CN109692676A - A kind of macropore kaolinite and its preparation and application - Google Patents
A kind of macropore kaolinite and its preparation and application Download PDFInfo
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- CN109692676A CN109692676A CN201710994914.8A CN201710994914A CN109692676A CN 109692676 A CN109692676 A CN 109692676A CN 201710994914 A CN201710994914 A CN 201710994914A CN 109692676 A CN109692676 A CN 109692676A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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Abstract
一种大孔高岭石及其制备和应用，所述大孔结构高岭石的平均孔直径为2‑50nm，所述大孔结构高岭石中孔直径为10‑50nm的孔的孔容占总孔容的80％以上。一种大孔结构高岭石的制备方法，包括如下步骤：将高岭土在650‑800℃焙烧0.5‑3小时进行第一焙烧，然后在酸性溶液中进行处理，再于650‑800℃焙烧0.5‑3小时进行第二焙烧，然后在扩孔剂存在下在酸溶液中进行处理，过滤、干燥。该大孔高岭石用于催化裂化催化剂，可以改善催化剂的裂化性能，提高抗积炭能力，改善抗金属污染性能。A kind of macroporous kaolinite and preparation and application thereof, the average pore diameter of the macroporous structure kaolinite is 2-50nm, and the pore volume of the pore diameter of the macroporous structure kaolinite is 10-50nm It accounts for more than 80% of the total pore volume. A method for preparing kaolinite with a macroporous structure, comprising the steps of: calcining kaolin at 650-800°C for 0.5-3 hours to perform first calcination, then treating in an acidic solution, and then calcining kaolin at 650-800°C for 0.5-3 hours A second calcination was carried out for 3 hours, then treated in an acid solution in the presence of a pore expander, filtered and dried. The macroporous kaolinite is used in a catalytic cracking catalyst, which can improve the cracking performance of the catalyst, improve the anti-coking ability, and improve the anti-metal pollution performance.
Description
Technical field
The present invention relates to a kind of kaolinite with macroporous structure and its preparation method and application methods.
Background technique
As petroleum resources are petered out, the use of poor residuum is the problem that petroleum refining industry faces, how to improve slag inferior
The refining effect of oil is the most important thing.Catalytic cracking (FCC) is because of adaptable, the clean or white high income, gasoline to raw material
The advantages that octane number is high is always most important crude oil secondary operation means in oil refining enterprise, China, and catalytic cracking undertakes at present
The gasoline in China 75%, the production task of the chemicals such as 35% diesel oil and propylene, ethylene.The core of catalytic cracking is that catalysis is split
Change catalyst, catalytically cracked material in poor quality causes Cracking catalyst performance to decline, and influences the product point of catalytic cracking unit
Cloth produces bigger effect oil refining income.
Traditional FCC catalyst is generally made of matrix and molecular sieve, and wherein molecular sieve is catalyst active center.To
The heavy oil conversion performance of FCC catalyst is improved, catalyst there must be higher reactivity, but the simple active component that increases contains
Amount cannot fully meet this demand for development, while active component is excessively high that coke output in product distribution can be brought excessively high, influence
Material, heat and the benefit balance of catalytic cracking unit.There is research to turn by improving substrate performance to improve catalyst heavy oil at present
Change ability, one of method are to Modification of kaolin.
Natural kaolin stable chemical performance, but after certain temperature roasts, phase transition occurs for kaolin, therein
Silicon and aluminium start with chemical activity, using acid or alkali process, so that it may so that kaolin is changed into the base with catalytic activity
Material.
US4836913 describes a kind of alkaline-modified kaolin method, including first roasts kaolin under 1700-1800 °F
- 6 hours 25 minutes, then reacted 1 hour or more with alkaline solutions such as sodium hydroxides, through filtering, washing and ion exchange, obtain
Alkaline-modified kaolin matrix.Because catalytic cracking catalyst is an acid system, therefore must be into the kaolin after alkali modification
Row is adequately washed and ion exchange, to guarantee that the alkali metal content of matrix reaches relatively low level, but because of kaolin partial size
Small, filtration difficulty necessarily causes industrial production cost excessively high.
CN1195014A discloses a kind of improvement of kaolin, and this method includes roasting kaolin at 850-920 DEG C
It burns 10 minutes to 5 hours, then at 90-150 DEG C, the molar ratio with inorganic monoacid and binary acid is 1.0-5.0, acid strength
For kaolin 4-40 hours after the mixed acid solution processing roasting of 0.4-4N.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of macroporous structure kaolinite (abbreviation macropore kaolinite) and its systems
Preparation Method, the invention solves other technical problem be to provide a kind of macroporous structure kaolinite in catalytic cracking catalyst
In application method.
The present invention provides a kind of macroporous structure kaolinite, and the kaolinic average pore diameter of macroporous structure is (referred to as average
Aperture) it is 2-50nm, for example, 10-30nm or 11-24nm or 11-16nm, the macroporous structure kaolinite median pore diameter is 10-
It is, for example, 80-95% or 81-92% that the Kong Rong in the hole of 50nm, which accounts for 80% of total pore volume or more,.
Macroporous structure kaolinite provided by the invention, it is preferred that total pore volume is that 0.20-0.30ml/g is, for example, 0.22-
0.28ml/g.Specific surface area is 100-250m2/ g is, for example, 100-200m2/g。
Macroporous structure kaolinite provided by the invention, wherein the Kong Rong and specific surface area in the hole of the total pore volume, 10-50nm
(referring to GB/T 5816-1995) is measured with nitrogen low-temperature adsorption, BJH method calculates pore size distribution, and hole of the present invention, which holds, is also referred to as hole body
Product.Average pore size is equal to that corresponding pore volume and corresponding specific surface are divided by as a result, its calculation formula is average pore sizes=k
× total pore volume/specific surface area, k=8.
Macroporous structure kaolinite provided by the invention, on the basis of dry weight, in the macroporous structure kaolinite
Al2O3Content is that 33-45 weight % is, for example, 35-42 weight % or 35-40 weight %.
Macroporous structure kaolinite provided by the invention, usual SiO2Content is 45-59.5 weight % such as 48-59 weight %
Or 50-59 weight % or 53-59 weight %.
Macroporous structure kaolinite provided by the invention, on the basis of dry weight (in terms of butt), iron content is with Fe2O3Meter
Preferably more than 1.5 weight % are, for example, 0.5-1.5 weight %.
