CN110876926B - Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst - Google Patents
Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst Download PDFInfo
- Publication number
- CN110876926B CN110876926B CN201811033115.5A CN201811033115A CN110876926B CN 110876926 B CN110876926 B CN 110876926B CN 201811033115 A CN201811033115 A CN 201811033115A CN 110876926 B CN110876926 B CN 110876926B
- Authority
- CN
- China
- Prior art keywords
- zirconium
- composite sol
- aluminum
- sol
- content
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J29/80—Mixtures of different zeolites
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the field of catalytic cracking catalysts, and discloses a zirconium-aluminum composite sol, a preparation method and application thereof, and a preparation method of a catalytic cracking catalyst. The preparation method of the composite sol comprises the following steps: acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant and water; the conditions for the acidification hydrolysis include: the temperature is 10-100 ℃ and the time is 0.2-5h. The preparation method of the invention can simplify the preparation process of the sol, and fully exerts the advantages of the alumina and the zirconia through the catalysis promotion of the zirconia, and the prepared cracking catalyst has better strength and cracking effect.
Description
Technical Field
The invention relates to the field of catalytic cracking catalysts, in particular to a zirconium-aluminum composite sol, a preparation method and application thereof, and a preparation method of a catalytic cracking catalyst.
Background
At present, the catalytic cracking catalyst in China mainly uses an aluminum binder, and the catalytic cracking catalyst taking alumina sol and peptized pseudo-boehmite as the binders has the characteristics of good strength and strong heavy oil cracking capability. Pseudoboehmite refers to a hydrated alumina containing one to two water molecules that is commonly peptized for cracking catalyst production. The peptized pseudo-boehmite as the substrate has the following characteristics: 1) The abrasion resistance is better than that of the silica-alumina gel matrix; 2) The catalyst has certain activity, can play a synergistic effect with a molecular sieve, and improves the heavy oil cracking capability of the catalyst; 3) Improving the mesoporous structure of the catalyst and increasing the specific surface of the catalyst; 4) The hydrothermal stability of the catalyst is improved; 5) Has certain metal pollution resistance, forms nickel aluminate spinel with Ni to passivate Ni, and has certain fixing effect on V. Peptization is a key step in the production of catalytic cracking catalysts, and fluctuations in the peptization properties and the degree of peptization of pseudo-boehmite can lead to fluctuations in the mechanical strength and pore volume of the prepared catalysts.
CN103031062A the present invention provides a method for preparing a peptized aluminum binder, which comprises mixing an aluminum binder with an acid and beating to obtain a first slurry, and then contacting with a base to obtain a second slurry. However, the physical and chemical properties of the aluminum binders prepared by the method in different batches are different, and the prepared cracking catalyst has low matrix activity and poor abrasion strength.
CN1209289C provides a method for preparing an aluminum sol, which is characterized in that: under the condition of room temperature, inorganic aluminum salt is taken as a raw material, and a precipitate is obtained by adding excessive alkali, so that the pH value is more than 9; washing, adding acid as dispergation catalyst, [ H ] + ]/[Al 3+ ]The range of the molar ratio is 0.07-0.50, stable and clear aluminum sol is formed under the action of ultrasonic waves, and the physical parameters of the ultrasonic waves are as follows: the frequency is 20-50KHz, and the sound intensity is 50-150W. Although the particle size of the alumina sol prepared by the inventionThe alumina sol has the advantages of uniformity and good stability, but does not mention whether the bonding performance of the obtained alumina sol is improved or not, and in addition, the preparation process is complex and the production cost is still very high.
CN102451768A discloses a preparation method of zirconia-alumina composite oxide dry glue, which comprises the following steps: (1) Carrying out gelling reaction on the aluminum-containing compound solution and a precipitator to obtain aluminum hydroxide sol; (2) Carrying out gelling reaction on the zirconium-containing compound solution and an acidic or alkaline precipitator to obtain zirconium-containing sol; (3) Mixing the aluminum hydroxide sol obtained in the step (1) and the zirconium-containing sol obtained in the step (2), stirring and then aging; wherein before mixing, the pH value of the aluminum hydroxide sol obtained in the step (1) and the pH value of the zirconium-containing sol obtained in the step (2) are different by 0-2; (4) And (4) washing, filtering and drying the material obtained in the step (3) to obtain the zirconia-alumina composite oxide dry glue. The method can obtain the composite oxide dry glue, improves the pore structure and the surface performance of a composite oxide carrier, can improve the sulfuration performance of a catalyst taking the composite oxide carrier as the carrier, and is easy to reduce the loaded active metal, but the composite oxide dry glue is suitable for being used as a carrier of a hydrofining catalyst and is not suitable for being used as a carrier of a catalytic cracking catalyst.
CN101433863A discloses a preparation method of a composite oxide carrier, which comprises the following steps: coprecipitating and aging precursor solutions of alumina, silicon dioxide and zirconia with an alkaline solution, washing, filtering and drying the precipitate to obtain composite oxide powder, and extruding, molding and activating to obtain a composite oxide carrier; characterized in that a surfactant is added in the co-precipitation and/or aging step. Since the coprecipitation method is a method in which two or more species are co-precipitated under certain conditions, the coprecipitation conditions cannot ensure that all the species are carried out in optimum conditions, and the method has inherent disadvantages and also causes ZrO 2 And the zirconium oxide enters a bulk phase in the coprecipitation process, so that the influence of the zirconium oxide on the surface of the carrier is weakened, and the physical and chemical properties of the final carrier are influenced.
