decreased, and also can reduce but benefit is the coke by-product of cracking reaction on the catalyst.Whether use rare earth and catalyst to contain how many rare earths in the Preparation of Catalyst and be advisable, depend primarily on the integration requirement of catalyst user active and coke selectivity.This catalyst has very high molecular sieve content, has flourishing central hole structure, better residual oil cracking reactivity, higher light oil productive rate, coke still less and hydrogen accessory substance.
Above-mentioned catalyst preparation process relates to the not kaolin of jljl phase, promptly gives birth to kaolin, metakaolin and spinelle kaolin.Here said " give birth to kaolin " is meant and do not pass through any heat treated kaolin, and it is kaolin crystal and other AMATs such as 15% following amorphous silicon oxide and aluminium oxide 85% or more that its thing is formed; " metakaolin " refers to give birth to kaolin in moderate temperature (500～800 ℃) down behind the roasting certain hour, and the complete avalanche of kaolin crystal structure does not but form other crystalline phase material, belongs to amorphous substance; " spinelle kaolin " refers to life kaolin behind the following roasting certain hour of higher temperature (900～110 ℃), and complete avalanche of kaolin crystal structure and commentaries on classics crystalline substance are the kaolin of spinelle phase structure, and a spot of mullite of association sometimes forms.
Y zeolite comprises the sodium type and (for example rare earth exchanged type REY, ammonium crossover HY, ultra steady type USY etc.) non-sodium type in the catalyst provided by the invention." initial Y zeolite " content is 20～70% in the catalyst provided by the invention, lattice constant is at 2.464nm～2.472nm, and " initial Y zeolite " content here refers to the NaY molecular sieve content that in crystallization microballoon JW, exists with the sodium type, the lattice constant that lattice constant also refers to the NaY molecular sieve.In the JW microballoon " initial Y zeolite " through above-mentioned ion-exchange and calcination process, major part is converted into rare-earth type REY, Hydrogen HY type, rare earth Hydrogen REHY, HUSY type, REUSY type, a kind of in the non-sodium type molecular sieves such as REHUSY type.
Catalyst provided by the invention has comprised the catalyst with different non-sodium type molecular sieves.
The chemical composition of catalyst provided by the invention (comprising zeolite component and non-zeolitic component) is SiO
2/ Al
2O
3Mol ratio is between being 1.6～3.0, Na
2O is between 0.3～0.8%, and rare earth is (with La
2O
3Meter) between 0.0～8.0%.
Catalyst provided by the invention has desirable size distribution, and its particle size range meets the commercial catalyst claimed range fully, and the small particle content below the 30 μ m is not more than 10% (V/V)), meso-position radius d
50Be about 65 μ m, reach granule content greater than 130 μ m and be not more than 12% (V/V)); Catalyst has better wear resistence, abrasion index 1.1～4.5%h
-1, representative value 1.5～3.5%h
-1, optimal value 1.5～2.5%h
-1
Catalyst provided by the invention has good porosity and abundant central hole structure, and the total pore volume that the water droplet method is measured can reach 0.65mLg
-1, the nitrogen method is measured total pore volume can reach 0.37mLg
-1, micropore (aperture is less than the 4nm) volume that the nitrogen adsorption method is measured can reach 0.15mLg
-1, mesopore (4-110nm) aperture volume can reach 0.22mLg
-1, the BJH method average pore size (d of mesopore (4-110nm) scope
Mean) reach 35nm, meta aperture (d
Median) reach 20nm, model aperture (d
Mode) reach 15nm.
Catalyst provided by the invention has well other physical and chemical index, and high specific surface area 280-710m is for example arranged
2G
-1Bulk density meets commercial FCC catalyst claimed range fully, and bulk density is between 0.75-1.20mLg
-1, representative value 0.80-0.95mLg
-1, optimum value 0.85mLg
-1
Catalyst provided by the invention has good hydrothermal stability.Prolongation along with ageing time; Its stability advantage is obvious more; REHY molecular sieve catalyst for example of the present invention and contrast medium relatively by FCC catalyst industry to the aging method (seeing CN1232862) of catalyst are: 800 ℃ of .100% steam aging 4 hours down, and catalyst activity of the present invention exceeds contrast medium more than 5 percentage points; And after aging 10 hours, exceed more than 9 percentage points.
Catalyst provided by the invention has very strong preventing from heavy metal performance.Along with the heavy metal pollution amount increases; Its preventing from heavy metal advantage is obvious more, and REHY molecular sieve catalyst for example of the present invention and comparative catalyst compare, under 5000ppm pollution of vanadium amount; Hydrothermal aging 17 hours, catalyst activity of the present invention exceed 26 percentage points of contrast medium.