Macroporous structure kaolinite provided by the invention, on the basis of dry weight, α-SiO2Content is no more than 2 weight %
For example 1-2 weight %.
Macroporous structure kaolinite provided by the invention, on the basis of dry weight, CaO+MgO content is no more than 2 weights
Measuring % is, for example, 1-2 weight %.
Macroporous structure kaolinite provided by the invention, wherein any method measurement can be used in element composition, for example, by using X-ray
Fluorescence spectrum method for measuring.
Macroporous structure kaolinite provided by the invention is modified kaolinite, is obtained by kaolinite raw by modification.It is described
Kaolinite raw such as kaolin.
The present invention provides a kind of kaolinic preparation method of macroporous structure, includes the following steps:
(1) common kaolin is roasted 0.5-3 hours at 650-800 DEG C, which is known as the first roasting, obtains
Kaolin after first roasting,
(2) by the kaolin and the first acid solution formation mixture after the first roasting, Yu Wendu 40-80 DEG C such as 50-
80 DEG C preferably 60-80 DEG C contacts at least such as 0.5-2 hours 0.5 hour (the referred to as first processing), and the first kaolin slurry is made；
Such as kaolin and water, acid-mixed after being roasted by the kaolin and the mixing of the first acid solution after the first roasting or by first
It closes, is warming up to 40-80 DEG C preferably 60-80 DEG C, and stir 0.5-2 hours at this temperature (40-80 DEG C preferably 60-80 DEG C)；
(3) the first kaolin slurry is filtered, it is dry, the first desciccate (kaolin after also referred to as drying) is obtained,
(4) the first desciccate is roasted 0.5-3 hours at 650-800 DEG C, which is known as the second roasting, obtains
Kaolin after two roastings；
(5) kaolin, the second acid solution and the expanding agent after the second roasting are formed into mixture, and in 40-80 DEG C
Such as at least 0.5 hour such as mixing time of 50-80 DEG C of preferably 60-80 DEG C of stirring is to obtain the second kaolinite soil paste in 0.5-2 hours
Liquid, which is known as second processing, such as appearance is added in kaolin, the second acid solution and the expanding agent after the second roasting together
In device and it is stirred continuously or by the slurries of kaolin and water formation after the second roasting, is then mixed with acid and expanding agent,
Preferably 60-80 DEG C of 40-80 DEG C of temperature is warming up under stirring, 40-80 DEG C preferably 60-80 DEG C stirring 0.5-2 hours；
The filtering of (6) second kaolin slurries, it is dry, obtain macroporous structure kaolinite.
Macroporous structure kaolinite preparation method provided by the invention, common kaolin described in step (1) are kaolin,
It is a kind of clay or clay rock based on kaolinite race clay mineral.Kaolinite race clay mineral such as kaolinite,
Galapectite, dickite, nacrite.The kaolin can be soft kaolin, hard kaoline, grittiness kaolin, Ai Luo
One of stone, gangue, halloysite are a variety of.In the common kaolin, the content of kaolinite race clay mineral is excellent
Choosing is, for example, 70-100 weight % or 70-95 weight % or 70-80 weight % not less than 65 weight %, and preferred kaolinite race is viscous
Native mineral are kaolinite and/or galapectite.A kind of embodiment, in the common kaolin, Al2O3Content is 35-40 weight
Measure %, Fe2O3Content is that 0.5-1.5 weight %, CaO+MgO content is 1-2 weight %, α-SiO2Content is 1-2 weight %, than
Surface area is less than 40m2/g；The kaolinic crystal structure is mainly laminated structure.Crystal kaolinite in the common kaolin
Stone content is, for example, 70-95 weight % or 70-80 weight % not less than 70 weight %.The common kaolin usually can be height
Mined kaolin raw ore powder in the soil mine of ridge is also possible to kaolin raw ore powder and for example washes or ammonium by carrying out washing treatment
The washing kaolin obtained after brine.The content of kaolinite race clay mineral can be used X-ray and spread out in common kaolin
Penetrate method measurement.In general, sample is first in 150-200 DEG C of drying before measurement.
Macroporous structure kaolinite preparation method provided by the invention, first roasting, maturing temperature 650-800
DEG C, preferably 650-750 DEG C, calcining time is 0.5-3 hours, preferably 1-2 hours.Second roasting, maturing temperature 650-
800 DEG C, preferably 650-750 DEG C, calcining time are 0.5-3 hours, preferably 1-2 hours.
Macroporous structure kaolinite preparation method provided by the invention, the first described processing (or first contact), wherein
First acid solution contains acid, and the acid can be organic and or inorganic acids, the acid for example hydrochloric acid, sulfuric acid,
One or more acid such as nitric acid, phosphoric acid, oxalic acid, acetic acid, citric acid；Sour molar concentration can be 0.5- in the acid type solution
5mol/L, such as 0.5-3mol/L or 1-5mol/L.In first acid solution water and first roasting after kaolin (in terms of butt)
Weight ratio be 1-10:1.The solid content of the first kaolin slurry wherein formed is that 10-50 weight % is, for example, 15-45 weight
Amount % or 15-35 weight % is 15-25 weight %.Preferably, the acid in first acid solution includes organic acid and nothing
The molar ratio of machine acid, inorganic acid and organic acid is 0.3-10:1 preferred 0.4-5:1 or 1-5:1 or 0.4-3:1.The acid is more excellent
It is selected as hydrochloric acid and oxalic acid, it is preferably 1-5:1 or 1-3:1 that the molar ratio of hydrochloric acid and oxalic acid, which is 0.5-10:1,.It is described to be roasted first
Kaolin and the first acid solution after burning form mixture, can be by the kaolin and the first acid solution after the first roasting
It is added in container and is mixed under stiring；Or kaolin and water mashing after being roasted first, then into slurries
Acid is added, it is preferred that sour concentration is 0.5-5mol acid/L in the solution of the mixture of formation.First processing, by first
Kaolin and the first acid solution after roasting form mixture, then heat up 40-80 DEG C preferably 60-80 DEG C, and at 40-80 DEG C
Preferred 60-80 DEG C of temperature stirs 0.5- hours down.
