CN106040217B - A kind of preparation method of the assistant for calalytic cracking containing boehmite - Google Patents
A kind of preparation method of the assistant for calalytic cracking containing boehmite Download PDFInfo
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- CN106040217B CN106040217B CN201610354111.1A CN201610354111A CN106040217B CN 106040217 B CN106040217 B CN 106040217B CN 201610354111 A CN201610354111 A CN 201610354111A CN 106040217 B CN106040217 B CN 106040217B
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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Abstract
A kind of preparation method of the assistant for calalytic cracking containing boehmite.This method includes：15 minutes modified boehmite A made above are mixed in part boehmite and siliceous solution, modified boehmite A is mixed with beating with remaining boehmite B, clay, heavy metal chelating agent, and slurries are through homogeneous, acidification, shaping and drying, ion exchange obtain assistant for calalytic cracking；Wherein, the butt quality ratio of modified boehmite A and remaining boehmite B are 0.2~2.5, and the addition of siliceous solution is with SiO2It is calculated as the 0.5%~8% of modified boehmite A dry weights；Silicon exists with ionic condition in the siliceous solution.Assistant for calalytic cracking heavy oil conversion performance prepared by this method is strong, coke selectivity is good.
Description
Technical field
The present invention relates to a kind of preparation methods of assistant for calalytic cracking.
Background technology
Deep processing with the continuous aggravation of crude oil heaviness, in poor quality trend in world wide, weight, crude oil with poor quality becomes
Realize that enterprise profit maximizes faced significant challenge in refinery.And it is transformed relatively with catalytic cracking unit, high-performance catalysis
The exploitation of cracking additive, auxiliary agent is the deep conversion that refinery promotes heavy crude, improves production capacity, and it is most to increase high value added product
For economic, flexible effective means.And traditional view is thought, heavy oil molecules hardly enter molecular sieve due to its big size
Internal cracking, cracking center are provided by molecular sieve outer surface and catalyst substrates, and due to the small outer surface of molecular sieve, heavy oil is big
Molecule mainly occurs on medium carrier precracked.To improve the cracking performance of heavy oil macromolecular, the acid to medium carrier is needed
Property and pore structure carry out modulation.
US4749672, US4836913 disclose a kind of CLS/mullite carrier materials, using kaolin as raw material, warp
~1000 DEG C of high-temperature roastings are crossed, the product for wherein generating a large amount of sial spinel structures and a small amount of mullite structure is made.Using
The Large Pore Cracking component of a high activity, high stability obtained from alkali density and ion exchange under control condition.The carrier
With preferable residual oil cracking performance.
USP5051385 describes a kind of synthetic method of mesoporous silica-alumina material, and aperture exists in 20-50nm, specific surface area
50-100m2g-1.Silica-alumina material prepared by CN03147975.8, aperture is in 10-20nm, and pore volume is up to 1cm3g-1More than.
The GO-ULTRA catalyst (NPRA, 2010AM-10-175) that Albemarle2009 is newly released, main feature
One of be exactly that macroporous structure greatly improves, the macropore between 100-400nm is significantly increased, be greatly reduced cross cracking it is anti-
It answers, excessive hydrogen transfer activity and coke polymerisation.GO-ULTRA compared with its company catalyst RUBY, identical oil ratio,
Under conversion ratio and coke difference, GO-ULTRA with high gasoline and diesel yield simultaneously, also preferable coke selectivity.
The method that US 165083 reports the addition sucrose in catalyst synthesis processes introduces macropore in matrix, makes to urge
The activity and preventing from heavy metal performance of agent are improved.CN1778676A discloses a kind of preparation side of in-situ crystallization catalyst
Method can be effectively improved the pore structure of catalyst by the addition of structural auxiliary agent starch, carboxymethyl cellulose fiber element.
US4624773 reports a kind of method preparing macropore catalytic cracking auxiliary agent using carbon black.Pass through the introducing of carbon black
At least 0.10cm can be generated3g-1The above aperture is more than the macropore of 100nm.Qi Yan equalitys are used by the way that different-grain diameter, difference is added
The polystyrene sphere of content has synthesized macropore catalytic cracking auxiliary agent, and it was found that the addition of polystyrene sphere not only introduces
Middle macropore, and improve catalyst activity (Energy Fuels, 24 (5), 2010,2825).
The DMS technologies of ENGHARD are the abbreviation of Distributed Matrix Structures technologies, are had between particle
Card form accumulation form, the matrix structure of high degree of dispersion, while the zeolite crystal of high degree of dispersion are covered in stromal surface and improve
Catalyst choice contains stabilization, mesoporous rich alumina supporter in addition, in order to improve the cracking capability of heavy oil in DMS products.It should
Rich alumina supporter is obtained (NPRA-AM-03-38) by alkali modification high-temperature roasting kaolin.