Catalyst provided by the invention has good coke selectivity and gasoline selective.
The specific embodiment
The main analytical method that the embodiment of the invention relates to is following: the kaolin material phase analysis adopts the general x-ray powder diffraction of material phase analysis; NaY molecular sieve content assay method employing " SH/T0840-1992; NaY molecular sieve crystallinity determination method " and " SH/T0839-1992; NaY molecular sieve cell parameter assay method " in the crystallization microballoon (see China Standard Press's volume. standard of chemical industry compilation-catalyst and molecular sieve [M]. Beijing: China Standard Press, 2000); The SA3100 analyzer of U.S. Beckman Coulter company is adopted in specific area, pore volume and pore-size distribution analysis, measures product adsorption isotherm to nitrogen under the 77K condition, calculates specific surface and pore volume according to BET and BJH method respectively in view of the above; To catalyst carry out method that artificial heavy metal pollution adopts by traditional M itchell pollute method (see B. R. Mitchell. Metal Contamination of Cracking Catalysts [J]. Ind. Eng. Chem. Prod. Res. Dev.; 1980, (19): 209-213); The Micromeritics Micromeritics Saturn Digisizer of company 5100 particle size analyzers are adopted in the kaolin granulometry, and the granulometry material that carries with instrument before measuring is proofreaded instrument; Catalyst grain size is measured and is adopted the WINA2000 laser particle analyzer, and the granulometry material that carries with instrument before measuring is proofreaded instrument; The macroelement analysis adopts the macroelement analysis to adopt chemical method (GB/T 14564-1993 standard); The Thermo Electron X7-ICP of company spectroscopic methodology is adopted in trace element analysis; Standard method (the Yang Cuiding that the equal reference literature of other assay method of catalyst provides; Wu Wenhui; Wu Wenhui compiles. petrochemical industry analytical method (RIPP test method) [M]; Beijing: Science Press, 1990), wherein bulk density sees that RIPP32-97 standard method, catalyst total pore volume adopt the water droplet method to see that RIPP 28-90 standard method, the wear-resistant indexer of catalyst microballoon see that RIPP29-90 standard method, catalyst activity are measured and see RIPP92-90 standard method (loaded catalyst 5.0g; Reaction temperature 460; Standard oil is the huge port light diesel fuel, and product is made up of gas chromatographic analysis, micro-activity (MA)=(being lower than gasoline output+coke output+gas yield of 216 ℃ in the product)/combined feed * 100%); The selective evaluation of catalyst reaction adopts conventional fixed fluidized bed (FFB) method (RIPP90-90 standard method).
Step (1): the kaolinic preparation of ultra-fine life: in the long-pending general stirring mill of kettle, add 3000 deionized waters for 10L; Open and stir mill stirring at low speed (about 50rpm); With meso-position radius 3.8 μ m, crystalline phase kaolinite content is that 85% soft natural kaolin raw material 3Kg slowly drops into and stirs in the mill; Drop into each 1.5kg of zirconia 1.5kg bead of diameter 0.5mm, diameter 1mm more respectively, speed of agitator is brought up to about 200rpm gradually, and airtight stirring stops after 3 hours stirring; It is subsequent use to filter out slurries, and the meso-position radius of measuring kaolin particle in the slurries is 0.65 μ m.Above step repeats 4 times, obtains to contain 12kg and gives birth to kaolinic slurries, as the living kaolin of preparation catalyst.
Step (2): the kaolinic preparation of ultra-fine spinelle: with the used soft natural kaolin raw material 0.5Kg of step (1) 1050 ℃ of roastings 3 hours; The roasting material ground 4 hours in stirring mill; Leave and take grinding milk, the meso-position radius of measuring kaolin particle in the slurries is 1.5 μ m.Other operation is rapid identical with step (1).Above step repeats 4 times, obtains to contain the kaolinic slurries of 12kg spinelle, as the spinelle kaolin of preparation catalyst.