Macroporous structure kaolinite preparation method provided by the invention, described second processing, wherein described second is acid
Acid in solution is organic and or inorganic acids, and the acid is, for example, to contain hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, phosphoric acid, lemon
The solution of one or more acid in acid；Sour molar concentration can be 0.5-10mol/L in second acid solution, for example,
0.5-5mol/L or 1-3mol/L.In second acid solution water and second roasting after kaolin (in terms of butt) weight ratio be 1-
10:1.The solid content of the second slurries formed is that 10-50 weight % is, for example, 15-45 weight % or 15-35 weight %, preferably
15-25 weight %.Kaolin after second roasting can be mixed with the second acid solution, then be heated up, preferably in 40-80 DEG C
At least 0.5 hour such as mixing time of 60-80 DEG C of stirring is 0.5-2 hours；It can also be by the kaolin and water after the second roasting
Then mashing is added acid, then heats up, be in 40-80 DEG C of preferred 60-80 DEG C of stirring at least 0.5 hour such as mixing time
0.5-2 hours, wherein the dosage of water and acid made concentration sour in the solution to be formed be, for example, 0.5-10mol/L, preferably
0.5-5mol/L is, for example, 1-3mol/L.A kind of embodiment, the acid are hydrochloric acid and oxalic acid, the molar ratio of hydrochloric acid and oxalic acid
Example is that 0.3-10:1 is preferably 0.3-5:1 or 1-5:1 or 0.35-3:1.
Expanding agent described in macroporous structure kaolinite preparation method provided by the invention can be selected from ammonium sulfate, ammonium phosphate, carbon
One or more of sour ammonium, organic amine, polyethylene glycol, polyacrylamide.A kind of embodiment, the expanding agent and the second roasting
It is, for example, 0.1-0.5:1 or 0.3-0.5:1 that kaolinic weight ratio after burning, which is 0.05-1:1,.The organic amine is fat
One of amine, aromatic amine and hydramine are a variety of；The general formula of the fatty amine is R3(NH2)n, wherein R3For with 1-4 carbon
The alkyl or alkylidene of atom, n=1 or 2；Its general formula of the hydramine is (HOR4)mNH(3-m), wherein R4For with 1-4
The alkyl of carbon atom, m=1,2 or 3；The aromatic amine is the amine with an armaticity substituent.Preferably, the rouge
Fat amine is one of ethamine, n-butylamine, butanediamine or hexamethylene diamine or a variety of；The hydramine is monoethanolamine, diethanol amine
Or one of triethanolamine or a variety of；The aromatic amine is one of aniline, toluidines, p-phenylenediamine or a variety of.
Macropore kaolinite provided by the invention, a kind of preferred preparation method include the following steps:
(1) common kaolin is roasted 1-2 hours at 700-750 DEG C, which is known as the first roasting, obtains
Kaolin after one roasting,
(2) by the kaolin and the first acid, water formation mixture after the first roasting, it is warming up to 60-80 DEG C and in 60-80 DEG C
Contact 1-2 hours carries out the first processing, the first kaolin slurry is made；Wherein the ratio of the first acid and water is 1-3 equimolar acid:
Kaolinic weight ratio after 1L water, water and the first roasting is 2-5:1；First acid is hydrochloric acid and oxalic acid, HCl and oxalic acid
Molar ratio is that the preferred 0.4-5:1 of 0.2-5:1 is, for example, 0.3-0.8:1；
(3) the first kaolin slurry is filtered, it is dry, the first desciccate (kaolin after also referred to as drying) is obtained,
(4) the first desciccate is roasted 1-2 hours at 700-750 DEG C, which is known as the second roasting, obtains second
Kaolin after roasting；
(5) by second roasting after kaolin, the second acid, water, expanding agent formation mixture, be warming up to 60-80 DEG C and in
60-80 DEG C of stirring obtains the second kaolin slurry at least 1-2 hours, which is known as second processing；Wherein the second acid and water
Ratio is 1-3 equimolar acid: 1L water, and the kaolinic weight ratio after water and the second roasting is 2-5:1；It is described second acid be hydrochloric acid and
The molar ratio of oxalic acid, HCl and oxalic acid be 0.1-5:1 be, for example, the preferred 0.3-5:1 of 0.2-0.5:1 be, for example, 0.2-0.5:1 or
0.35-1:1；Kaolinic weight ratio is the preferred 0.1-0.5:1 of 0.05-0.8:1 such as 0.3- after expanding agent and the second roasting
0.5:1；
The filtering of (6) second kaolin slurries, it is dry, obtain macroporous structure kaolinite.
The kaolinic preparation method of macroporous structure of the present invention, the first processing and/or second processing, it is preferred that
It carries out under confined conditions, acid volatilization is avoided to lead to sour usage amount increase or modified kaolin degradation.
Macroporous structure kaolinite preparation method provided by the invention, it is preferred that in obtained macroporous structure kaolinite, with
On the basis of dry weight, the content of iron oxide is no more than 1.5 weight % such as Fe2O3Content is 0.5-1.5 weight %, CaO+MgO
Content be no more than 2 weight % such as CaO+MgO content be 1-2 weight %, α-SiO2It is, for example, 1- that content, which is no more than 2 weight %,
2 weight %.
Macroporous structure kaolinite preparation method provided by the invention, a kind of embodiment, prepared macroporous structure kaolinite
Stone, including form as follows: Al2O3Content is in 35-42 weight %, Fe2O3Content is in 0.5-1.5 weight %, CaO+MgO content 1-2
Weight %, α-SiO2Content 1-2 weight %, specific surface area 100-250m2/ g is, for example, 100-200m2/ g, pore volume (refer to total
Pore volume) it is 0.20-0.30ml/g such as 0.22-0.28ml/g.The kaolinic average pore diameter of macropore is 10-50nm,
Preferably 10-30nm is, for example, 11-24nm or 11.5-16nm, the hole of macropore kaolinite bore dia 10-50nm of the present invention
It is, for example, the preferred 81-92% of 80-95% that appearance, which accounts for 80% of total pore volume or more,.In the macroporous structure kaolinite, SiO2Content
Can for 45-59.5 weight % such as 46-58 weight % or 47-55 weight % or 48-51 weight % or 51-55 weight % or
49-59 weight %.
The present invention further provides a kind of catalytic cracking catalyst, containing molecular sieve, binder and optional clay and
The macroporous structure kaolinite that aforementioned present invention provides.
Preferably, in catalytic cracking catalyst provided by the invention, the kaolinic content of macroporous structure is 2-50 weight
Measure %, preferably 15-44 weight %.
Preferably, in the catalytic cracking catalyst provided by the invention the content of molecular sieve more than 25 weight % for example
The content of molecular sieve is that 25-50 weight % is preferably 25-35 weight %.