CN201210062013.2 discloses a kind of preparation method of macropore catalytic cracking auxiliary agent, by being boiled in spray slurry
Point temperature is less than or equal to decompose the introducing for the compound for being fully converted to gas at 150 DEG C or 150 DEG C, is dried in catalyst spray
Macropore in being introduced into the process.
Since the big molecular diameter of heavy oil molecules hardly enters molecular sieve pore passage, the cracking of heavy oil molecules mainly occurs
On catalyst substrates.For current domestic assistant for calalytic cracking, the acidity and meso-hole structure of matrix are mainly by active oxidation
Aluminium provides, and mainly based on double aluminum matrix of boehmite and Aluminum sol.Therefore technical staff is also often used modified oxygen
Change aluminium to improve the pore structure of catalyst.
Zheng Jinyu etc. (petroleum journal (PETROLEUM PROCESSING), 26 (6), 2010,846) is using ethyl orthosilicate to boehmite
It is modified, in order to make silicon atom enter in boehmite crystalline phase, it is modified in experience acid catalyzed reaction, heating aging, filter, wash
It washs, dry and the reaction step of a series of complex such as high-temperature roasting, silicone hydroxyl and aluminium hydroxyl condensation, silicon enter crystalline phase, and then adjust
Become the hydrothermal stability and acidity of aluminium oxide.But the pore volume of boehmite and aperture are apparent there is no occurring before and after Si modification
Variation, Si modification be significantly improve material hydrothermal stability and introduce B acid；Simultaneously as Si modification intends thin water aluminium
Stone experienced 550 degree of high-temperature roastings, and high-temperature roasting boehmite will cause its surface hydroxyl to be largely condensed, and peptization performance will
Drastically decline, adhesive property is deteriorated, and under the conditions of identical Aluminum sol, the wear-resistant index of catalyst/auxiliary agent will be decreased obviously, and be
Ensure that the binder contents such as Aluminum sol need to be significantly increased in catalyst/auxiliary agent intensity, inevitably results in cost increase.
CN03147975 discloses a kind of mesoporous silica-alumina material suitable for assistant for calalytic cracking, which, which has, intends thin water
The phase structure of aluminium stone, the anhydrous chemical expression in terms of oxide weight are：(0~0.3) Na2O (40~90) Al2O3·
(10-60) SiO2, specific surface area 200-400m20.5~2.0ml/g of/g, Kong Rongwei, average pore size are 8~20nm, most
Can several apertures be 5~15nm.The material is that silicon source and aqueous slkali are carried out neutralization plastic, silicon source and aging is then added, finally
Made of ion exchange, drying, roasting.Pore distribution concentration in the material remains the central hole structure feature of aluminium oxide, has
Good hydrothermal stability has stronger macromolecular cracking energy when being used as assistant for calalytic cracking carrier than existing silica-alumina material
Power, higher feedstock oil conversion ratio, lower heavy oil yield.Its shortcoming is that this method prepares mesoporous silicon using sol-gal process
Aluminium, by control, two kinds of sial acid group is interionic is condensed to yield porous material, is carried out using the silicon source of low concentration, silicon source anti-
It answers, product yield is low；Step is complicated, requires pH value and reaction temperature high；Because introducing more anion and sodium ion, need
A large amount of water carry out ion exchange or washing process, and water consume is high.
CN200510068164.9 discloses a kind of catalyst for cracking petroleum hydrocarbons, by dry basis, contains 10~50
The y-type zeolite of weight %, the shape-selective zeolite of 0~5 weight %, the modified alumina composition of 10~60 weight %, the clay of 5~45 weight %
With the inorganic oxide binder of 2~35 weight %, the modified alumina composition is measured by Pyridine adsorption IR spectra method
Surface acid center only has Lewis acid, changes wherein oxidation silicon components are dispersed in alumina body phase without Bronsted acid
Property alumina composition still keeps γ-Al2O3XRD diffraction phase characters.It, should due to the use of silica modified aluminium oxide
Catalyst has preferable isomerizating straight-chain catalytic performance.The preparation method of the catalyst is：(1) in the aqueous solution of aluminium salt
Middle addition alkaline silicate solution adjusts pH value 3~9, until forming gel；(2) by hydrogel warms to 45~95 DEG C, always
Change, filter, washing removes sodium ion therein, obtains silica modified alumina composition；(3) by the composition with
Boehmite is mixed with beating, and addition is mineral acid acidified, stirs evenly, obtains mixed serum；(4) zeolite and clay material are mixed
After conjunction, inorganic oxide binder mashing is added, stirs evenly, obtains mixed serum；(5) by step (4) mixing slurry
Liquid is mixed with step (3) described mixed serum, is continued after being stirred until homogeneous, and slurries are taken out, and drying, roasting are obtained containing modified oxygen
Change the Cracking catalyst of aluminium composition.In the preparation of the catalyst, it is still silicon that silica modified alumina composition is substantive,
Solgel reaction between aluminium ion, this method is equally with yield is low, step is complicated, pH value and temperature requirement are high, washings
Consume big disadvantage.