Step (3): the preparation of polycrystalline phase kaolin microsphere: get kaolin slurry that step (1) and (2) obtain and in making beating jar, mix to such an extent that be sprayed to slurries (in the kaolin base that burns by metering; Its weight ratio is: give birth to kaolin: spinelle kaolin=40:60), the kaolin total amount is 6kg in the mixed serum.Under agitation, (waterglass consists of 27.6%SiO to add water glass solution
2And 9.6%Na
2O) 445g adds 28% sodium hydroxide solution 536g, in the pulp jar, stirs pulp and obtains spray slurry in 1 hour; These slurries can precipitate after stopping stirring, neutralize slurries retrogradation this moment so slowly add 3M dilute sulfuric acid 150g again; Continue to stir the stable kaolin colloid slurries of formation after 0.5 hour, stop to stir, slurries granulation on small-sized and stream spray tower; Obtain atomized microball PW 5.8kg (water content 11-13%); Get 5g PW and be used to detect granularity in 2 hours, obtain the meso-position radius 69 μ m of microballoon 800 ℃ of roastings, 99% microballoon at 20-170 μ m, 95% microballoon at the 20-150 mu m range.The control of size distribution be the charging rate that gets into shower nozzle through adjustment with and the pressure that flows air realize; This will be according to the characteristic of institute's use spray tower; Repetition test could be confirmed its operating condition in advance; Because operating condition is relevant with the design parameter of used spray tower, so the spray operation condition does not have generality.
Get above-mentioned PW microballoon 600g, put into sapphire discs, the about 30mm of thickness of feed layer 700 ℃ of following roastings 2 hours, obtains roasting microballoon BW.The mullite that contains spinelle kaolin, metakaolin and minute quantity thereof among the BW simultaneously.
Step (4): the preparation of crystallization microballoon JW: in stainless steel crystallization device, drop into employed water glass solution 4.90kg in the step (3), stirring down, input orientation agent 280g (forms Na
2O:Al
2O
3: SiO
2: H
2O=9.5:1:10:720), 28% NaOH solution 146g, microballoon BW 700g.This moment, the liquid phase material mole composition proportion of composing of crystallization system was: Na
2O/SiO
2=0.367, H
2O/Na
2O=23.7; The crystallization device is warmed up to 90 ℃ and keep this temperature and stop crystallization after 24 hours, removes by filter mother liquor, spend the deionised water filter cake; Reach about 11.5 up to cleaning solution pH, dry cake obtains the about 1150g of crystallization microballoon JW; Through measuring, its degree of crystallinity is 71%, and lattice constant is 24.70..
Step (5): Preparation of catalysts: in stainless steel ion-exchange reactions device, add the 5kg deionized water, get the about 1.1kg of step (4) resulting crystallization microballoon JW, stir adding ion-exchange reactions device down, add 165g solid (NH again
3)
2SO
4, being warmed up to 85 ℃ and carrying out the ammonium ion exchange first time (hand over), the process of exchange reaction is that the liquid phase ammonium ion progressively replaces sodium ion among the microballoon JW to reduce the sodium ions content in the catalyst.React after 1 hour, stop to stir, sedimentation separation goes out mother liquor, and microspheres with solid is stayed in the agitated reactor.In order further to reduce sodium ion, carry out secondary ammonium exchange (two hand over), operating procedure is handed over ammonium one.After two friendships finish, still leave and take microspheres with solid in agitated reactor, carry out three rare earth exchanged (three hand over), method is that ammonium two is handed over adding 5kg water and 24g solid lanthanum chloride (LaCl in the filter cake that obtains
36H
2O), be warmed up to 85 ℃ of exchange reactions 1 hour.Reaction removes by filter mother liquor after finishing, and carries out first roasting (roasting) behind the filtration cakes torrefaction.Method of roasting is that desciccate is placed sapphire discs; Then sapphire discs is placed the van-type resistance furnace; Be warmed up to 120 ℃ in the resistance furnace and begin to feed steam later on, sample is in the steam atmosphere in whole roasting process, kept this temperature 1 hour after continuing to be warmed up to 550 ℃; Cut off steam then, cool to room temperature naturally.Obtain a roasting product.One roasting product carries out rare earth exchanged (four hand over) once more, and switching method and rare earth consumption are handed over three fully.Three hand over the product that obtains to carry out after baking (two roastings) again, and method of roasting is fully identical with a roasting process.Product of roasting is used (NH again
3)
2SO
4Additional exchange is (five hand over) once.Switching method and (NH
3)
2SO
4Consumption and two friendship processes are identical.The filter cake that five friendship processes obtain after finishing is 120 ℃ of following dried overnight, and desciccate is catalyst of the present invention (being designated as CAT-A1).