The catalytic cracking catalyst provided by the invention, (dry weight on the basis of the dry weight of catalytic cracking catalyst
It is 800 DEG C, the weight after calcination in 1 hour), contain molecular sieve (in terms of butt) 25-50 weight %, preferably 25-35 weight %；It is viscous
Soil (in terms of butt) 0-50 weight %, preferably 0-30 weight %；Binder (in terms of oxide) 10-30 weight %, preferably 15-26
Weight %；Macropore kaolinite (in terms of butt) 2-50 weight %, preferably 15-44 weight %.The binder preferably aoxidizes
Al binder, with Al2O3Meter alumina bound agent content is 10-30 weight %.
The present invention provides a kind of preparation method of catalytic cracking catalyst, this method comprises: by binder, optional viscous
Soil, molecular sieve and macropore kaolinite are beaten to obtain catalyst slurry, the catalyst slurry are spray-dried, optionally
Washing, optionally drying and optionally roasting.
Catalytic cracking catalyst preparation method according to the present invention is high by binder, optional clay, molecular sieve and macropore
Ridge stone is beaten to obtain catalyst slurry, can be carried out according to any existing method, the solid content of the catalyst slurry can
In 15-45 weight %, to be, for example, 30 weight %-40 weight % preferably more than 30 weight %.
Catalytic cracking catalyst preparation method of the invention, the clay that the clay is well known to those skilled in the art
Raw material, common clay types may be incorporated for the present invention, and for the present invention, the clay is preferably kaolin, more water kaolinites
In soil, montmorillonite, diatomite, galapectite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite
It is one or more.The clay is more preferably in kaolin and galapectite one or more kinds of.
Catalytic cracking catalyst preparation method according to the present invention, the binder can be in catalytic cracking catalyst
One of the binder used, such as acidification pseudo-boehmite, Aluminum sol, silica solution, magnalium colloidal sol, zirconium colloidal sol, titanium colloidal sol
Or a variety of, preferably acidification pseudo-boehmite and Aluminum sol.
Catalytic cracking catalyst preparation method according to the present invention, the molecular screen primary that the molecular sieve is well known in the art
Material, molecular sieve type commonly used in the art may be incorporated for the present invention, for the preferably molecular sieve of the invention refer to REY,
REHY, REUSY, USY, using gas chemistry method (SiCl4De- Al mends Si method), liquid chemical method ((NH4)2SiF6Aluminium-eliminating and silicon-replenishing
Method) and the preparation of other methods the modified Y zeolite or their mixture of different silica alumina ratios, and contain other all kinds of high silica alumina ratios
ZSM-5 class, β class zeolite or their mixture.Preparation method according to the present invention, in the preferably described catalytic cracking catalyst
The content of molecular sieve is more than 25 weight %.
The present invention also provides the catalytic cracking catalysts that preparation method of the invention obtains.
Macroporous structure kaolinite provided by the invention, average pore size is high, and the ratio of the mesoporous of 10-50nm is high, has higher
Heavy oil cracking ability and anti-metallic contamination performance.Macroporous structure kaolinite provided by the invention can replace clay and be used to prepare
Catalytic cracking catalyst.
Macroporous structure kaolin preparation method provided by the invention, the available macroporous structure kaolin, has
Higher total pore volume and higher 10-50nm mesopore content.
Cracking catalyst provided by the invention, heavy oil cracking ability and anti-metallic contamination ability more preferably, yield of gasoline yield
Higher, yield of light oil is higher, and coke selectivity is lower.
Detailed description of the invention
Fig. 1 is macropore kaolinite B electron microscope looks prepared by embodiment 1.
Specific embodiment
The following examples are described further the features of the present invention, but the contents of the present invention are not by embodiment
Limitation.
Former material specification used in embodiment is as follows:
Feed kaolin: 72 weight % of solid content, China Kaolin Clay Co., Ltd. (Suzhou) production are hard kaoline,
Its crystal kaolinite content is 70 weight %, is known as kaolin A in subsequent embodiment.
Hydrochloric acid, oxalic acid: analysis is pure；Polyethylene glycol: analysis is pure；
Aluminum sol: Al2O322 weight % of content, the production of Sinopec catalyst asphalt in Shenli Refinery, Co., Ltd；
Boehmite: 72 weight % of solid content, Shandong Province of China Chinalco；
Molecular sieve used is REY type molecular sieve: Sinopec catalyst Co., Ltd Shandong in Catalyst Preparation Example
Branch company's production, 80 weight % of solid content, 17.4 weight % of content of rare earth；
It forms to calculate by the inventory of each raw material in the catalyst that catalyst preparation example obtains and determine.
Analysis method:
(1) (RIPP 117-90 standard method is (see " petrochemical analysis method " (RIPP test for XRF fluorescence analysis method
Method) the surely equal volume of Yang Cui, Science Press, nineteen ninety publication)) measurement.
(2) institute is detected using U.S. Kang Ta company Autosorb-1 nitrogen adsorption desorption instrument according to GB/T 5816-1995 method
The specific surface area and pore volume of Cracking catalyst are stated, sample needs deaerate 6 hours at 300 DEG C before testing.
(3) scanning electron microscope sem measures: laboratory apparatus: QUANTA 200F+EDAX.Experiment condition: acceleration voltage 20kV, point
Resolution 2nm, beam spot size 3.0-4.0, operating distance 9.8-10.3mm, model LFD, ETD of popping one's head in, operating pressure 80Pa.
(4) crystal kaolinite content, α-SiO2Content is measured using x-ray powder diffraction.Sample is dry at 150 DEG C
3h post analysis.
Macroporous structure kaolin prepares embodiment 1
Kaolin A is roasted at 750 DEG C and obtains within 2 hours roasting material (the referred to as first roasting material), by 168g (butt
Meter, similarly hereinafter) the first roasting material, decationized Y sieve water (pH=3.1, similarly hereinafter) stirring is added, it is 25 weight %'s that solid content, which is made,
The hydrochloric acid 500g and oxalic acid 100g of concentration 1mol/L is added in slurries, is warming up to 70 DEG C, stirs 1 hour, is then filtered to remove mother
Liquid, filter cake drying, obtains first step product；First step product 120g is roasted at 750 DEG C and obtains within 2 hours roasting material (referred to as
Second roasting material), 100g (butt, similarly hereinafter) second roasts material and the stirring of decationized Y sieve water is added, and obtaining solid content is 25 weights
The slurries of % are measured, hydrochloric acid 200g and oxalic acid 50g, the polyethylene glycol 50g of concentration 1mol/L is added, are warming up to 70 DEG C, stirring 1 is small
When, it is then filtered to remove mother liquor, filter cake is simultaneously dried, and macroporous structure kaolinite B is obtained, and preparation process parameter is shown in Table 1, phenetic analysis
Data are shown in Table 2, scanning electron microscope (SEM) photograph and see Fig. 1.