Conventional catalytic cracking auxiliary agent is usually made of carrier and molecular sieve active component two parts, and heavy oil conversion is helped
For agent, since it is mainly for heavy oil macromolecular cracking, molecular sieve active component can not also be contained.Intercat companies of the U.S.
Be proposed the bottoms of tower BCA-105 oil cracking additive in the 1990s, the heavy oil pyrolysis auxiliary agent be free of zeolite component, using with
Certain activity and acid amorphous silicon aluminium.
CN99121917.1 discloses a kind of cracking assistant for catalytic cracking of heavy oil, and the auxiliary agent is by aluminium oxide, clay and oxidation
Silicon forms, and on the basis of the total amount of auxiliary agent, the content of aluminium oxide is 10-85 weights %, clay content is 10-85 weights %, silica
Content is 1-20 weight %, and the weight ratio of silica and aluminium oxide is 0.01-0.5.The auxiliary agent has higher macromolecular cracking energy
Power is used together with major catalyst zeolite-containing, can improve the conversion ratio of heavy oil, reduces slurry oil yield, is increased light oil and is received
Rate.
Jinling Petrochemical Co. develops (petroleum refining and chemical industry, 2000,31 (12)：8~11) it develops and improves residual oil catalysis
The carrier of the auxiliary agent of cracking light oil yield, the auxiliary agent includes tetra- kinds of components of A1, Si, Mg and P, and active component selects rare earth gold
Belong to and two component of transition metal, the auxiliary agent have preferable slag oil cracking activity and stronger hydrothermal stability.
CN201110026948.0 discloses a kind of catalytic cracking compositions and assistant for calalytic cracking, catalytic cracking combination
Object contains the silicon magnesium glue of 2-65 weights %, the rare earth compound of 1-25 weights %, a diaspore of 15-85 weights %.
Assistant for calalytic cracking without zeolite component usually requires larger pore volume and specific surface area, a good anti-huge sum of money
Attribute energy.Enhance heavy oil conversion performance, matrix specific surface area should be increased.Boehmite is current assistant for calalytic cracking matrix
Important component, however due to boehmite peptization after, viscosity is significantly increased, if only contained by increasing boehmite
It measures to increase matrix specific surface area declining to a great extent the solid content for bringing auxiliary agent slurries, influences assistant for calalytic cracking yield.Together
When, the fine particle generated after boehmite peptization will also block assistant for calalytic cracking duct.Since assistant for calalytic cracking is ground
The adhesive property for damaging exponent pair material is very sensitive, and boehmite provides not only the cracking place of heavy oil molecules, while also rising
It is acted on to binder, enhances the wear-resistant index of assistant for calalytic cracking；It is introduced directly into other activated alumina materials then also normal band
Carry out being substantially increased for catalyst abrasion index, will be unable to reach industrial dose of mark when the abrasion index of assistant for calalytic cracking is excessively high
It is accurate.
Therefore, assistant for calalytic cracking, pore volume, heavy oil are directly prepared as key component using boehmite at present
Conversion capability etc. is still difficult to reach perfect condition.
Invention content
The present invention provides catalysis prepared by a kind of preparation method of the assistant for calalytic cracking containing boehmite, this method
Cracking additive has good heavy oil conversion performance and coke selectivity while ensureing to have preferable wear resistance.
A kind of preparation method of assistant for calalytic cracking containing boehmite of the present invention, including：Part is quasi- thin
15 minutes modified boehmite A made above are mixed with siliceous solution in diaspore, and modified boehmite A and residue are quasi-
Boehmite B, clay, heavy metal chelating agent are mixed with beating, and slurries are urged through homogeneous, acidification, shaping and drying, ion exchange
Change cracking additive；Wherein, the butt quality ratio of modified boehmite A and remaining boehmite B are 0.2~2.5, preferably
0.3~2.0, more preferable 0.3~1.5, the addition of siliceous solution is with SiO2It is calculated as modified boehmite A dry weights
0.5%~8%, preferably 1.5%~6%.
A kind of preparation method of assistant for calalytic cracking containing boehmite disclosed in this invention, the part is intended thin
Diaspore and siliceous solution are mixed 15 minutes modified boehmite A made above, preferably 25-40 minutes.
