CN108097285A - A kind of preparation method of the catalytic cracking catalyst containing mesoporous aluminas/clay composite material - Google Patents
A kind of preparation method of the catalytic cracking catalyst containing mesoporous aluminas/clay composite material Download PDFInfo
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- CN108097285A CN108097285A CN201611067785.XA CN201611067785A CN108097285A CN 108097285 A CN108097285 A CN 108097285A CN 201611067785 A CN201611067785 A CN 201611067785A CN 108097285 A CN108097285 A CN 108097285A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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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
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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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
The present invention relates to a kind of preparation methods of the catalytic cracking catalyst containing mesoporous aluminas/clay composite material.The method includes：Zeolite molecular sieve, binding agent and mesoporous aluminas/clay composite material with water are mixed, stirred, spray shaping after mashing, then cured, washing, drying are made；Wherein the preparation method of mesoporous aluminas/clay composite material is that clay, the acid after roasting are mixed with a kind of solvent in ethyl alcohol or methanol or water, is beaten, and 1 3h of reflow treatment at a temperature of 60 80 DEG C cools down to obtain clay slurry；Polyoxyethylene/polyoxypropylene block copolymer template agent is dissolved in ethyl alcohol, obtains template slurries；After above-mentioned clay slurry and template slurries are mixed, baked again, obtained solid sample is roasted.Preventing from heavy metal pollution ability that is simple and practicable and can further improving FCC catalyst is prepared for FCC catalyst using the method.
Description
Technical field
The present invention relates to a kind of preparation methods of catalytic cracking catalyst, are specifically that one kind has good preventing from heavy metal pollution
The preparation method of the catalytic cracking catalyst of ability.
Background technology
Important means of the fluid catalytic cracking (FCC) as crude oil secondary operation has very important in petroleum refining industry
Status.However, with the world's crude oil heaviness and in poor quality increasingly, the content of beary metal such as Ni-V-Fe, copper are continuous in crude oil
Rise.Particularly nickel and vanadium constantly deposit on a catalyst during FCC, catalyst cracking activity can be caused to decline, production
Object is selectively deteriorated, and light oil yield reduces, and dry gas and hydrogen output rise, and carbon deposition quantity increases, and whens too high levels can also destroy point
The structure of son sieve, makes catalyst complete deactivation.In addition, nickel and vanadium also result in the gas compressor of FCC apparatus and air blower surpasses
Load operation, regenerator temperature rise, the supplement speed of fresh catalyst are accelerated, and energy consumption are caused to increase, FCC apparatus conversion per pass
Rate reduces.Therefore, exploitation preventing from heavy metal pollution technology is particularly anti-nickel, pollution of vanadium technology is that one, FCC fields have important meaning
The research topic of justice.
At present, different FCC preventing from heavy metal pollution technologies continue to bring out, to sum up, mainly there is matal deactivator and urge
Agent is modified two major classes.
It is liquid metals passivator first.Such as CN1068588 discloses a kind of metal for FCC catalyst and is passivated
Agent, the matal deactivator are to be made of the carboxyl compound of antimony or bismuth, reaction medium and solubilizer three parts with good flow
The mixing liquid of property；CN1294173 discloses a kind of water-soluble matal deactivator, using antimony, aluminium and Rare Earth Lanthanum as key component,
The heavy metal poisoning inactivation of catalyst can be significantly decreased, gasoline and light oil yield is improved, reduces hydrogen yield.
These liquid metals passivator achieve good preventing from heavy metal effect, but since it is often containing harmful group
Point, environment can be caused greatly to pollute, so as to limit its application among reality.
Another preventing from heavy metal pollution technology is catalyst modification technology, can be improved by different method of modifying
The preventing from heavy metal pollution ability of FCC catalyst.Among these, being introduced into FCC catalyst has solid nickel, the elemental constituent of vanadium effect
It is more common method.Such as CN85106050A, US4921824, EP347248, JP07126661 are by FCC catalyst
Lanthanide series or compound are introduced to improve catalyst preventing from heavy metal pollution ability；And CN88102585, EP303372,
US4585545, EP141988 and US4504381 then added in FCC catalyst preparation process bismuth, antimony, tin, the elements such as phosphorus or
Compound improves the preventing from heavy metal pollution ability of catalyst；In addition, EP461851,4944865, US4944864,
US4824815, US4504381, US4290919, EP303372, JP61235491 and CN100510015C using alkaline-earth metal,
The elements such as copper, zinc, cadmium and tungsten or compound are modified FCC catalyst, improve the preventing from heavy metal pollution energy of catalyst
Power.