At present, most of catalytic cracking catalysts adopt alumina sol and peptized pseudo-boehmite as binders, and the matrix activity is low and the selectivity is poor. However, zirconium sol is not used alone because it is highly acidic and provides active sites, but it easily destroys active components in the catalyst. The zirconia-alumina composite oxides of the prior patents are all used as carriers in hydrogenation catalysts. Therefore, the development of a binder for a catalytic cracking catalyst, which has both an active center and a good strength of the catalyst, has important research significance.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, the aluminum sol and the pseudo-boehmite sol are used as binders, the matrix activity is low, the selectivity is poor, and the zirconium sol cannot be used independently, and provides a zirconium-aluminum composite sol, a preparation method and application thereof, and a preparation method of a catalytic cracking catalyst.
In order to achieve the above objects, a first aspect of the present invention provides a zirconium aluminum composite sol in which the content of aluminum element is 1 to 10% by weight and the content of zirconium element is 0.5 to 10% by weight, which is dried at 100 ℃ for 6 hours and then calcined at 600 ℃ for 6 hours to obtain a solid in which zirconium dioxide exists in the form of monoclinic phase and tetragonal phase.
The second aspect of the present invention provides a method for preparing a zirconium-aluminum composite sol, comprising:
acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant and water; the acidification hydrolysis conditions comprise: the temperature is 10-100 ℃ and the time is 0.2-5h.
Preferably, the method further comprises: and (3) carrying out reaction on a product obtained by acidification and hydrolysis under the ultrasonic condition.
The third aspect of the invention provides the zirconium-aluminum composite sol prepared by the preparation method.
The fourth aspect of the invention provides the application of the zirconium-aluminum composite sol as a binder in the preparation of a catalytic cracking catalyst.
A fifth aspect of the present invention provides a method for preparing a catalytic cracking catalyst, wherein the method comprises: pulping a binder, clay and a molecular sieve to obtain catalyst slurry, and spray-drying the catalyst slurry, wherein the binder contains the zirconium-aluminum composite sol.
The zirconium-aluminum composite sol provided by the invention is prepared by mixing and acidifying an alumina precursor, a zirconium dioxide precursor and an acid, and is possible to be added into Al 3+ And Zr 4+ Bond bridge Al-O-Zr is formed between the two, and the formed new bridge bond introduces auxiliary agent ions into alumina crystal lattices or forms a new compound with alumina, thereby enhancing the bonding strength. The agglomeration phenomenon is easy to occur in the preparation process, and the surfactant is added, so that the dispersion of the colloid is facilitated. In addition, preferably, the method further comprises: the product obtained by acidification and hydrolysis is reacted under the ultrasonic condition, which is more favorable for improving the stability of the matrix.
The preparation method of the invention can simplify the preparation process of the sol, and fully exerts the advantages of the alumina and the zirconia through the catalysis promotion of the zirconia, and the prepared cracking catalyst has better strength and cracking effect.
Drawings
FIG. 1 is an XRD spectrum of a solid obtained by drying and calcining a zirconium-aluminum composite sol C1 obtained in example 1;
FIG. 2 is a TEM image of the zirconium-aluminum composite sol C1 obtained in example 1.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are given by way of illustration and explanation only, not limitation.
The first aspect of the present invention provides a zirconium-aluminum composite sol in which the content of aluminum element is 1 to 10% by weight and the content of zirconium element is 0.5 to 10% by weight, which is dried at 100 ℃ for 6 hours and then calcined at 600 ℃ for 6 hours to obtain a solid in which zirconium dioxide exists in the form of monoclinic phase and tetragonal phase. The zirconium-aluminum composite sol provided by the invention is roasted, so that not only monoclinic-phase zirconium dioxide but also tetragonal-phase zirconium dioxide exist.
According to a preferred embodiment of the present invention, the solid has an XRD pattern with diffraction peaks at 28 ° ± 0.5 ° 2 θ, 31.4 ° ± 0.5 ° 2 θ and 30.3 ° ± 0.5 ° 2 θ, 35 ° ± 0.5 ° 50 ° ± 0.5 ° 60 ° ± 0.5 ° 2 θ, as shown in figure 1. Wherein, the diffraction peak at the 2 theta position of 28 degrees +/-0.5 degrees and 31.4 degrees +/-0.5 degrees corresponds to monoclinic-phase zirconium dioxide, and the diffraction peak at the 2 theta position of 30.3 degrees +/-0.5 degrees, 35 degrees +/-0.5 degrees, 50 degrees +/-0.5 degrees and 60 degrees +/-0.5 degrees corresponds to tetragonal-phase zirconium dioxide.