A kind of preparation method of assistant for calalytic cracking containing boehmite disclosed in this invention, described is siliceous molten
Liquid, silicon exists with ionic condition in solution.Siliceous solution is selected from sodium metasilicate, sodium metasilicate, methyl orthosilicate, ethyl orthosilicate
In one or more, preferably waterglass and ethyl orthosilicate.
A kind of preparation method of assistant for calalytic cracking containing boehmite disclosed in this invention, the catalytic cracking
Auxiliary agent is in terms of 100 parts by assistant for calalytic cracking each component gross mass of feeding intake, and the boehmite addition in terms of aluminium oxide is 15
~75 parts, preferably 20~65 parts, wherein remaining boehmite B is 8~45 parts, particularly preferred 10~40 parts, Si modification is intended thin
Diaspore A is 7~30 parts, particularly preferred 10~25 parts；1~10 part of heavy metal chelating agent；The clay 20~84 calculated with butt
Part, preferably 30~79 parts.
A kind of preparation method of assistant for calalytic cracking containing boehmite disclosed in this invention, the catalytic cracking
In addition to the boehmite, clay matrix in auxiliary agent, it also may include that other common matrix, the common matrix of others are not done
It is specific to limit, it is the common knowledge of this field；Other common matrix are generally selected from aluminium oxide, aluminum oxide precursor object, silica, oxygen
The mixture of one or more substances in SiClx predecessor, magnesia, precursor compound for MgO.The aluminium oxide is selected from α-oxygen
Change one or more, described aluminium oxide in aluminium, beta-alumina, gama-alumina, δ-aluminium oxide, η-aluminium oxide, θ-aluminium oxide
Predecessor is one or more in Aluminum sol, aluminium hydroxide；The silica is selected from Ludox, silica gel, mesoporous dioxy
One or more in SiClx, white carbon, aerosil, the silica predecessor is selected from sodium metasilicate, metasilicic acid
It is one or more in sodium, positive esters of silicon acis；The precursor compound for MgO is selected from magnesium chloride, magnesium hydroxide, magnesium nitrate, magnesium carbonate
In it is one or more.
Clay in the present invention is kaolin, halloysite, montmorillonite, bentonite, diatomite, sepiolite, concave convex rod
It is one or more in stone, rectorite, galapectite, hydrotalcite, saponite.More preferably kaolin, halloysite, diatomite,
It is one or more in sepiolite, attapulgite, rectorite, galapectite.
The present invention, without particular/special requirement, can be heavy metal chelating agent commonly used in the art to the heavy metal chelating agent.
Such as petrochemical industry 2000,29, (368-373) and Journal of Molecular Catalysis, 2005,19 (6) 504-510, in disclose different metals
Trapping agent, there is magnesia, strontium oxide strontia, barium monoxide, rare earth oxide, aluminium oxide, silica, the forerunner of zirconium oxide or these substances
Object.Present invention preferably employs the predecessors of rare earth oxide and/or rare earth oxide as metal traps.Before the rare earth oxide
It is preferably the one or more of rare earth chloride, nitric acid rare earth, carbonated rare earth and hydrogen-oxygen rare earth to drive object.Wherein, rare earth element can be with
It is one or more in lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium.
A kind of assistant for calalytic cracking preparation method containing boehmite of the present invention, except part boehmite exists
It is mixed with Si modification solution before acidification and is modified within 15 minutes or more outer, remaining can refer to the prior art and carries out.Meanwhile this
Invention does not do particular determination to charging sequence.Also exist as clay, heavy metal chelating agent can be added before boehmite acidification
It is added after acidification；Si modification boehmite is acidified jointly after being mixed with unmodified boehmite, after being also acidified respectively
It is mixed again.
A kind of preparation method of assistant for calalytic cracking containing boehmite disclosed in this invention, realization method are selected from
One of following mode.Mode 1 will include clay, heavy metal chelating agent, modified boehmite A and remaining boehmite
B, deionized water, after being mixed with beating homogeneous, acid adding aging, in 20~90 DEG C of agings 0.5~3 hour.Mode 2, will be modified quasi- thin
Diaspore A, deionized water are beaten homogeneous, obtain slurries 1, by clay, heavy metal chelating agent, remaining boehmite B, deionization
After water is mixed with beating homogeneous, slurries 2 are obtained, slurries 1 and slurries 2 distinguish acid adding heating aging, in 20~90 DEG C of agings 0.5~3
After hour, slurries 1 and slurries 2 mix homogeneous and obtain catalyst slurry.The acid is inorganic acid, can be hydrochloric acid, phosphoric acid, sulphur
It is one or more in acid, nitric acid.