Step (6): kaolin proportion of composing in the spray slurry in the step (3) is adjusted into: give birth to kaolin: spinelle kaolin=30:70; Other set by step (3) method prepare polycrystalline phase kaolin microsphere; (4) method prepares the crystallization microballoon set by step, through measuring, through detecting; The degree of crystallinity of crystallization is 68%, and lattice constant is 24.67..With this crystallization microballoon is presoma, and (5) method prepares catalyst (being designated as CAT-A2) set by step
Comparative Examples 1:
The metakaolin microballoon prepares catalyst: the kaolin slurry that earlier step (1) method is prepared; The method of (3) prepares spray slurry set by step; Kaolin in the spray slurry is all from ultra-fine living kaolin slurry; The charge ratio of kaolin and waterglass and NaOH and step (3) is identical in the spray slurry, and the method for (3) is carried out mist projection granulating and promptly obtained atomized microball set by step, and atomized microball was obtained the roasting microballoon in 2 hours 700 ℃ of roastings; Because sintering temperature is in the temperature range that generates metakaolin, so have only the metakaolin phase in this roasting microballoon.With this roasting is presoma, and the method for operating of (4) and charge ratio thereof carry out hydrothermal crystallizing and obtain the crystallization microballoon set by step, and through detecting, the NaY content of this crystallization microballoon is 53%, the lattice constant of NaY is 24.73; With this crystallization microballoon set by step the method for operating and the charge ratio thereof of (5) carry out ion-exchange and roasting, obtain catalyst CAT-B1
Comparative Examples 2:
The spinelle kaolin microsphere prepares catalyst: the kaolin slurry that earlier instance 1 method is prepared; The method of (3) prepares spray slurry set by step; Kaolin in the spray slurry is all from ultra-fine living kaolin slurry, and the charge ratio of kaolin and waterglass and NaOH and step (3) is identical in the spray slurry, and the method for (3) is carried out mist projection granulating and promptly obtained atomized microball set by step; Atomized microball was obtained the roasting microballoon in 2 hours 980 ℃ of roastings; Because sintering temperature is generating the kaolinic temperature range of spinelle,, and follows and be less than 5% mullite so the overwhelming majority is a spinelle kaolin phase in the roasting microballoon.With this roasting microballoon is presoma, and the method for operating of (4) and charge ratio thereof carry out hydrothermal crystallizing and obtain the crystallization microballoon set by step; With this crystallization microballoon set by step the method for operating and the charge ratio thereof of (5) carry out ion-exchange and roasting, obtain catalyst CAT-B2
Comparative Examples 3:
Catalyst CAT-B3 according to the preparation of CN101537368A instance 9 methods
Implementation result
Physicochemical property and catalytic reaction character with catalyst provided by the invention and Comparative Examples catalyst compares below.
When the physicochemical property of catalyst was with catalytic reaction character in the present invention relatively, table 1. was physicochemical property and light oil microactivity mensuration results of catalyst.Find out from the physicochemical property and the micro-activity of table 1, catalyst provided by the invention (like CAT-2) have relatively good abrasion resistance, higher specific area, bigger pore volume, more in macropore, higher micro-activity.
The physicochemical property of table 1. catalyst and light oil microactivity
Table is annotated: A.I.-abrasion index (Attrition Index); B.D.-bulk density (Bulk Density); The S.A.-specific area
(Specific Area); P.V.-pore volume (Pore Volumes); M.A.-micro-activity (Micro Activity)
With fixed fluidized bed (FFB) the cracked product distribution of catalyst is estimated.During the FFB evaluate catalysts; Adopt the related control methods of sample with commercial catalyst; Rather than adopt the method for measuring absolute figure, and reason is to different operation person and sensing equipment, measured value is understood some variation; If adopt the method for sample and commercial standard (CS) catalyst comparative determination, just can overcome human error and equipment error.The commercial comparative catalyst who adopts is the catalyst for cracking heavy oil Ramcat that a kind of people know and use always
, this catalyst uses in industry has residual oil cracking effect preferably (see oil refining design [J], 2002,32 (2), pp29-33), this catalyst is up to also on a lot of commercial plants, using at present.It is 65% mixed gatch and 35% decompression residuum that FFB estimates used feedstock oil, and its character is seen table 2.The FFB condition is: earlier catalyst was worn out 10 hours in 800 ℃ of .100% steam in the FFB ager, the 150g aging catalyst is loaded into the FFB reactor, oil inlet quantity is 40.5 g, oil ratio 3.7, and the oil-feed time is 70 s, the about 16h of air speed
-1, 500 ℃ of reaction temperatures, product merges behind three grades of water condensations, and cutting initial boiling point～204 ℃ cut is a gasoline, and 204 ℃ of-350 ℃ of cuts are diesel oil (being light cycle oil LCO), and cut is an oil (VTB) at the bottom of the tower more than 350 ℃.Spent agent is a coke output through the loss of weight that burns after white.Make gas yield with normalization method.FFB sees that to evaluation result table 3. is in table 3; Total recovery is all product yield sums of (comprising target product and accessory substance); Conversion ratio=(dry gas yield+yield of liquefied gas+yield of gasoline+coking yield), yield of light oil=(yield of gasoline+diesel yield).Dry gas selectivity=dry gas yield/conversion ratio * 100%, gasoline selective, coke selectivity all adopt optionally computational methods of dry gas.