1 macroporous structure kaolin of table prepares each step condition of embodiment
Macroporous structure kaolinite prepares embodiment 2
Kaolin A is roasted at 650 DEG C and obtains within 0.5 hour roasting material (the referred to as first roasting material), 168g first
It roasts material and decationized Y sieve water is added, stirring obtains the slurries that solid content is 25 weight %, the hydrochloric acid of concentration 1mol/L is added
500g and oxalic acid 100g is warming up to 70 DEG C, mixing time 1 hour, is then filtered to remove mother liquor, filter cake drying obtains first step production
Object；First step product 120g is roasted at 650 DEG C and obtains within 0.5 hour roasting material (referred to as second roasting material), 100g the
Acid water (decationized Y sieve water) stirring is added in two roasting materials, obtains the slurries that solid content is 25 weight %, concentration 1mol/L is added
Hydrochloric acid 200g and oxalic acid 50g, polyethylene glycol 50g, be warming up to 70 DEG C, mixing time 1 hour, be then filtered to remove mother liquor, filter
Cake is simultaneously dried, and macroporous structure kaolinite C is obtained, and preparation process parameter and analysis data are shown in Table 1, table 2.
Macroporous structure kaolinite prepares embodiment 3
Ridge soil A is roasted 2 hours at 750 DEG C, obtains roasting material (the referred to as first roasting material), 168g first is roasted
Material is added deionized water and stirs to get the slurries that solid content is 25 weight %, and the hydrochloric acid 500g of concentration 5mol/L, heating is added
To 70 DEG C, mixing time 1 hour, it is then filtered to remove mother liquor, filter cake drying obtains first step product；By first step product 120g
It is roasted at 750 DEG C and obtains within 2 hours roasting material (the referred to as second roasting material), 100g second roasts material and deionized water is added
Stirring obtains the slurries that solid content is 25 weight %, hydrochloric acid 200g, the polyethylene glycol 50g of concentration 5mol/L is added, is warming up to 70
DEG C, mixing time 1 hour, it is then filtered to remove mother liquor, filter cake is simultaneously dried, and macroporous structure kaolinite D, preparation process parameter are obtained
And analysis data are shown in Table 1, table 2.
Macroporous structure kaolinite prepares embodiment 4
Kaolin A is roasted at 750 DEG C and obtains within 2 hours roasting material (the referred to as first roasting material), 168g is (with butt
Meter) the first roasting material addition decationized Y sieve water stirring, the slurries that solid content is 25% weight are obtained, are added concentration 1mol/L's
Phosphoric acid 500g and citric acid 100g, is warming up to 70 DEG C, mixing time 1 hour at 70 DEG C, is then filtered to remove mother liquor, and filter cake dries
It is dry, obtain first step product；120g first step product is roasted at 750 DEG C obtain within 2 hours roasting material be known as the second calcining matter
Material, 100g second roast material and the stirring of decationized Y sieve water are added, and obtain the slurries that solid content is 25 weight %, concentration 1mol/L is added
Phosphoric acid 200g and citric acid 50g, 50g ammonium sulfate, be warming up to 70 DEG C, mixing time 1 hour, is then filtered to remove at 70 DEG C
Mother liquor, filter cake are simultaneously dried, and macroporous structure kaolinite E is obtained, and preparation process parameter and analysis data are shown in Table 1, table 2.
Macroporous structure kaolinite prepares embodiment 5
Macroporous structure kaolinite is prepared according to the method for macroporous structure kaolinite preparation embodiment 1, unlike, the first roasting
The temperature of burning is 650 DEG C, is roasted 2 hours, and the temperature of the second roasting is 750 DEG C and roasts 1 hour, the first processing, and sour concentration is
0.5M, wherein the molar ratio of hydrochloric acid and oxalic acid be 5:1. second processing, sour concentration be 5M, hydrochloric acid and oxalic acid 5:1, expanding agent and
Kaolin ratio after second roasting is weight ratio 0.1:1.Gained macroporous structure kaolinite is denoted as F.Preparation process parameter is shown in Table
1, phenetic analysis data are shown in Table 2.
Macroporous structure kaolinite prepares embodiment 6
Macroporous structure kaolinite is prepared according to the method for macroporous structure kaolinite preparation embodiment 1, unlike, the first roasting
The temperature of burning is 750 DEG C, is roasted 1 hour, and the temperature of the second roasting is 650 DEG C and roasts 2 hours, the first processing, and sour concentration is
5M, wherein the molar ratio of hydrochloric acid and oxalic acid is 1:1..Second processing, sour concentration are 0.5M, hydrochloric acid and oxalic acid 1:1, expanding agent
Kaolin ratio after polyethylene glycol and the second roasting is 0.5:1 weight ratio.Gained macroporous structure kaolinite is denoted as G.It prepared
Journey parameter is shown in Table 1, phenetic analysis data and is shown in Table 2.
Macroporous structure kaolin prepares embodiment 7
Macroporous structure kaolinite is prepared according to the method for macroporous structure kaolin preparation embodiment 1, unlike, it is used
Kaolinic weight ratio is 0.3:1 after expanding agent and the second roasting.The temperature of first processing be 1 hour 80 DEG C of times, second
It is 2 hours that the temperature of processing, which is 60 DEG C of times,.The kaolinic total pore volume of gained macropore, specific surface area, average pore size, 10-
The pore volume in the hole 50nm account for total pore volume ratio and embodiment 1 it is unanimous on the whole, composition is close.
Macroporous structure kaolin prepares embodiment 8
Macroporous structure kaolinite is prepared according to the method for macroporous structure kaolin preparation embodiment 1, unlike, it is used
Kaolinic weight ratio is 0.3:1 after expanding agent and the second roasting, and expanding agent is n-butylamine.When the temperature of first processing is 60 DEG C
Between be 2 hours, the temperature of second processing is 80 DEG C, and the time is 1 hour.The kaolinic total pore volume of gained macropore, specific surface area,
Average pore size, the hole 10-50nm pore volume account for total pore volume ratio and embodiment 1 it is unanimous on the whole, composition is close.