According to a preferred embodiment of the present invention, the solid has an XRD pattern with diffraction peaks at 46 ° ± 0.5 ° and 66.6 ° ± 0.5 ° 2 θ as shown in figure 1. The diffraction peak at this position corresponds to the diffraction peak of gamma-alumina.
According to the composite sol provided by the invention, preferably, the content of the aluminum element is 2-6 wt%, and the content of the zirconium element is 1-6 wt%; further preferably, the content of the aluminum element is 4.5 to 6% by weight and the content of the zirconium element is 1.8 to 2.2% by weight.
According to the composite sol provided by the invention, the weight ratio of the aluminum element to the zirconium element is preferably (0.3-6): 1, more preferably (0.5-5): 1, more preferably (1-4): 1, most preferably (2.2-3.1): 1.
according to the composite sol provided by the invention, the pH value of the composite sol is preferably 0.5-5, more preferably 1-4, and even more preferably 2.2-2.6.
In the invention, the element content in the composite sol can be measured by ICP-OES inductively coupled plasma-atomic emission spectrometry GB/T30902-2014.
According to the present invention, the composite sol preferably further contains a surfactant, and the content of the surfactant is preferably 0.5 to 10 wt% of the content of the aluminum element, and more preferably 0.5 to 1.5 wt% of the content of the aluminum element.
According to the present invention, the surfactant may be an ionic surfactant or a nonionic surfactant, and the present invention is not particularly limited thereto, and preferably, the surfactant is selected from the group consisting of nonionic surfactants, more preferably at least one selected from the group consisting of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glycerol ester, fatty acid sorbitan, polysorbate, triethanolamine soap sucrose ester, and polyhydric alcohol sucrose ester, more preferably at least one selected from the group consisting of polyoxyethylene-8-octylphenyl ether, fatty alcohol polyoxyethylene ether, and polysorbate, and most preferably polyoxyethylene-8-octylphenyl ether. The preferred embodiment of the invention is more favorable for improving the dispersibility of the composite sol, and the composite sol is more favorable for improving the hydrothermal stability and abrasion strength of the catalyst when being used in the catalytic cracking catalyst.
According to the invention, the composite sol also contains water.
The composite sol provided by the invention has more uniform colloidal particle size distribution, and the colloidal particle size is about 20nm probably as can be seen through the representation of a transmission electron microscope. In addition, the wear strength is effectively improved on the premise that the activity of the catalyst meets the industrial requirements by applying the binder provided by the invention to a catalytic cracking catalyst.
The second aspect of the invention provides a preparation method of a zirconium-aluminum composite sol, which comprises the following steps:
acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant and water; the acidification hydrolysis conditions comprise: the temperature is 10-100 ℃ and the time is 0.2-5h.
In the present invention, although the specific mode for obtaining the mixture is not particularly limited, in order to further improve the properties of the obtained composite sol, it is preferable that an alumina precursor, a zirconia precursor, an acid and water are mixed to obtain a first mixture, and then a surfactant is added to the first mixture to obtain the mixture.
The embodiment of the present invention for obtaining the first mixture is not particularly limited, and for example, the alumina precursor and the zirconia precursor may be mixed with an acid solution, respectively, and then the two may be mixed to obtain the first mixture; or adding an alumina precursor and a zirconium dioxide precursor into the acid solution under the stirring condition; alternatively, the alumina precursor may be mixed with an acid solution and then an aqueous solution of the zirconia precursor may be added.
According to the preparation method provided by the present invention, preferably, the acid is used in an amount such that the pH of the first mixture is 0.5 to 5, and more preferably 1 to 4.
According to the preparation method provided by the invention, the aluminum oxide precursor and the zirconium dioxide precursor are preferably used in an amount such that the content of aluminum element in the prepared zirconium-aluminum composite sol is 1-10 wt%, more preferably 2-6 wt%, and even more preferably 4.5-6 wt%; the content of zirconium element is 0.5 to 10% by weight, further preferably the content of zirconium element is 1 to 6% by weight, still further preferably the content of zirconium element is 1.8 to 2.2% by weight.
According to the preparation method provided by the invention, the surfactant is preferably used in an amount such that the content of the surfactant in the prepared zirconium-aluminum composite sol is 0.5-10 wt% of the content of the aluminum element, and more preferably 0.5-1.5 wt% of the content of the aluminum element.
According to the invention, the alumina precursor refers to an aluminum-containing substance which can exist in the form of alumina by calcination after the acid hydrolysis treatment. Preferably, the alumina precursor is at least one selected from the group consisting of SB powder, pseudo-boehmite, alumina trihydrate, boehmite, alumina sol, and amorphous aluminum hydroxide, and is further preferably SB powder and/or pseudo-boehmite.
According to the invention, the zirconium dioxide precursor refers to a zirconium-containing substance which can be present in the form of zirconium dioxide by calcination after the acid hydrolysis treatment. Preferably, the zirconia precursor is selected from at least one of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, zirconium sulfate, hydrous zirconium oxide, and amorphous zirconium dioxide, and further preferably zirconium tetrachloride and/or zirconium oxychloride.
The acid according to the present invention may be selected from at least one of inorganic acids and organic acids dissolved in water, preferably at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid, and most preferably hydrochloric acid.