A kind of preparation method of assistant for calalytic cracking containing boehmite of the present invention, the shaping and drying are
Refer to granulating and forming and the drying of assistant for calalytic cracking, this is technology known in those skilled in the art, assistant for calalytic cracking
Preparation is generally dried using spray shaping, and process conditions are that spray tower fire box temperature is controlled at 450~550 DEG C, tail gas of spraying
Temperature is controlled at 150~300 DEG C.
A kind of preparation method of assistant for calalytic cracking containing boehmite of the present invention, the catalytic cracking of gained help
Agent can be further processed with ion exchange, ion exchange can remove assistant for calalytic cracking prepare each link bring into it is various miscellaneous
Matter ion, including Na+, SO4 2-, Cl-Etc., it is washed using massive laundering or ammonium salt under usual acid condition.What the present invention recommended
The process conditions of ion exchange：Ion exchange is exchanged using acid or ammonium exchanges, pH value 2.5~3.5, and swap time is 0.3~2 small
When.
A kind of assistant for calalytic cracking preparation method containing boehmite of the present invention, passes through boehmite and silicon
The use in conjunction of modified boehmite can increase its macropore hole simultaneously in effectively control assistant for calalytic cracking abrasion index and hold,
In conversion heavy oil macromolecular, secondary cracking is reduced, improvement catalyst coke selective meter is revealed more more superior than conventional method
Reactivity worth, while it uses cheap modified feedstock, it is easy to operate, there is prospects for commercial application.
Specific implementation mode
Embodiment further instruction technical solutions according to the invention will be passed through below.
1, primary analysis method
1 primary analysis method of the present invention of table
| Project | Method | Standard code |
| RE2O3, m% | XRF methods | / |
| Na2O | XRF methods | / |
| Pore volume, cm3.g-1 | Water droplet method | Q/SYLS0521-2002 |
2. abrasion index test method
The tear strength of atomized microball is thought of a way measurement using gas, and before measurement, atomized microball is without any roasting：It will
Atomized microball is placed in the device MS-C type wear index analyzers for measuring abrasion index, with gas shock 5 hours, first 1 hour
The fine powder amount of collection is that itself (is less than 15 containing band, the latter 4 hours fine powder amounts collected as the fine powder amount generated in prepared by microballoon
μm), it is abrasion index that the latter 4 hours fine powder quality collected, which account for the percentage of sample gross mass,.
3. evaluating catalyst：
Catalyst of the present invention and comparative catalyst are respectively with industrial catalyst LDO-70 by weight 1:4, which carry out physics, mixes
Close, mixing rear catalyst by deposit 3000ppmNi, 5000ppmV carry out heavy metal pollution, pollution rear catalyst through 800 DEG C,
It is evaluated using ACE devices after 100% vapor aging 4h, feedstock oil used is that wide fraction wax oil and Xinjiang decompression are depressurized in Xinjiang
Residual oil, intermingled dregs ratio 30%.Raw material oil nature is shown in Table 2.
2 catalyst choice of table evaluates raw materials used oil nature
Embodiment 1
1.154 kilograms of boehmites (solid content 65.0%, Shanxi Aluminium Plant product, similarly hereinafter) are weighed, 4.5 kilograms is added and goes
Ionized water is added with stirring 228 milliliters of waterglass (SiO2250g/l, Na2O88g/l, Lanzhou Petrochemical Company production), continue to stir
After 30 minutes, 1.154 kilograms of boehmite, 2.943 kilograms of kaolin (solid content 83.41%, butt, Chinese kaolinites are added
Scholar company industrial products, similarly hereinafter), 2.062 kilograms of Aluminum sol (contains Al2O319.4wt%, Catalyst Factory of Lanzhou Petrochemical Company production,
Similarly hereinafter), 1.634 kilograms of Ludox (solid content 30.6%, similarly hereinafter), earth solution 346.3ml (content 288.75gL-1, La,
Ce mischmetals pick up from Lanzhou Petrochemical catalyst plant, similarly hereinafter), solid oxidation magnesium 50g stirs two hours, adds 254 milliliters
37 weight % hydrochloric acid, stirring 1 hour after, at 50 DEG C aging be spray-dried after 2 hours.
The microballoon of spray drying gained is then stirred 30 minutes in pH=3 aqueous hydrochloric acid solutions through 600 DEG C of roasting 1h,
It filters, it is 6 hours dry at 120 DEG C, obtain assistant for calalytic cracking CAT-1 provided by the invention.
The group of assistant for calalytic cracking CAT-1 becomes：48.10 heavy % of kaolin, the oxidation from unmodified boehmite
Aluminium is 15 heavy %, and the aluminium oxide of the boehmite from Si modification is 15 heavy %, and the aluminium oxide from Aluminum sol is 8 heavy %,
10 heavy % of silica from Ludox, the silica from waterglass are 0.9 heavy %, and silica accounts for modified quasi- thin in waterglass
The mass percent of diaspore is 6wt%, and magnesia is 1 heavy %, and rare earth oxide is 2 heavy %.