Macroporous structure kaolinite prepares comparative example 1
Kaolin A is roasted at 750 DEG C and obtains within 2 hours roasting material (the referred to as first roasting material), 168g first is roasted
It burns material and the slurries that decationized Y sieve water stirs into solid content as 25 weight % is added, the hydrochloric acid 700g and grass of concentration 1mol/L is added
Sour 150g is warming up to 70 DEG C, mixing time 1 hour, is then filtered to remove mother liquor, filter cake drying obtains first step product；By first
Step product 120g is roasted 2 hours at 750 DEG C, is obtained roasting material and is known as the second roasting material, 100g (butt) second is roasted
The stirring of decationized Y sieve water is added in material, obtains the slurries that solid content is 25 weight %, 50g polyethylene glycol is added, is warming up to 70 DEG C, stirs
It mixes the time 1 hour, is then filtered to remove mother liquor, filter cake is simultaneously dried, and comparison kaolinite F, preparation process parameter and analysis number are obtained
According to being shown in Table 1, table 2.
The kaolinic butt chemical composition of 2 macropore of table and property
Constituent content is in terms of butt in table 2, and wherein the measuring condition of butt is 800 DEG C of roastings 1 hour.
As can be seen from Table 2, the macroporous structure kaolinite that method provided by the invention obtains, has biggish specific surface area and hole
For the average pore diameter of volume macroporous structure kaolinite B-G simultaneously in 10-30nm, macroporous structure kaolinite B-G median pore diameter is 10-
The Kong Rong in the hole of 50nm accounts for 80% of total pore volume or more.As seen from Figure 1, macropore kaolinite B pattern is with tubular structure and sheet
The form that structure combines exists.
Catalyst Preparation Example 1
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), decationized Y sieve water (present invention is also referred to as acid water) 60.69Kg is added, stirring 40min is added
23.19Kg macropore kaolinite B and kaolin A 31.94Kg is added the hydrochloric acid that 2Kg concentration is 22 weight % after stirring 60min, stirs
Mix 30min.It is added molecular sieve pulp 116.67Kg (wherein molecular sieve 43.75Kg, decationized Y sieve water 73.79Kg), stirring
30min, spray drying, obtains catalyst microspheres.By gained catalyst microspheres in 500 DEG C of roasting 1h, wash twice, it is every all over washing
With the decationized Y sieve water washing of 8 times of catalyst microspheres dry weights, 120 DEG C freeze-day with constant temperature 2 hours, obtain sample C1.Catalyst
Formula and properties of product are shown in Table 3.
Catalyst Preparation Example 2
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
Decationized Y sieve water 60.69Kg is added in 72 weight % of solid content, and stirring 40min is added 63.77Kg macropore kaolinite B, stirs 60min
The hydrochloric acid that 2Kg concentration is 22 weight % is added afterwards, stirs 30min.Molecular sieve pulp 111.29Kg (wherein molecular sieve is added
37.5Kg, decationized Y sieve water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.By gained catalyst microspheres
It in 500 DEG C of roasting 1h, washs twice, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing, 120 DEG C
Freeze-day with constant temperature 2 hours, obtain sample C2.Catalyst formulation and properties of product are shown in Table 3.
Catalyst Preparation Example 3
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), decationized Y sieve water 60.69Kg is added, 56.52Kg macropore kaolinite B, stirring is added in stirring 40min
The hydrochloric acid that 2Kg concentration is 22% weight is added after 60min, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecule is added
Sieve 43.75Kg, decationized Y sieve water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.Gained catalyst is micro-
Ball washs twice in 500 DEG C of roasting 1h, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing, and 120
DEG C freeze-day with constant temperature 2 hours, obtain sample C3.Catalyst formulation and properties of product are shown in Table 3.
Catalyst Preparation Example 4
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), deionized water 60.69Kg is added, stirring 40min is added 57.35Kg macropore kaolinite C, stirs 60min
The hydrochloric acid that 2Kg concentration is 22 weight % weight is added afterwards, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecular sieve is added
43.75Kg, deionized water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.Gained catalyst microspheres are existed
500 DEG C of roasting 1h are washed twice, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing, 120 DEG C of perseverances
Temperature is 2 hours dry, obtains sample C4.Catalyst formulation and properties of product are shown in Table 3.
Catalyst Preparation Example 5
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), decationized Y sieve water 60.69Kg is added, 57.35Kg macropore kaolinite D, stirring is added in stirring 40min
The hydrochloric acid that 2Kg concentration is 22 weight % is added after 60min, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecule is added
Sieve 43.75Kg, decationized Y sieve water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.Gained catalyst is micro-
Ball washs twice in 500 DEG C of roasting 1h, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing, and 120
DEG C freeze-day with constant temperature 2 hours, obtain sample C5.Catalyst formulation and properties of product are shown in Table 3.
Catalyst Preparation Example 6
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), decationized Y sieve water 60.69Kg is added, 57.18Kg macropore kaolinite E, stirring is added in stirring 40min
The hydrochloric acid that 2Kg concentration is 22 weight % is added after 60min, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecule is added
Sieve 43.75Kg, decationized Y sieve water water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.By gained catalyst
Microballoon washs twice in 500 DEG C of roasting 1h, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing,
120 DEG C freeze-day with constant temperature 2 hours, obtain sample C6.Catalyst formulation and properties of product are shown in Table 3.
Catalyst Preparation Example 7
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), decationized Y sieve water 60.69Kg is added, 57.18Kg macropore kaolinite F, stirring is added in stirring 40min
The hydrochloric acid that 2Kg concentration is 22 weight % is added after 60min, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecule is added
Sieve 43.75Kg, decationized Y sieve water water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.By gained catalyst
Microballoon washs twice in 500 DEG C of roasting 1h, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing,
120 DEG C freeze-day with constant temperature 2 hours, obtain sample C7.Catalyst formulation and properties of product are shown in Table 3.
Catalyst Preparation Example 8
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), decationized Y sieve water water 60.69Kg is added, 56.93Kg macropore kaolinite G, stirring is added in stirring 40min
The hydrochloric acid that 2Kg concentration is 22 weight % is added after 60min, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecule is added
Sieve 43.75Kg, decationized Y sieve water water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.By gained catalyst
Microballoon washs twice in 500 DEG C of roasting 1h, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing,
120 DEG C freeze-day with constant temperature 2 hours, obtain sample C8.Catalyst formulation and properties of product are shown in Table 3.