Except above-mentioned single element modified method, by being introduced into FCC catalyst with heavy metals trapping ability
Structural unit can also effectively improve the preventing from heavy metal pollution ability of catalyst.Among these, Al2O3As a kind of solid acid, add
The catalytic activity of catalyst can not only be improved by being added in FCC catalyst, while can significantly improve the preventing from heavy metal of catalyst
Pollutant performance.US5147836, US5304526 and US5306417 disclose a kind of anti-nickel, the auxiliary agent of vanadium, and the auxiliary agent is by SiO2Change
Bayerite/Al of property2O3Composition has preferable preventing from heavy metal nickel, vanadium ability.EP176150 develops the Al that a kind of P is modified2O3
Anti- Ni, V auxiliary agent can significantly improve anti-nickel, the pollution of vanadium ability of FCC catalyst so that yield of gasoline is significantly increased, while hydrogen
Gas and coke descent.(Industrial Catalysis, 2002,10 (2) such as Pang Xinmei:50-53；Petrochemical technology and application, 2003,21 (2)：
107-109.) have studied the Al of different specific surfaces and pore-size distribution2O3As matrix addO-on therapy to the shadow of FCC catalyst performance
It rings, the results showed that, addition large aperture, the aluminium oxide of macropore volume can not only improve the heavy oil conversion performance of FCC catalyst, together
When can significantly improve the preventing from heavy metal pollution performance of catalyst.CN1436835A discloses a kind of material containing macroporous aluminium oxide
Catalytic cracking catalyst preparation method, the average pore size of used macroporous aluminium oxide are not less than 3nm.With conventional catalyst phase
Than the heavy oil conversion performance enhancing of the catalyst, gasoline and coke selectivity are obviously improved, while preventing from heavy metal pollution ability increases
By force.CN1879960A discloses a kind of assistant for calalytic cracking of preventing from heavy metal and preparation method thereof, and the auxiliary agent is using kaolin as original
Material introduces additive and magnesia or its precursor during kaolin pulp, and spray shaping is microballoon, by microballoon in 900-
It extracts through aqueous slkali after being roasted at 1100 DEG C, washing drop sodium, then can be prepared after being handled with rare earth predecessor, which has
The advantages that specific surface area, big pore volume, can significantly improve the reactivity of FCC bodying agents.
Compared with above-mentioned conventional oxidation aluminum material, mesoporous aluminas material has higher specific surface, the pore volume of bigger,
And mesoporous pore passage structure, so as to possess more good heavy metals trapping ability, it is expected to for the preparation of FCC catalyst into one
Step improves the preventing from heavy metal pollution ability of FCC catalyst.
The content of the invention
The present invention is intended to provide a kind of preparation side of the catalytic cracking catalyst containing mesoporous aluminas/clay composite material
Method, this method are made with mesoporous aluminas/clay composite material with macropore volume, Large ratio surface, ordered mesoporous pore passage structure
For matrix components, prepared catalyst has preferable preventing from heavy metal pollution ability.
The present invention provides a kind of preparation method of the catalytic cracking catalyst containing mesoporous aluminas/clay composite material,
Including：By zeolite molecular sieve, binding agent, mesoporous aluminas/clay composite material mixed with water, be beaten after spray shaping, washing,
It is dry, catalytic cracking catalyst is made；Wherein, the preparation method of the mesoporous aluminas/clay composite material includes to roast
Clay after burning, acid are mixed with a kind of solvent in ethyl alcohol or methanol or water, are beaten, in 60-80 DEG C of reflow treatment 1-3h,
Obtain clay slurry；Polyoxyethylene/polyoxypropylene block copolymer template agent is dissolved in ethyl alcohol, obtains template slurries；It will be upper
It states clay slurry and after template slurries are mixed, bake, obtained solid sample is roasted.