According to the preparation method provided by the invention, the type of the surfactant is as described above, and details are not repeated here.
According to the preparation method provided by the invention, preferably, the conditions of the acidification hydrolysis comprise: the temperature is 10-60 deg.C, and the time is 0.5-2 hr, preferably 20-45 deg.C, and the time is 0.5-1 hr.
According to a preferred embodiment of the invention, the acidification hydrolysis is carried out under stirring.
According to a specific embodiment a of the present invention, the method comprises: adding the alumina precursor into the acid solution, dispersing for 10-60min (preferably in a homogenizer), adding the aqueous solution of the zirconium dioxide precursor, and dispersing for 10-60min (preferably in a homogenizer) to obtain a first mixture; adding a surfactant to the first mixture to perform acidification hydrolysis.
According to a specific embodiment B of the present invention, the method comprises: adding an aluminum oxide precursor and a zirconium dioxide precursor into an acid solution under the stirring condition, and continuously stirring for 10-60min to obtain a first mixture; adding a surfactant into the first mixture to carry out acidification and hydrolysis.
In the present invention, the rotation speed of the stirring may be 100 to 200r/min.
According to a preferred embodiment of the invention, the method further comprises: and (3) carrying out reaction on a product obtained by acidification and hydrolysis under the ultrasonic condition. By adopting the preferred implementation mode, the reaction time is more favorably shortened, the grain size distribution of colloidal particles is more uniform, and the abrasion strength of the catalyst is more favorably improved when the prepared composite sol is used for a catalytic cracking catalyst.
According to a preferred embodiment of the present invention, the reaction conditions comprise: the temperature is 10-100 deg.C, preferably 10-60 deg.C, more preferably 20-45 deg.C, and the time is 0.1-5 hr, preferably 0.1-3 hr, more preferably 0.5-2 hr.
According to the invention, the ultrasound may be water bath ultrasound or oil bath ultrasound, preferably water bath ultrasound.
Preferably, the frequency of the ultrasound is 35 to 200KHz, more preferably 50 to 150KHz, and still more preferably 50 to 100KHz. For example, 35KHz, 50KHz, 80KHz, 100KHz may be used.
The power selection range of the ultrasonic wave is wide, and the proper power can be selected according to the quality of the ultrasonic treated material, for example, the ultrasonic wave can be used for ultrasonic treatment of 1kg of material, and the power of the ultrasonic wave can be 200-600W.
The third aspect of the invention also provides the zirconium-aluminum composite sol prepared by the preparation method. The zirconium-aluminum composite sol has the characteristics described above, and is not described in detail herein.
As previously mentioned, a fourth aspect of the present invention provides the use of the zirconium aluminium composite sol of the present invention as a binder in the preparation of a catalytic cracking catalyst.
The fifth aspect of the present invention provides a method for preparing a catalytic cracking catalyst, wherein the method comprises: pulping a binder, clay and a molecular sieve to obtain catalyst slurry, and spray-drying the catalyst slurry, wherein the binder contains the zirconium-aluminum composite sol.
According to a preferred embodiment of the present invention, the binder is the zirconium-aluminum composite sol provided by the present invention.
According to a preferred embodiment of the present invention, the preparation method of the catalytic cracking catalyst comprises:
(1) Pulping clay and water, adding the zirconium-aluminum composite sol, and stirring to obtain slurry A;
(2) Pulping a molecular sieve and water to obtain molecular sieve slurry;
(3) Mixing the slurry A and the molecular sieve slurry, then adding alumina sol into the mixture, pulping the mixture to obtain catalyst slurry, and carrying out spray drying on the catalyst slurry.
The clay of the present invention is a clay raw material well known to those skilled in the art, and any kind of commonly used clay can be used in the present invention, and for the present invention, the clay is preferably one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, pseudohalloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. For the present invention, the clay is preferably one or more of sepiolite, kaolin and halloysite, and further preferably kaolin.
In the invention, the molecular sieve is a well-known molecular sieve raw material in the field, the molecular sieves commonly used in the field can be used in the invention, and the molecular sieves are preferably REY, REHY, REUSY and USY in the invention, and the gas phase chemical method (SiCl) is adopted 4 Al removal and Si supplement method), liquid phase chemical method ((NH) 4 ) 2 SiF 6 Aluminum extraction and silicon supplement method) and other methods, as well as ZSM-5 type and beta type zeolites with high silicon-aluminum ratio or the mixture thereof. Preferably, the molecular sieve is a ZSP-3 molecular sieve and a DASY molecular sieve.
According to the method for preparing the catalytic cracking catalyst of the present invention, the solid content of the catalyst slurry is preferably 20 wt% or more, preferably 20 to 40 wt%.
According to a preferred embodiment of the present invention, the catalyst slurry has a molecular sieve content of 10 to 50 wt.%, preferably 25 to 35 wt.%, based on the dry weight of the catalyst slurry; the clay content is 10-50 wt.%, preferably 35-45 wt.%; the content of the zirconium-aluminum composite sol is 6-30 wt%, preferably 10-20 wt%, and the content of the aluminum sol is Al 2 O 3 Calculated) is 3 to 20 wt.%, preferably 5 to 15 wt.%.