Embodiment 2
1.923 kilograms of boehmites are weighed, 6.4 kilograms of deionized waters are added, are added with stirring 253 milliliters of waterglass,
After continuing stirring 30 minutes, 1.538 kilograms of boehmite, 2.458 kilograms of kaolin, 1.804 kilograms of Aluminum sol, rare earth is added
Solution 1039ml is stirred 1.5 hours, adds the hydrochloric acid of 320 milliliter of 37 weight %, after stirring 1 hour, at 70 DEG C aging 40 divide
It is spray-dried after clock.
By the microballoon of spray drying gained through 550 DEG C of roasting 2h, 40 points are then stirred in pH=3.2 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking CAT-2 provided by the invention.
The group of assistant for calalytic cracking CAT-2 becomes：41 heavy % of kaolin, the aluminium oxide from unmodified boehmite are
The aluminium oxide of 20 heavy %, the boehmite from Si modification are 25 heavy %, and the aluminium oxide from Aluminum sol is 7 heavy %, is come from
The silica of waterglass is 1.0 heavy %, and the mass percent that silica accounts for modified boehmite in waterglass is 4wt%, oxygen
Change rare earth is 6 heavy %.
Embodiment 3
1.538 kilograms of boehmites are weighed, 9.0 kilograms of deionized waters are added, are added with stirring 185.8 milliliters of positive silicic acid
After continuing stirring 30 minutes, 1.923 kilograms of boehmite, 2.638 kilograms of kaolin, Aluminum sol 1.546 thousand is added in ethyl ester
Gram, earth solution 692.6ml is stirred 2 hours, adds the hydrochloric acid of 280 milliliter of 37 weight %, old at 60 DEG C after stirring 1 hour
It is spray-dried after changing 2 hours.
By the microballoon of spray drying gained through 650 DEG C of roasting 2h, 20 points are then stirred in pH=2.8 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking CAT-3 provided by the invention.
The group of assistant for calalytic cracking CAT-3 becomes：41 heavy % of kaolin, the aluminium oxide from unmodified boehmite are
The aluminium oxide of 25 heavy %, the boehmite from Si modification are 20 heavy %, and the aluminium oxide from Aluminum sol is 6 heavy %, is come from
The silica of waterglass is 1.0 heavy %, and the mass percent that silica accounts for modified boehmite in ethyl orthosilicate is
5wt%, rare earth oxide are 7 heavy %.
Embodiment 4
0.769 kilogram of boehmite is weighed, 11.0 kilograms of deionized waters are added, are added with stirring 76 milliliters of waterglass,
After continuing stirring 30 minutes, 2.308 kilograms of boehmite, 2.440 kilograms of kaolin, 2.32 kilograms of Aluminum sol, rare earth is added
Solution 1731.6ml is stirred 2 hours, adds the hydrochloric acid of 328 milliliter of 37 weight %, after stirring 1 hour, aging 2 hours at 55 DEG C
After be spray-dried.
The microballoon of spray drying gained is then stirred 60 points through 500 DEG C of roasting 2h in pH=3.5 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking CAT-4 provided by the invention.
The group of assistant for calalytic cracking CAT-4 becomes：40.7 heavy % of kaolin, the aluminium oxide from unmodified boehmite
For 30 heavy %, the aluminium oxide of the boehmite from Si modification is 10 heavy %, and the aluminium oxide from Aluminum sol is 9 heavy %, is come
It is 0.3 heavy % from the silica of waterglass, it is 3wt% that silica, which accounts for the mass percent of modified boehmite, in waterglass,
Rare earth oxide is 10 heavy %.
Embodiment 5
1.154 kilograms of boehmites are weighed, 13.0 kilograms of deionized waters are added, are added with stirring 76 milliliters of waterglass,
After continuing stirring 30 minutes, 2.692 kilograms of boehmite is added, 2.2 kilograms of kaolin, 1.289 kilograms of Aluminum sol, rare earth is molten
Liquid 1385.3ml is stirred 2 hours, adds the hydrochloric acid of 363 milliliter of 37 weight %, after stirring 1 hour, at 65 DEG C after aging 2 hours
Spray drying.
The microballoon of spray drying gained is then stirred 60 points through 620 DEG C of roasting 2h in pH=3.3 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking CAT-5 provided by the invention.