A kind of preparation side of catalytic cracking catalyst containing mesoporous aluminas/clay composite material disclosed in this invention
In prepared by the mesoporous aluminas/clay composite material, filtration step is not contained in mixing and baking process for method.
A kind of preparation side of catalytic cracking catalyst containing mesoporous aluminas/clay composite material disclosed in this invention
Method, the clay after being roasted in the preparation of the mesoporous aluminas/clay composite material is known to those skilled in the art, this
Inventing the roasting technique condition recommended is：The temperature of roasting is 800-1000 DEG C, roasting time 1-4h.The clay slurry
Solid content 10-40wt%, clay are mixed with a kind of solvent in ethyl alcohol or methanol or water, are beaten.It is described acid addition be
Regulation system [H+- the 1.0mol/L of]=0.1, preferably 0.1-0.5mol/L.The polyoxyethylene/polyoxypropylene block polymer
Template, addition be clay butt quality 2-20wt%, preferably 2~15%, more preferably 4-12wt%.Described is viscous
The process conditions that processing is known to those skilled in the art, and the present invention recommends are baked after soil paste liquid and the mixing of template slurries
For：Temperature is 40-80 DEG C, 1-4 days time.The temperature that the solid sample is roasted is 400-900 DEG C, time 2-6h.
Clay used is the alumino-silicate clays ore deposits such as kaolin, halloysite, montmorillonite, saponite, rectorite, bentonite
One kind in object.The acid is hydrochloric acid, one kind in nitric acid, sulfuric acid, citric acid, is preferably nitric acid.The polyoxyethylene/
Polyoxypropylene block polymer template be selected from polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO), polyoxypropylene-
Polyoxyethylene (PPO-PEO), polyoxyethylene-polyoxyethylene (PEO-PEO) and polyoxypropylene polyoxyethylene-polyoxypropylene (PPO-
PEO-PPO) one kind in polymer, preferably polyoxyethylene-poly-oxypropylene polyoxyethylene (PEO-PPO-PEO).Institute of the invention is public
A kind of preparation method for the catalytic cracking catalyst containing mesoporous aluminas/clay composite material opened, catalytic cracking catalyst
In zeolite molecular sieve can be REY, REX, REHY, USY, REUSY, HZSM-5, REZSM-5, REHZSM-5 and beta-zeolite molecular sieve
One or more of；Binding agent is one kind or several in Ludox, Aluminum sol, sial complex sol, the molten boehmite of acid
Kind.
A kind of preparation side of catalytic cracking catalyst containing mesoporous aluminas/clay composite material disclosed in this invention
Method, for the catalyst in terms of total weight 100%, the catalyst includes following component：10-50wt% zeolite molecular sieves, 5-
40wt% binding agents, 20-80wt% mesoporous aluminas/clay composite material.
A kind of preparation side of catalytic cracking catalyst containing mesoporous aluminas/clay composite material disclosed in this invention
Method, it is described that zeolite molecular sieve, binding agent and mesoporous aluminas/clay composite material with water are mixed, stirred, it sprays after mashing
Shaping, mixing, stirring, mashing, spray shaping these technological means are the general technology of this field, such as
Just there is more detailed narration in CN1552801A, CN103506155B, CN101837301B, CN101134906B.Typically,
Zeolite molecular sieve, binding agent and mesoporous aluminas/clay composite material with water can be mixed respectively, stirred, be beaten, make respectively
Standby is slurries；Can also by optional two kinds in zeolite molecular sieve, binding agent and mesoporous aluminas/clay composite material jointly with
Water is mixed with beating, and a kind of remaining material is mixed with beating with water；Can also all materials be mixed with beating.Compared with prior art, originally
The disclosed preparation method of invention, due to what is generated in the preparation of mesoporous aluminas/clay composite material with acid extracting clay
Aluminium species are silicon source, and the self assembly through template is constructed in situ on caly structure unit, without introducing in preparation process
Additional silicon source, and it is simple, easy, which has macropore volume, Large ratio surface, ordered mesoporous pore passage structure, and the material will
Mesoporous aluminas and clay material organic composite.Compared with traditional handicraft catalytic cracking catalyst, method system of the present invention
Standby catalyst shows more excellent preventing from heavy metal pollution performance.