According to the preparation method of the catalytic cracking catalyst of the present invention, preferably, the catalytic cracking catalyst is obtained by spray drying and then calcining.
The catalytic cracking catalyst prepared by the zirconium-aluminum composite sol has higher abrasion strength.
The present invention will be described in detail below by way of examples.
The element content in the zirconium-aluminum composite sol is measured by ICP-OES inductively coupled plasma-atomic emission spectrometry GB/T30902-2014.
The raw material specifications used in the zirconium-aluminum composite sol and catalyst preparation examples are as follows:
SB powder: commercially available from Sasol, germany, with a solids content of 75% by weight;
zirconium oxychloride: commercially available from Aldrich, analytical pure, 98.5%;
hydrochloric acid: chemical purity, which is a product from Beijing chemical plants and has a concentration of 36 to 38 weight percent;
nitric acid: chemical purity, product of Beijing chemical plant, concentration 69.2% by weight;
triton X-100: polyoxyethylene-8-octylphenyl ether, commercially available from dow corporation, analytically pure, 99%;
fatty alcohol polyoxyethylene ether: MOA-3, purchased from Haian petrochemical plant of Jiangsu province, and analytically pure;
kaolin: a solid content of 75% by weight, produced by Kaolin corporation of China (Suzhou);
DASY molecular sieve: qilu catalyst division, rare earth content 2.3 wt%;
ZSP-3 molecular sieve: qilu catalyst division, P 2 O 5 Is contained in an amount of 3.02% by weight.
Example 1
This example illustrates a zirconium-aluminum composite sol and a method for preparing the same according to the present invention.
(1) Adding 332g of deionized water into a beaker, then adding 53g of SB powder, slowly adding 7.2g of hydrochloric acid, and dispersing in a homogenizer for 30min; to another beaker was added 63.5g of water followed by 33g of zirconium oxychloride; mixing the materials in the two beakers, and dispersing in a homogenizer for 20min to obtain a first mixture (pH 2.52); adding 0.3g surfactant Triton X-100 into the first mixture, and stirring at 20 deg.C for 30min at 150r/min.
(2) And (2) putting the reaction product obtained in the step (1) into an ultrasonic water bath, and reacting for 120min at the reaction temperature of 20 ℃ under the frequency of 50KHz and the power of 280W to obtain the zirconium-aluminum composite sol C1.
The obtained zirconium-aluminum composite sol C1 was subjected to ICP-OES analysis, and the results are shown in Table 1, and the ratio of the surfactant to the aluminum element was calculated from the charge ratio.
Drying the obtained zirconium-aluminum composite sol C1 at 100 ℃ 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrum is shown as figure 1, and as can be seen from figure 1, diffraction peaks corresponding to ZrO exist at positions with 2 theta of 28 degrees +/-0.5 degrees and 31.4 degrees +/-0.5 degrees in the XRD spectrum 2 Has diffraction peaks at 2 theta of 30.3 DEG + -0.5, 35 DEG + -0.5, 50 DEG + -0.5 and 60 DEG + -0.5 degrees, corresponding to ZrO 2 The tetragonal phase of (1); diffraction peaks corresponding to gamma-Al exist at the positions of 46 DEG +/-0.5 DEG and 66.6 DEG +/-0.5 DEG of 2 theta 2 O 3 The diffraction peak of (4).
The obtained zirconium-aluminum composite sol C1 was diluted 1000 times and analyzed by a transmission electron microscope, and the TEM image was shown in fig. 2. As can be seen from FIG. 2, the colloidal particle size distribution of the zirconium aluminum composite sol C1 is uniform, and is about 20 nm.
Comparative example 1
332g of deionized water was added to the beaker, 53g of SB powder was added, and then 7.2g of hydrochloric acid was slowly added and dispersed in a homogenizer for 60min to obtain an alumina sol D1.
Comparative example 2
396g of deionized water was added to the beaker, and 48.4g of zirconium tetrachloride was slowly added under stirring (rotation speed of 150 r/min), followed by 22.4g of ammonia (25% by weight) and dispersed in a homogenizer for 30min to obtain a zirconium sol D2. XRD analysis is carried out on the solid, and only tetragonal-phase ZrO in the XRD spectrogram 2 。
Comparative example 3
(1) Adding 332g of deionized water into a beaker, then adding 53g of SB powder, slowly adding 7.2g of hydrochloric acid, and dispersing in a homogenizer for 30min;
(2) Adding 63.5g of ethanol and deionized water (the volume concentration of the ethanol is 15%) into another beaker, then adding 33g of zirconium oxychloride, dropwise adding ammonia water (25 wt%), adjusting the pH value to 6.5, and reacting at 45 ℃ for 30min to obtain zirconium sol;
(3) Mixing the materials in the two beakers, dispersing in a homogenizer for 20min to obtain a first mixture (pH 3.02), and stirring at 20 deg.C for 30min at a rotation speed of 150r/min to obtain zirconium-aluminum composite sol D3.