The group of assistant for calalytic cracking CAT-5 becomes：36.7 heavy % of kaolin, the aluminium oxide from unmodified boehmite
For 35 heavy %, the aluminium oxide of the boehmite from Si modification is 15 heavy %, and the aluminium oxide from Aluminum sol is 5 heavy %, is come
It is 0.3 heavy % from the silica of waterglass, it is 2wt% that silica, which accounts for the mass percent of modified boehmite, in waterglass,
Rare earth oxide is 8 heavy %.
Comparative example 1
It is prepared for comparison assistant for calalytic cracking with reference to embodiment 2, boehmite content is modified quasi- thin in embodiment 2
The sum of diaspore and unmodified boehmite.
3.461 kilograms of boehmites are weighed, 12 kilograms of deionized waters, 2.518 kilograms of kaolin, Aluminum sol is added
1.804 kilograms, earth solution 1039ml is stirred 1.5 hours, adds the hydrochloric acid of 320 milliliter of 37 weight %, after stirring 1 hour,
Aging is spray-dried after forty minutes at 70 DEG C.
By the microballoon of spray drying gained through 550 DEG C of roasting 2h, 40 points are then stirred in pH=3.2 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking DB-CAT1 provided by the invention.
The group of assistant for calalytic cracking DB-CAT1 becomes：The aluminium oxide of 42 heavy % of kaolin, boehmite are 45 heavy %,
Aluminium oxide from Aluminum sol is 7 heavy %, and rare earth oxide is 6 heavy %.
Comparative example 2
It is prepared for comparative catalyst with reference to embodiment 3, replaces ethyl orthosilicate to intending thin be modified using Ludox.
1.538 kilograms of boehmites are weighed, 9.0 kilograms of deionized waters are added, are added with stirring 253g Ludox (Qingzhou
City Yongxing silica gel product Co., Ltd, SiO2Content 25wt%), after continuing stirring 30 minutes, boehmite 1.923 thousand is added
Gram, 2.638 kilograms of kaolin, 1.546 kilograms of Aluminum sol, earth solution 692.6ml stirs 2 hours, adds 280 milliliter 37
Weight % hydrochloric acid, stirring 1 hour after, at 60 DEG C aging be spray-dried after 2 hours.
By the microballoon of spray drying gained through 650 DEG C of roasting 2h, 20 points are then stirred in pH=2.8 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking DB-CAT2 provided by the invention.
The group of assistant for calalytic cracking DB-CAT2 becomes：41 heavy % of kaolin, the aluminium oxide from unmodified boehmite
For 25 heavy %, the aluminium oxide from silica sol modified boehmite is 20 heavy %, and the aluminium oxide from Aluminum sol is 6
Weight %, the silica from waterglass are 1.0 heavy %, and the mass percent that silica accounts for modified boehmite in Ludox is
5wt%, rare earth oxide are 7 heavy %.
Comparative example 3
Method with reference to described in (petroleum journal (PETROLEUM PROCESSING), 26 (6), 2010,846) such as Zheng Jinyu prepares Si modification
Hydrochloric acid acidification is added in alumina material, boehmite, and acid-aluminum ratio 0.19 introduces tetraethoxy-silicane, heats up 60 DEG C after stirring 1h,
It is stirred for 1h, is then stood at 25 DEG C for 24 hours, Si modification is prepared then at 550 DEG C of roasting 4h in 100 DEG C of dry 12h after filtering
Alumina material Al2O3- Si, the mass percent that modified silicon oxide accounts for boehmite are 5wt%.
Weigh 1.601 kilograms of Al2O39.0 kilograms of deionized waters are added in-Si, after continuing stirring 30 minutes, are added and intend thin water
1.923 kilograms of aluminium stone, 2.638 kilograms of kaolin, 1.546 kilograms of Aluminum sol, earth solution 692.6ml are stirred 2 hours, are added
280 milliliter 37 weight % hydrochloric acid, stirring 1 hour after, at 60 DEG C aging be spray-dried after 2 hours.
By the microballoon of spray drying gained through 650 DEG C of roasting 2h, 20 points are then stirred in pH=2.8 aqueous hydrochloric acid solutions
Clock filters, 6 hours dry at 120 DEG C, obtains assistant for calalytic cracking DB-CAT3 provided by the invention.
The group of assistant for calalytic cracking DB-CAT3 becomes：41 heavy % of kaolin, the aluminium oxide from unmodified boehmite
For 25 heavy %, the Al from Si modification2O3- Si is 21 heavy %, and the aluminium oxide from Aluminum sol is 6 heavy %, the oxygen from waterglass
SiClx is 1.0 heavy %, and rare earth oxide is 7 heavy %.
3 assistant for calalytic cracking physicochemical property of table
* pore volume is measured using water droplet method.
As shown in Table 3, since the abrasion index of DB-CAT3 is up to 5.8%, the index request of industrial catalyst is not met.