Description of the drawings
Fig. 1 is the small angle X-ray diffraction figure of mesoporous aluminas/kaolin composite material prepared by embodiment 2.
Fig. 2 is the small angle X-ray diffraction figure of mesoporous aluminas/kaolin composite material prepared by embodiment 4.
Fig. 3 is the small angle X-ray diffraction figure of mesoporous aluminas/kaolin composite material prepared by embodiment 5.
Fig. 4 is the small angle X-ray diffraction figure of mesoporous aluminas/kaolin composite material prepared by embodiment 6.
Fig. 5 is the small angle X-ray diffraction figure of mesoporous aluminas/kaolin composite material prepared by embodiment 7.
Fig. 6 is the small angle X-ray diffraction figure of mesoporous aluminas/montmorillonite composite material prepared by embodiment 8.
Fig. 7 is the small angle X-ray diffraction figure of mesoporous aluminas/rectorite composite material prepared by embodiment 9.
Fig. 8 is the small angle X-ray diffraction figure of the single acid extracting kaolin clay sample prepared by comparative example 1.
Specific embodiment
With reference to embodiment, the present invention is further illustrated, but the invention is not limited in following embodiments.
Raw material sources and leading indicator：Kaolin, montmorillonite and rectorite are provided by Catalyst Factory of Lanzhou Petrochemical Company；Second
Alcohol, nitric acid, hydrochloric acid, citric acid, triblock polymer template P123 (PEO20PPO70PEO20, molecular weight 5800), three block gathers
Close object template F127 (PEO106PPO70PEO106, molecular weight 12600), triblock polymer template F68
(PEO77PPO29PEO77, molecular weight 8400) and it is commercial goods reagent.REY zeolite molecular sieves (Si/Al=6.3) and Aluminum sol
(11wt%) is provided by Petrochina Lanzhou Petrochemical Company's catalyst plant, industrial goods.
Catalyst preventing from heavy metal pollution performance evaluation：
It is dry by prepared catalyst dipping incipient impregnation nickel, vanadium solution, 3h then is roasted in 540 DEG C, obtains a huge sum of money
Belong to pollution catalyst sample；Wherein Ni additions are the 3000ppm of 1 mass parts of catalyst, and V additions are 1 mass parts of catalyst
5000ppm.On ACE (Advanced cracking evaluation, Kayser R+MultiMode microreactors)
Evaluate the heavy oil catalytic cracking performance of catalyst.
Embodiment 1：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 4h by 600 DEG C.
2) above-mentioned kaolin by solid content 30wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
0.1mol/L, reflow treatment 3h under 60 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ kaolin mass ratio=4wt%, itself and ethyl alcohol are mixed
Conjunction stirring is completely dissolved up to P123, obtains template slurries.
4) mixes both above-mentioned slurries, and acquired solution then is placed in 50 DEG C bakes processing 48h, finally consolidates gained
Body sample obtains final solid sample in 500 DEG C of roasting temperature 6h.
The preparation of catalytic cracking catalyst：
By solid masses percentage 30:10:60 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 2：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 3h by 700 DEG C.
2) above-mentioned kaolin by solid content 10wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
0.3mol/L, reflow treatment 1h under 80 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ kaolin mass ratio=6wt%, itself and ethyl alcohol are mixed
Conjunction stirring is completely dissolved up to P123, obtains template slurries.
4) mixes both above-mentioned slurries, and acquired solution then is placed in 60 DEG C bakes processing 36h, finally consolidates gained
Body sample obtains final solid sample in 550 DEG C of roasting temperature 4h.
Fig. 1 shows the small angle X-ray diffraction figure of 2 sample of embodiment.As seen from the figure, sample is attached in 0.8 ° of angle of diffraction
Near a diffraction maximum occur, which is the characteristic diffraction peak of mesoporous aluminas material, shows successfully to have constructed mesoporous in sample
Aluminium oxide structure.
The preparation of catalytic cracking catalyst：
By solid masses percentage 25:10:65 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 3：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 1h by 900 DEG C.
2) above-mentioned kaolin by solid content 20wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
0.5mol/L, reflow treatment 2h under 70 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ kaolin mass ratio=8wt%, itself and ethyl alcohol are mixed
Conjunction stirring is completely dissolved up to P123, obtains template slurries.