And (3) diluting the obtained zirconium-aluminum composite sol D3 by 1000 times, and analyzing by using a transmission electron microscope to obtain a TEM image. As can be seen from the figure, the particle size distribution of the colloidal particles of the zirconium-aluminum composite sol D3 is not uniform, and the sizes are different.
Example 2
This example illustrates a zirconium-aluminum composite sol and a method for preparing the same according to the present invention.
(1) Adding 332g of deionized water into a beaker, adding 71g of SB powder, slowly adding 9.6g of hydrochloric acid, and dispersing in a homogenizer for 20min; to another beaker was added 63.5g of water followed by 33g of zirconium oxychloride; mixing the materials in the two beakers, and dispersing in a homogenizer for 30min to obtain a first mixture (pH of 2.46); adding 0.3g of surfactant Triton X-100 into the first mixture, and stirring at 45 deg.C for 30min at 150r/min.
(2) And (2) putting the reaction product obtained in the step (1) into an ultrasonic water bath, and reacting for 30min at the reaction temperature of 45 ℃ under the frequency of 80KHz and the power of 280W to obtain the zirconium-aluminum composite sol C2.
The obtained zirconium-aluminum composite sol C2 was subjected to ICP-OES analysis, and the results are shown in Table 1, and the ratio of the surfactant to the aluminum element was calculated according to the charge ratio.
Drying the obtained zirconium-aluminum composite sol C2 at 100 ℃ for 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrogram is similar to that of figure 1, and monoclinic-phase zirconium and tetragonal-phase ZrO exist on the XRD spectrogram 2 And gamma-Al 2 O 3 The diffraction peak of (1).
The obtained zirconium-aluminum composite sol C2 is diluted 1000 times and analyzed by a transmission electron microscope, and the obtained TEM image is similar to that in FIG. 2. The particle size distribution of the colloidal particles of the zirconium-aluminum composite sol C2 is uniform and is about 20 nm.
Comparative example 4
The procedure of example 2 was followed, except that the first mixture was stirred at a temperature of 45 ℃ for 30min without adding a surfactant thereto, and then the step (2) was carried out, to obtain a zirconium aluminum composite sol D4.
The obtained zirconium-aluminum composite sol D4 was subjected to ICP-OES analysis, and the results are shown in table 1.
The obtained zirconium-aluminum composite sol D4 is diluted by 1000 times and analyzed by a transmission electron microscope, and an obtained TEM image shows that the particle size distribution of the colloidal particles of the zirconium-aluminum composite sol D4 is uneven, and the range is about 10-90 nm.
Example 3
This example illustrates a zirconium-aluminum composite sol and a method for preparing the same according to the present invention.
(1) Adding 396g of deionized water into a beaker, slowly adding 8.3g of hydrochloric acid, adding 39.5g of zirconium tetrachloride and 61g of pseudo-boehmite under the stirring condition (the rotating speed is 150 r/min), and continuously stirring for 20min to obtain a first mixture (the pH value is 2.42); adding 0.3g of surfactant Triton X-100 into the first mixture, and stirring at 35 deg.C for 60min at 150r/min.
(2) And (2) putting the reaction product obtained in the step (1) into an ultrasonic water bath, and reacting for 60min at the reaction temperature of 35 ℃ under the frequency of 100KHz and the power of 280W to obtain the zirconium-aluminum composite sol C3.
The XRF analysis of the zirconium aluminium composite sol C3 obtained is given in table 1.
Drying the obtained zirconium-aluminum composite sol C3 at 100 ℃ for 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrogram is similar to that of figure 1, and monoclinic-phase zirconium and tetragonal-phase ZrO exist on the XRD spectrogram 2 And gamma-Al 2 O 3 The diffraction peak of (4).
The obtained zirconium-aluminum composite sol C3 is diluted 1000 times and analyzed by a transmission electron microscope, and the obtained TEM image is similar to that in FIG. 2. The particle size distribution of the colloidal particles of the zirconium-aluminum composite sol C3 is uniform and is about 20 nm.
Example 4
The procedure is as in example 1, except that the process does not comprise step (2) and the product obtained in step (1) is designated as zirconium-aluminium composite sol C4.
The XRF analysis of the resulting zirconium aluminium composite sol C4 was carried out and the results are given in table 1.
Drying the obtained zirconium-aluminum composite sol C4 at 100 ℃ for 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrogram of the solid is as shown in figure 1Similarly, monoclinic-phase zirconium and tetragonal-phase ZrO exist on XRD spectrogram 2 And gamma-Al 2 O 3 The diffraction peak of (1).
The obtained zirconium-aluminum composite sol C4 is diluted 1000 times and analyzed by a transmission electron microscope, and a TEM image is similar to that of the graph in FIG. 2. The particle size distribution of the colloidal particles of the zirconium-aluminum composite sol C4 is uniform and is about 20 nm.
Example 5
A zirconium-aluminum composite sol C5 was obtained in the same manner as in example 1, except that the hydrochloric acid was replaced with nitric acid having the same molar concentration.
The ICP-OES analysis was carried out on the obtained zirconium-aluminum composite sol C5, and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol C5 at 100 ℃ for 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrogram is similar to that of figure 1, and monoclinic-phase zirconium and tetragonal-phase ZrO exist on the XRD spectrogram 2 And gamma-Al 2 O 3 The diffraction peak of (4).