CATALYST PREPARATION Comparative's example 1
Aluminum sol 45.45Kg is added in a kettle, stirs, addition 22.22Kg boehmite (Shandong Aluminium Industrial Corp,
72 weight % of solid content), acid water 60.69Kg is added, stirring 40min is added 57.18Kg and compares kaolinite H, after stirring 60min
The hydrochloric acid that 2Kg concentration is 22% weight is added, stirs 30min.Molecular sieve pulp 116.67Kg (wherein molecular sieve is added
43.75Kg, acid water 73.79Kg), 30min is stirred, spray drying obtains catalyst microspheres.Gained catalyst microspheres are existed
500 DEG C of roasting 1h are washed twice, every decationized Y sieve water washing all over 8 times of catalyst microspheres dry weights of washing, 120 DEG C of perseverances
Temperature is 2 hours dry, obtains sample D1.Catalyst formulation and properties of product are shown in Table 3.
Evaluating catalyst
Evaluate the cracking reaction performance of catalyst and comparative catalyst of the present invention.
Feedstock oil is military mixed three feedstock oils, and physico-chemical property data are shown in Table 4.
Table 5 lists the evaluation result on fixed fluidized bed device.Catalyst passes through 800 DEG C, and 17 hours, 100% water steamed
Vapour aging inactivation processing, catalyst loading 9g, oil ratio be 5 (weight ratios), 500 DEG C of reaction temperature.
Wherein, conversion ratio=yield of gasoline+yield of liquefied gas+dry gas yield+coking yield
Yield of light oil=yield of gasoline+diesel yield
Liquid yield=liquefied gas+gasoline+diesel oil
Coke selectivity=coke yield/conversion ratio
Table 3
Table 4
Table 5
| Catalyst | C1 | C2 | C3 | C4 | C5 | C6 | C7 | C8 | D1 (comparative example 1) |
| Product yield, weight % | |||||||||
| Dry gas | 1.86 | 1.93 | 2.06 | 1.98 | 2.12 | 2.22 | 2.15 | 2.26 | 2.45 |
| Liquefied gas | 16.01 | 16.22 | 15.8 | 16.45 | 16.57 | 16.23 | 17.15 | 16.79 | 16.6 |
| Gasoline | 49.78 | 50.11 | 51.1 | 48.56 | 47.46 | 47.15 | 46.89 | 46.49 | 45.02 |
| Diesel oil | 14.22 | 13.34 | 12.36 | 14.21 | 15.02 | 15.45 | 14.34 | 15.69 | 15.08 |
| Heavy oil | 10.98 | 9.99 | 9.69 | 9.78 | 9.88 | 9.86 | 9.96 | 9.9 | 11.41 |
| Coke | 7.15 | 8.41 | 8.99 | 9.02 | 8.95 | 9.09 | 9.51 | 8.87 | 9.44 |
| It is total | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Micro-activity, % | 79 | 78 | 82 | 79 | 78 | 77 | 77 | 77 | 75 |
| Conversion ratio, % | 74.8 | 76.67 | 77.95 | 76.01 | 75.1 | 74.69 | 75.7 | 74.41 | 73.51 |
| Yield of light oil, % | 64 | 63.45 | 63.46 | 62.77 | 62.48 | 62.6 | 61.23 | 62.18 | 60.1 |
| Coke selectivity, % | 9.56 | 10.97 | 11.53 | 11.87 | 11.92 | 12.17 | 12.56 | 11.92 | 12.84 |
Table 5 statistics indicate that, the catalyst prepared of macropore kaolinite prepared using the method for the present invention is compared with the prior art
The catalyst of preparation under the premise of identical molecular sieve usage amount, has better residual oil cracking sexuality compared with contrast medium
And higher conversion ratio, yield of gasoline with higher, heavy oil yield is lower, and yield of light oil is higher, and coke selectivity is good；?
Still had more preferably more using can be seen that the catalyst C2 prepared in content more low molecule sieve embodiment 2 compared to comparative example
Excellent residual oil cracking performance and higher conversion ratio and yield of gasoline.
Catalyst C1-C8 and D1 is subjected to cyclic polluting (deposit Ni and V) on circulation aging equipment, after cyclic polluting
Catalyst mixture on Ni, V content be shown in Table 6, wherein
After catalyst mixture introduces heavy metal (Ni and V) by meter Xie Er infusion process, then cyclic polluting step includes:
By introduce heavy metal after catalyst object be packed into small fixed flowing bed, on small fixed fluidized bed unit as follows into
Row processing:
(a) in a nitrogen atmosphere, with the heating rate of 20 DEG C/min, 600 DEG C are heated to；
(b) with the heating rate of 1.5 DEG C/min, after being heated to 780 DEG C, constant temperature is at 780 DEG C, by following step in thermostatic process
Rapid replacement processing atmosphere；
(i) with the nitrogen (wherein, the propylene containing 5 volume % in nitrogen) containing 40 volume %, the water of 60 volume % steams
The atmosphere of gas is handled 10 minutes,
(ii) with the nitrogen (pure nitrogen gas, no propylene) containing 40 volume %, the atmosphere processing 10 of the vapor of 60 volume %
Minute,
(iii) 4000ppmSO (is contained with the air containing 40 volume %2), the atmosphere processing 10 of the vapor of 60 volume %
Minute,
(iv) with the nitrogen containing 40 volume %, the atmosphere of the vapor of 60 volume % is handled 10 minutes；Then by aforementioned
It is each primary sequentially to repeat circulation step (i)-(iv), then repeatedly step (i), end loop pollute step；
Then the step of carrying out aging: the catalyst mixture after cyclic polluting is containing 100 volume % at 800 DEG C
Steam atmosphere in aging 8 hours；
Then the catalytic performance of the catalyst mixture after cyclic polluting-aging is investigated on ACE device, wherein former
Expect that oily (property is shown in Table 4) enters in reactor bottom to contact with catalyst mixture, specific evaluation condition and the results are shown in Table 6.
Table 6
Table 6 statistics indicate that, the catalyst prepared of macropore kaolinite prepared using the method for the present invention is had preferable
Anti-metallic contamination ability, cracking activity are declined compared to untainted fresh dose of activity, but still compared with comparative catalyst
With preferable cracking activity, while compared to the contrast medium conversion ratio with higher and yield of gasoline after pollution.