4) mixes both above-mentioned slurries, and acquired solution then is placed in 70 DEG C of baking processing for 24 hours, finally consolidates gained
Body sample obtains final solid sample in 600 DEG C of roasting temperature 2h.
The preparation of catalytic cracking catalyst：
By solid masses percentage 30:5:65 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 4：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 1h by 800 DEG C.
2) above-mentioned kaolin is pressed solid content 20wt% and ethyl alcohol and mixed in hydrochloric acid, the mashing, [H of system by+]=
0.2mol/L, reflow treatment 1h under 80 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ kaolin mass ratio=12wt%, itself and ethyl alcohol are mixed
Conjunction stirring is completely dissolved up to P123, obtains template slurries.
4) mixes both above-mentioned slurries, and acquired solution then is placed in 65 DEG C bakes processing 48h, finally consolidates gained
Body sample obtains final solid sample in 550 DEG C of roasting temperature 3h.
The small angle X-ray diffraction figure (Fig. 2) of 4 sample of embodiment shows the characteristic diffraction peak of mesoporous aluminas material.
The preparation of catalytic cracking catalyst：
By solid masses percentage 35:10:55 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 5：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 4h by 600 DEG C.
2) above-mentioned kaolin by solid content 15wt% with ethyl alcohol and citric acid is mixed, is beaten, [the H of system by+]=
0.4mol/L, reflow treatment 3h under 70 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ kaolin mass ratio=5wt%, by itself and ethyl alcohol room
Mixing is completely dissolved up to P123, obtains template slurries.
4) mixes both above-mentioned slurries, then acquired solution is placed in baking oven, processing 48h is baked in 70 DEG C, finally
By obtained solid sample in 500 DEG C of roasting temperature 4h, final solid sample is obtained.
The small angle X-ray diffraction figure (Fig. 3) of 5 sample of embodiment shows the characteristic diffraction peak of mesoporous aluminas material.
The preparation of catalytic cracking catalyst：
By solid masses percentage 35:5:60 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 6：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 3h by 700 DEG C.
2) above-mentioned kaolin by solid content 10wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
1.0mol/L, reflow treatment 2h under 80 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template F127 by F127/ kaolin mass ratio=4wt%
(PEO106PPO70PEO106, molecular weight 12600), it is mixed with ethyl alcohol until P123 is completely dissolved, obtains template slurries.
4) both above-mentioned slurries mixing at room temperature, is then placed in 80 DEG C of baking processing for 24 hours, finally by institute by acquired solution
Solid sample is obtained in 600 DEG C of roasting temperature 2h, obtains final solid sample.
The small angle X-ray diffraction figure (Fig. 4) of 6 sample of embodiment shows the characteristic diffraction peak of mesoporous aluminas material.
The preparation of catalytic cracking catalyst：
By solid masses percentage 30:15:55 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 7：
It is prepared by mesoporous aluminas/kaolin composite material：
1) kaolin is roasted 1h by 1000 DEG C.
2) above-mentioned kaolin by solid content 40wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
0.7mol/L, reflow treatment 3h under 60 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template F68 (PEO by F68/ kaolin mass ratio=10wt%77PPO29PEO77,
Molecular weight 8400), it is mixed with ethyl alcohol until P123 is completely dissolved, obtains template slurries.
4) acquired solution, is then placed in baking oven and processing 36h is baked in 65 DEG C by both above-mentioned slurries mixing at room temperature,
Obtained solid sample is finally obtained into final solid sample in 550 DEG C of roasting temperature 3h.
The small angle X-ray diffraction figure (Fig. 5) of 7 sample of embodiment shows the characteristic diffraction peak of mesoporous aluminas material.
The preparation of catalytic cracking catalyst：
By solid masses percentage 25:10:65 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/kaolin multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 8：
It is prepared by mesoporous aluminas/montmorillonite composite material：
1) montmorillonite is roasted 3h by 800 DEG C.
2) above-mentioned montmorillonite by solid content 10wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
1.0mol/L, reflow treatment 2h under 70 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ montmorillonites mass ratio=6wt%, itself and ethyl alcohol are mixed
Conjunction stirring is completely dissolved up to P123, obtains template slurries.