Find out that from table 3 catalyst of the present invention is being superior to the comparative catalyst aspect dry gas selectivity, gasoline selective, the coke selectivity.
Table 2. mixes the main character of decompressed wax oil and decompression residuum
Table 3. fixed fluidized bed (FFB) evaluation result
Above disclosedly be merely preferred embodiment of the present invention, can not limit the present invention's interest field certainly with this, the equivalent variations of therefore doing according to claim of the present invention still belongs to the scope that the present invention is contained.
Claims (5)
1. the preparation method of the in-situ crystallization type Cracking catalyst of polycrystalline phase kaolin microsphere preparation is characterized in that may further comprise the steps:
(1), living kaolin of ultra-fineization of preparation and spinelle kaolin slurry are as the base stock of preparation catalyst; Wherein: the kaolinic preparation temperature of spinelle is 850～1100 ℃; Ultra-fineization given birth to kaolinic granularity less than 2.5 μ m, and the kaolinic particle of spinelle is less than 2.0 μ m;
(2), will give birth to kaolin slurry and the spinelle kaolin slurry mixes with low amounts of water glass, mixed serum is prepared into stable spray slurry through adding the acid neutralization, is the atomized microball of 20～150 μ m again with the spray slurry spray shaping; The kaolinic weight proportion of composing of the different crystalline phases kaolin of making a living in the atomized microball: spinelle kaolin=20～90:10～80;
(3), will hour obtain the roasting microballoon at 500～900 ℃ of roasting temperature atomized microball numbers, contain the mullite of spinelle kaolin, metakaolin and minute quantity thereof in the roasting microballoon simultaneously; The kaolinic weight proportion of composing of different crystalline phases is a metakaolin in the roasting microballoon: spinelle kaolin=20～90:10～80;
(4), with the roasting microballoon mix with waterglass, NaY directed agents, NaOH the back hydrothermal crystallizing, make the crystallization microballoon that contains the NaY molecular sieve;
(5), the crystallization microballoon carries out conventional ion-exchange, hydrothermal calcine, washing, dried, obtains containing the FCC catalyst of Y zeolite.
2. the preparation method of the in-situ crystallization type Cracking catalyst of polycrystalline phase kaolin microsphere as claimed in claim 1 preparation is characterized in that: polycrystalline phase kaolin microsphere be via the atomized microball roasting obtain a kind ofly contain metakaolin simultaneously, spinelle kaolin is roasting microballoon main, that association has a small amount of mullite.
3. the preparation method of the in-situ crystallization type Cracking catalyst of polycrystalline phase kaolin microsphere as claimed in claim 1 preparation is characterized in that: during the preparation atomized microball, add slurries pH after the acid neutralization greater than 9.5; The acid that neutralization is used is sulfuric acid or hydrochloric acid or formic acid.
4. the preparation method of the in-situ crystallization type Cracking catalyst of polycrystalline phase kaolin microsphere preparation as claimed in claim 1; It is characterized in that: contain in the crystallization microballoon of NaY molecular sieve; The weight content of NaY molecular sieve is 20～72%, and the structure cell lattice constant of corresponding NaY molecular sieve is 2.464nm～2.472nm.
5. the in-situ crystallization type Cracking catalyst of polycrystalline phase kaolin microsphere preparation is characterized in that: the scope of its middle rare earth weight content is 0.0～11.0%, Na
2O content range 0.25～0.80%; Wherein active component comprises the non-sodium type Y molecular sieve of ultra steady and non-super stabilizing, and non-sodium type Y molecular sieve comprises REHY, HUSY type, the REUSY type of rare-earth type REY, Hydrogen HY, rare earth Hydrogen, the compound of one or more in the non-sodium type of the REHUSY type molecular sieve.
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| US5395809A (en) * | 1993-11-01 | 1995-03-07 | Engelhard Corporation | Modified microsphere FCC catalysts |
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| CN104211084A (en) * | 2014-09-03 | 2014-12-17 | 中国海洋石油总公司 | Preparation method of integrated NaY molecular sieve with high silica-alumina ratio |
| CN104211084B (en) * | 2014-09-03 | 2016-06-15 | 中国海洋石油总公司 | A kind of preparation method of monoblock type high silica alumina ratio NaY molecular sieve |
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