4 assistant for calalytic cracking of the present invention of table is respectively with industrial agent catalytic cracking catalyst LDO-70 by weight 1:4 compoundings
Afterwards, ACE reaction evaluatings data
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
It should all belong to the scope of protection of the present invention.
Claims (11)
1. a kind of preparation method of the assistant for calalytic cracking containing boehmite, it is characterised in that this method includes：Part is quasi-
15 minutes modified boehmite A made above, modified boehmite A and residue is mixed with siliceous solution in boehmite
Boehmite B, clay, heavy metal chelating agent are mixed with beating, and slurries are obtained through homogeneous, acidification, shaping and drying, ion exchange
Assistant for calalytic cracking；Wherein, the butt quality ratio of modified boehmite A and remaining boehmite B are 0.2~2.5, are contained
The addition of silicon solution is with SiO2It is calculated as the 0.5%~8% of modified boehmite A dry weights；In the siliceous solution
Silicon exists with ionic condition.
2. preparation method according to claim 1, it is characterised in that the addition of siliceous solution is with SiO2It is calculated as modified quasi- thin
The 1.5%~6% of diaspore A dry weights.
3. preparation method according to claim 1 or 2, it is characterised in that modified boehmite A intends thin water aluminium with remaining
The butt quality ratio of stone B is 0.3~2.0.
4. preparation method according to claim 3, it is characterised in that modified boehmite A and remaining boehmite B
Butt quality ratio be 0.3~1.5.
5. preparation method according to claim 1 or 2, it is characterised in that part boehmite is mixed with siliceous solution and stirred
It mixes 25~40 minutes.
6. preparation method according to claim 1 or 2, it is characterised in that the siliceous solution is selected from sodium metasilicate, inclined silicon
It is one or more in sour sodium, methyl orthosilicate and ethyl orthosilicate.
7. preparation method according to claim 1 or 2, it is characterised in that each component in the assistant for calalytic cracking
Addition is in terms of 100 parts by assistant for calalytic cracking each component gross mass of feeding intake, and the boehmite addition in terms of aluminium oxide is
15~75 parts, wherein remaining boehmite B is 8~45 parts, modified boehmite A is 7~30 parts；Heavy metal chelating agent 1
~10 parts；20~84 parts of the clay calculated with butt.
8. preparation method according to claim 7, it is characterised in that each component in the assistant for calalytic cracking adds
Enter amount, is in terms of 100 parts by assistant for calalytic cracking each component gross mass of feeding intake, the boehmite addition in terms of aluminium oxide is 20
~65 parts, wherein remaining boehmite B is 10~40 parts, modified boehmite A is 10~25 parts；It is calculated with butt viscous
30~79 parts of soil；1~10 part of heavy metal chelating agent.
9. preparation method according to claim 1 or 2, it is characterised in that comprising selected from oxidation in the assistant for calalytic cracking
It is one or more in aluminium, aluminum oxide precursor object, silica, silica predecessor, magnesia and precursor compound for MgO.
10. preparation method according to claim 9, it is characterised in that the aluminium oxide be selected from Alpha-alumina, beta-alumina,
It is one or more in gama-alumina, δ-aluminium oxide, η-aluminium oxide and θ-aluminium oxide, aluminum oxide precursor object be selected from Aluminum sol and
It is one or more in aluminium hydroxide；The silica is selected from Ludox, silica gel, mesoporous silicon oxide, white carbon and titanium dioxide
It is one or more in silica aerogel, the one kind or more of silica predecessor in sodium metasilicate, sodium metasilicate and positive esters of silicon acis
Kind；The precursor compound for MgO is one or more in magnesium chloride, magnesium hydroxide, magnesium nitrate and magnesium carbonate.
11. preparation method according to claim 1 or 2, it is characterised in that the heavy metal chelating agent is selected from magnesia, oxygen
Change magnesium predecessor, strontium oxide strontia, strontium oxide strontia predecessor, barium monoxide, barium monoxide predecessor, rare earth oxide, rare earth oxide predecessor,
It is one or more in zirconium oxide and zirconium oxide predecessor.
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| CN109833861B (en) * | 2017-11-28 | 2022-01-04 | 中国石油天然气股份有限公司 | Modified preparation method of silica gel carrier |
| CN115228457B (en) * | 2021-04-23 | 2023-12-26 | 国家能源投资集团有限责任公司 | Hydrocracking catalyst carrier, preparation method thereof, hydrocracking catalyst and application thereof |
| CN115957798A (en) * | 2021-10-09 | 2023-04-14 | 中国石油化工股份有限公司 | Catalytic cracking catalyst with rich mesoporous structure and preparation method thereof |
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