4) both above-mentioned slurries mixing at room temperature, is then placed in 70 DEG C of baking processing for 24 hours, finally by institute by acquired solution
Solid sample 500 DEG C of roasting temperature 4h in Muffle furnace are obtained, obtain final solid sample.
The small angle X-ray diffraction figure (Fig. 6) of 8 sample of embodiment shows the characteristic diffraction peak of mesoporous aluminas material.
The preparation of catalytic cracking catalyst：
By solid masses percentage 20:10:70 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/montmorillonite multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Embodiment 9：
It is prepared by mesoporous aluminas/rectorite composite material：
1) rectorite is roasted 2h by 900 DEG C.
2) above-mentioned rectorite by solid content 30wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
0.5mol/L, reflow treatment 1h under 80 DEG C of water bath conditions, obtains kaolin slurry.
3) weighs triblock polymer template P123 by P123/ rectorites mass ratio=4wt%, itself and ethyl alcohol are mixed
Conjunction stirring is completely dissolved up to P123, obtains template slurries.
4) then acquired solution is placed in 80 DEG C and bakes processing 12h, finally by institute by both above-mentioned slurries mixing at room temperature
Solid sample 550 DEG C of roasting temperature 3h in Muffle furnace are obtained, obtain final solid sample.
The small angle X-ray diffraction figure (Fig. 7) of 9 sample of embodiment shows the characteristic diffraction peak of mesoporous aluminas material.
The preparation of catalytic cracking catalyst：
By solid masses percentage 35:5:60 to weigh REY zeolite molecular sieves, Aluminum sol and mesoporous aluminas/rectorite multiple
Three with chemical water is mixed, is beaten by condensation material, is washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Comparative example 1：
1) kaolin is roasted 1h for 900 DEG C by.
2) above-mentioned kaolin by solid content 20wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
Then gained slurries are placed in 70 DEG C of bakings processing for 24 hours, finally by institute by 0.5mol/L, reflow treatment 2h under 70 DEG C of water bath conditions
Solid sample is obtained in 600 DEG C of roasting temperature 2h, obtains final solid sample.
Acid extracting kaolin X ray diffracting spectrum is as shown in Figure 8 prepared by comparative example 1.As seen from the figure, sample is small
Do not occur the characteristic diffraction peak of mesoporous aluminas material in angular range, show to be free of mesoporous aluminas ingredient in sample.
The preparation of catalytic cracking catalyst：
By solid masses percentage 30:5:65 weigh REY zeolite molecular sieves, Aluminum sol and acid extracting kaolin, by three
It mixes, be beaten with chemical water, washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Comparative example 2：
1) montmorillonite is roasted 3h for 800 DEG C by.
2) above-mentioned montmorillonite by solid content 10wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
Then acquired solution is placed in 70 DEG C of bakings processing for 24 hours, finally by institute by 1.0mol/L, reflow treatment 2h under 70 DEG C of water bath conditions
Solid sample is obtained in 500 DEG C of roasting temperature 4h, obtains final solid sample.
The preparation of catalytic cracking catalyst：
By solid masses percentage 20:10:70 weigh REY zeolite molecular sieves, Aluminum sol and acid extracting montmorillonite, by three
It mixes, be beaten with chemical water, washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
Comparative example 3：
1) rectorite is roasted 2h for 900 DEG C by.
2) above-mentioned rectorite by solid content 30wt% with ethyl alcohol and nitric acid is mixed, is beaten, [the H of system by+]=
Then acquired solution is placed in 80 DEG C and bakes processing 12h, finally by institute by 0.5mol/L, reflow treatment 1h under 80 DEG C of water bath conditions
Solid sample is obtained in 550 DEG C of roasting temperature 3h, obtains final solid sample.
The preparation of catalytic cracking catalyst：
By solid masses percentage 35:5:60 weigh REY zeolite molecular sieves, Aluminum sol and acid extracting rectorite, by three
It mixes, be beaten with chemical water, washed after spray shaping, dry i.e. obtained catalytic cracking catalyst.