The obtained zirconium-aluminum composite sol C5 is diluted 1000 times and analyzed by a transmission electron microscope, and the obtained TEM image is similar to that in FIG. 2. The particle size distribution of the colloidal particles of the zirconium-aluminum composite sol C5 is uniform and is about 20 nm.
Example 6
A zirconium-aluminum composite sol C6 was obtained in accordance with the procedure of example 1 except that polyoxyethylene-8-octylphenyl ether, a surfactant, was replaced with an equal mass of fatty alcohol-polyoxyethylene ether (commercially available from Haian petrochemical plant, inc. of Jiangsu province under the designation MOA-3).
The ICP-OES analysis was carried out on the obtained zirconium-aluminum composite sol C6, and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol C6 at 100 ℃ for 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrogram is similar to that of figure 1, and monoclinic-phase zirconium and tetragonal-phase ZrO exist on the XRD spectrogram 2 And gamma-Al 2 O 3 The diffraction peak of (1).
The obtained zirconium-aluminum composite sol C6 is diluted 1000 times and analyzed by a transmission electron microscope, and the obtained TEM image is similar to that in FIG. 2. The grain diameter of the colloidal particles of the zirconium-aluminum composite sol C6 is uniformly distributed and is about 20 nm.
Example 7
The method of example 1 was followed except that the temperature in the acidification hydrolysis in step (1) and the ultrasonic treatment in step (2) were both 60 ℃ to obtain a zirconium-aluminum composite sol C7.
The ICP-OES analysis was carried out on the obtained zirconium-aluminum composite sol C7, and the results are shown in Table 1.
Drying the obtained zirconium-aluminum composite sol C7 at 100 ℃ for 6h, then roasting at 600 ℃ for 6h to obtain a solid, and carrying out XRD analysis on the solid, wherein an XRD spectrogram is similar to that of figure 1, and monoclinic-phase zirconium and tetragonal-phase ZrO exist on the XRD spectrogram 2 And gamma-Al 2 O 3 The diffraction peak of (4).
The obtained zirconium-aluminum composite sol C7 is diluted 1000 times and analyzed by a transmission electron microscope, and the obtained TEM image is similar to that in FIG. 2. The particle size distribution of the colloidal particles of the zirconium-aluminum composite sol C7 is uniform and is about 20 nm.
TABLE 1
It can be seen from the results in table 1 that the zirconium-aluminum composite sol prepared by the method provided by the present invention satisfies all the technical characteristics of the zirconium-aluminum composite sol provided by the present invention. Compared with the common sol, the zirconium-aluminum composite sol provided by the invention has the advantages that the zirconium dioxide exists in a monoclinic phase and a tetragonal phase after being roasted, and the particle size distribution of the colloid is more uniform.
Examples of preparation of catalysts
Pulping kaolin and water, adding the sol prepared in the above examples and comparative examples, and stirring to obtain slurry A; pulping ZSP-3 molecular sieve and DASY molecular sieve with water to obtain molecular sieve slurry, mixing slurry A and molecular sieve slurry, adding aluminum sol (available from Qilu catalyst division, with an alumina content of 22.5 wt%), pulping, stirring for 120min to obtain catalyst slurry (with a solid content of 35 wt%), and adding dry catalyst slurryBased on the weight, the content of the ZSP-3 molecular sieve is 8 weight percent, the content of the DASY molecular sieve is 24 weight percent, the content of the kaolin is 40 weight percent, and the content of the aluminum sol is (according to Al) 2 O 3 Calculated) 8 wt%; the content of the zirconium-aluminum composite sol (on a dry basis) was 20 wt%. And (3) carrying out spray drying on the catalyst slurry, and roasting the obtained catalyst microspheres for 2 hours at 500 ℃ to obtain the catalytic cracking catalyst.
Catalyst characterization:
the pore volume and the abrasion index of the catalyst were measured by RIPP28-90 and RIPP29-90 methods in petrochemical analysis and RIPP test (published by Yangchi, scientific Press, 1990), respectively. The results are shown in Table 3.
Evaluation of catalyst:
the catalyst is aged and deactivated for 17 hours at 800 ℃ by 100 percent water vapor. Evaluation was performed on immobilized fluidized bed micro-reactor ACE, the feed oil was hydrotreated oil (composition and physical properties see table 2), and the evaluation conditions were: the reaction temperature is 520 ℃, and the weight space velocity is 16 hours -1 The agent-oil ratio (by weight) is 4. The results are shown in Table 3.