Claims (16)
1. a kind of macroporous structure kaolinite, which is characterized in that the kaolinic average pore diameter of macroporous structure is 2-50nm, institute
The Kong Rong for stating the hole that macroporous structure kaolinite median pore diameter is 10-50nm accounts for 80% of total pore volume or more.
2. macroporous structure kaolinite described in accordance with the claim 1, which is characterized in that the macroporous structure kaolinite median pore diameter
The 80%-95% or 81-92% of total pore volume are accounted for for the Kong Rong in the hole of 10-50nm.
3. macroporous structure kaolinite according to claim 1 or 2, which is characterized in that the kaolinic ratio of macroporous structure
Surface area is 100-250m2/ g such as 100-200m2/ g, total pore volume 0.20-0.30ml/g.
4. according to macroporous structure kaolinite described in claims 1 or 2 or 3, which is characterized in that the macroporous structure is kaolinic
Average pore diameter is 10-30nm.
5. according to macroporous structure kaolinite described in claim 1,2,3 or 4, which is characterized in that on the basis of dry weight, institute
State the kaolinic Al of macroporous structure2O3Content is that 33-45 weight % is, for example, 35-42 weight %, SiO2Content is 45-59.5 weight
Measure %.
6. according to macroporous structure kaolinite described in claim 1,2,3,4 or 5, which is characterized in that the macroporous structure kaolinite
Shi Zhong, Fe2O3It is, for example, 0.5-1.5 weight %, CaO+MgO content for no more than 2 weight % that content, which is no more than 1.5 weight %,
For example 1-2 weight %, α-SiO2It is, for example, 1-2 weight % that content, which is no more than 2 weight %,.
7. a kind of kaolinic preparation method of macroporous structure, includes the following steps:
Common kaolin is subjected to the first roasting for roasting 0.5-3 hours at 650-800 DEG C；
It is 40-80 DEG C preferably 60-80 DEG C anti-in temperature by the kaolin and the first acid solution formation mixture after the first roasting
It answers and carries out within 0.5-2 hours the first contact, the first kaolin slurry is made, it is dry to be dried to obtain first for the filtering of the first kaolin slurry
Dry product；
First desciccate is subjected to the second roasting for roasting 0.5-3 hours in 650-800 DEG C, the kaolinite after obtaining the second roasting
Soil；
Kaolin, the second acid solution and expanding agent mixing after second roasting, Yu Wendu 40-80 DEG C preferably 60-80 DEG C of reaction
The second contact is carried out within 0.5-2 hours, filtering, drying obtain macroporous structure kaolinite.
8. according to the method for claim 7, which is characterized in that the common kaolin is soft kaolin, hard height
One of ridge soil, grittiness kaolin, gangue, halloysite are a variety of.
9. according to the method for claim 7, which is characterized in that first maturing temperature is 650-750 DEG C, when roasting
Between be 1-2 hours.
10. according to method described in claim 7 or 9, which is characterized in that the maturing temperature of second roasting is 650-
750 DEG C, calcining time is 1-2 hours.
11. according to the method for claim 7, which is characterized in that first acid solution contains hydrochloric acid, sulfuric acid, nitre
One of acid, phosphoric acid, oxalic acid, acetic acid, citric acid are a variety of；In second acid solution containing hydrochloric acid, sulfuric acid, phosphoric acid,
One of nitric acid, oxalic acid, citric acid are a variety of；It is preferred that the acid in first acid solution includes hydrochloric acid and oxalic acid, hydrochloric acid
Be the preferred 0.4-5:1 of 0.3-10:1 with the ratio of oxalic acid, the acid in second acid solution includes hydrochloric acid and oxalic acid, hydrochloric acid and
The ratio of oxalic acid is the preferred 0.3-5:1 of 0.3-10:1.
12. according to the method for claim 7, which is characterized in that first acid solution and the second acid solution mole
Concentration is individually 0.5-5mol/L；In first contact, kaolinic weight ratio is 1-10 after the first acid solution and the first roasting:
1,；In second contact, the kaolinic weight ratio after the second acid solution and the second roasting is 1-10:1.
13. according to the method for claim 7, which is characterized in that the expanding agent be ammonium sulfate, ammonium phosphate, ammonium carbonate,
Organic amine, polyethylene glycol, polyacrylamide it is one or more.
14. according to the method for claim 13, which is characterized in that the expanding agent with second roasting after it is kaolinic heavy
Amount is than being 0.05-1:1 such as 0.1-0.5:1.
15. a kind of catalytic cracking catalyst, which is characterized in that contain molecular sieve, macroporous structure kaolinite, binder and optional
Clay, wherein the macroporous structure kaolinite content is 2-50 weight %, molecular sieve content is 25-50 weight %, binder
Content is 10-30 weight %, and the content of clay is 0-50 weight %, and the macroporous structure kaolinite is appointed for claim 1-6
The macroporous structure kaolinite of quilt caused by macroporous structure kaolinite described in one or claim any one of 7-14.
16. a kind of preparation method of catalytic cracking catalyst, wherein this method comprises: by binder, optional clay, molecule
Sieve and macroporous structure kaolinite are beaten to obtain catalyst slurry, and the catalyst slurry is spray-dried, described big
Hole kaolinite is the big of quilt caused by macroporous structure kaolinite described in any one of claims 1-6 or claim any one of 7-14
Pore structure kaolinite.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115475612A (en) * | 2021-05-31 | 2022-12-16 | 中国地质大学（北京） | A method for improving catalytic performance of FCC catalyst |
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| CN101045202A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Method for modifying kaolinite |
| CN101491764A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Residual oil hydrogenation catalyst and preparation method and use thereof |
| WO2016175706A1 (en) * | 2015-04-30 | 2016-11-03 | Nanyang Technological University | A pillared clay catalyst |
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| CN101045202A (en) * | 2006-03-31 | 2007-10-03 | 中国石油化工股份有限公司 | Method for modifying kaolinite |
| CN101491764A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Residual oil hydrogenation catalyst and preparation method and use thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115475612A (en) * | 2021-05-31 | 2022-12-16 | 中国地质大学（北京） | A method for improving catalytic performance of FCC catalyst |
| CN115475612B (en) * | 2021-05-31 | 2024-02-27 | 中国地质大学（北京） | Method for improving catalytic performance of FCC catalyst |
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