The object structure property of 1 mesoporous aluminas of table/clay composite material
As can be seen from Table 1, compared with clay original soil, after being handled using classical acid extraction process, the specific surface of clay and hole
Volume has a degree of increase.And compared with classical acid extraction process, the technology of the present invention treated clay specific surface is used
It is further dramatically increased with pore volume, this is because the mesoporous aluminas tool that the technology of the present invention is constructed in situ in kaolin structure
Caused by the specific surface and pore volume of standby bigger.
The object structure property of 2 different catalysts of table
Table 2 contains mesoporous aluminas/clay as can be seen that compared with conventional clay substrate catalyst prepared by the present invention
The specific surface and pore volume of compound matrix material catalyst have significant increase.
The ACE evaluation results of 3 different catalysts of table
There are significance differences for the preventing from heavy metal pollution ability of different catalysts it can be seen from 3 Catalytic Cracking Evaluation result of table
It is different.Compared with the catalyst for using conventional clay host material, prepared by the present invention contains mesoporous aluminas/clay composite base material
Material catalyst shows stronger heavy oil conversion performance, lower slurry oil yield, higher heavy oil conversion ratio, shows skill of the present invention
Catalyst prepared by art possesses better preventing from heavy metal pollution performance.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (11)
1. a kind of preparation method of the catalytic cracking catalyst containing mesoporous aluminas/clay composite material, including zeolite is divided
Sub- sieve, binding agent, mesoporous aluminas/clay composite material are mixed with water, spray shaping after mashing, and washing, drying, feature exist
In：The preparation method of the mesoporous aluminas/clay composite material includes the clay after roasting, acid with being selected from ethyl alcohol or methanol
Or a kind of mixing of solvent, mashing in water, in 60-80 DEG C of reflow treatment 1-3h, obtain clay slurry；By polyoxyethylene/polyoxy third
Alkene block copolymer template agent is dissolved in ethyl alcohol, obtains template slurries；Above-mentioned clay slurry and template slurries are mixed
It closes, after baking, obtained solid sample is roasted.
2. preparation method according to claim 1, it is characterised in that：Based on the total weight 100% of the catalyst, catalysis
Agent contains 10-50wt% zeolite molecular sieves, 5-40wt% binding agents, 20-80wt% mesoporous aluminas/clay composite material.
3. preparation method according to claim 1 or 2, it is characterised in that：The solid content of the clay slurry is 10-
40wt%.
4. preparation method according to claim 1 or 2, it is characterised in that：[the H of the clay slurry+] for 0.1-
1.0mol/L, preferably 0.1-0.5mol/L.
5. preparation method according to claim 1 or 2, it is characterised in that：The temperature roasted to the solid sample
For 400-900 DEG C, time 2-6h.
6. preparation method according to claim 1 or 2, it is characterised in that：The polyoxyethylene/polyoxypropylene block polymerization
Object template dosage be clay butt quality 2-20wt%, preferably 2~15%, more preferably 4-12wt%.
7. preparation method according to claim 1 or 2, it is characterised in that：Clay after the roasting refers to that clay passes through
It is 800-1000 DEG C to cross calcination temperature, the calcination process of roasting time 1-4h.
8. preparation method according to claim 1 or 2, it is characterised in that：Clay used for kaolin, halloysite,
One or more of bentonite, montmorillonite, rectorite.
9. preparation method according to claim 1 or 2, it is characterised in that：Acid used is nitric acid, hydrochloric acid, sulfuric acid and lemon
One kind in acid.
10. preparation method according to claim 1 or 2, it is characterised in that：Polyoxyethylene/polyoxypropylene block used gathers
Close object template for polyoxyethylene-poly-oxypropylene polyoxyethylene, polyoxypropylene polyoxyethylene, polyoxyethylene-polyoxyethylene and
One kind in polyoxypropylene polyoxyethylene-polyoxypropylene polymer.
11. preparation method according to claim 1 or 2, it is characterised in that：The zeolite molecular sieve for REY, REX,
One or more of REHY, USY, REUSY, HZSM-5, REZSM-5, REHZSM-5 and beta-zeolite molecular sieve, binding agent are silicon
One or more of colloidal sol, Aluminum sol, sial complex sol, the molten boehmite of acid.
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| CN116120045A (en) * | 2022-12-30 | 2023-05-16 | 新化县顺达电子陶瓷有限公司 | Ceramic material for light low-heat-conduction 5G signal base station |
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