Wherein, the conversion rate = gasoline yield + liquefied gas yield + dry gas yield + coke yield
TABLE 2
TABLE 3
The results in table 3 show that when the zirconium-aluminum composite sol provided by the invention is used for preparing a catalytic cracking catalyst, the zirconium-aluminum composite sol has better adhesive property and good hydrothermal stability, and the obtained catalyst has obviously lower abrasion index and better abrasion strength (i.e. high strength). When the zirconium-aluminum composite sol provided by the invention is used for preparing a catalytic cracking catalyst, the conversion rate of the catalyst is further improved, and the coke yield is low.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the specific features in any suitable way, and the invention will not be further described in relation to the various possible combinations in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
Claims (22)
1. A method for preparing a catalytic cracking catalyst, wherein the method comprises: pulping a binder, clay and a molecular sieve to obtain catalyst slurry, and performing spray drying on the catalyst slurry, wherein the binder is zirconium-aluminum composite sol; in the composite sol, the content of aluminum element is 1-10 wt%, the content of zirconium element is 0.5-10 wt%, the composite sol is dried for 6h at 100 ℃, and then is roasted for 6h at 600 ℃ to obtain a solid, and zirconium dioxide existing in the form of monoclinic phase and tetragonal phase exists in the solid; the composite sol also contains a surfactant, wherein the content of the surfactant is 0.5-10 wt% of the content of aluminum element;
the surfactant is selected from at least one of polyoxyethylene-8-octyl phenyl ether, fatty alcohol polyoxyethylene ether, fatty acid methyl ester polyoxyethylene ether, polyethylene glycol, hydroxypropyl cellulose, fatty acid polyoxyethylene ester, fatty acid glyceride, fatty acid sorbitan, polysorbate, triethanolamine sucrose soap ester and polyol sucrose ester;
the preparation method of the zirconium-aluminum composite sol comprises the following steps:
acidifying and hydrolyzing a mixture containing an alumina precursor, a zirconia precursor, an acid, a surfactant and water; the acidification hydrolysis conditions comprise: the temperature is 10-100 ℃, and the time is 0.2-5h; the method further comprises the following steps: carrying out reaction on a product obtained by acidification and hydrolysis under the ultrasonic condition, wherein the reaction condition comprises the following steps: the temperature is 10-100 ℃, and the time is 0.1-5h;
wherein the alumina precursor is at least one selected from the group consisting of SB powder, pseudo-boehmite, alumina trihydrate, boehmite, alumina sol and amorphous aluminum hydroxide.
2. The production method according to claim 1, wherein the content of the aluminum element is 2 to 6% by weight and the content of the zirconium element is 1 to 6% by weight.
3. The production method according to claim 1 or 2, wherein the weight ratio of the aluminum element to the zirconium element is (0.3-6): 1.
4. the production method according to claim 3, wherein the weight ratio of the aluminum element to the zirconium element is (0.5-5): 1.
5. the production method according to claim 4, wherein the weight ratio of the aluminum element to the zirconium element is (1-4): 1.
6. the production method according to claim 1 or 2, wherein the pH of the composite sol is 0.5 to 5.
7. The method according to claim 6, wherein the pH of the composite sol is 1 to 4.
8. The production method according to claim 1 or 2, wherein the solid has an XRD pattern having diffraction peaks at 28 ° ± 0.5 ° 2 θ and at 30.3 ° ± 0.5 °, 35 ° ± 0.5 °, 50 ° ± 0.5 ° and 60 ° ± 0.5 ° 2 θ.
9. The preparation method according to claim 8, wherein the solid has an XRD pattern having diffraction peaks at 46 ° ± 0.5 ° and 66.6 ° ± 0.5 ° in 2 theta.
10. The production method according to claim 1 or 2, wherein the content of the surfactant is 0.5 to 1.5 wt% of the content of aluminum element.
11. The production method according to claim 1 or 2, wherein the mixture is obtained by mixing an alumina precursor, a zirconia precursor, an acid and water to obtain a first mixture and then adding a surfactant to the first mixture.
12. The production method according to claim 1 or 2, wherein the acid is used in an amount such that the pH of the first mixture is 0.5 to 5.
13. The method of claim 12, wherein the acid is used in an amount such that the pH of the first mixture is 1-4.
14. The method according to claim 1, wherein the alumina precursor and the zirconia precursor are used in such amounts that the resulting zirconium-aluminum composite sol contains 1 to 10% by weight of the aluminum element and 0.5 to 10% by weight of the zirconium element.
15. The method according to claim 14, wherein the alumina precursor and the zirconia precursor are used in such amounts that the resulting zirconium-aluminum composite sol contains 2 to 6% by weight of the aluminum element and 1 to 6% by weight of the zirconium element.
16. The method according to claim 1, wherein the surfactant is contained in an amount of 0.5 to 1.5 wt% based on the content of the aluminum element.
17. The production method according to claim 1 or 2, wherein the zirconia precursor is at least one selected from the group consisting of zirconium tetrachloride, zirconium oxychloride, zirconium acetate, hydrous zirconia and amorphous zirconia;
the acid is selected from at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
18. The preparation method according to claim 1 or 2, wherein the conditions of the acidification hydrolysis comprise: the temperature is 10-60 ℃ and the time is 0.5-2h.
19. The method of claim 18, wherein the conditions of the acidulated hydrolysis comprise: the temperature is 20-45 deg.C, and the time is 0.5-1h.
20. The production method according to claim 1 or 2,
the reaction conditions include: the temperature is 10-60 ℃, and the time is 0.1-3h.
21. The production method according to claim 20,
the reaction conditions include: the temperature is 20-45 ℃ and the time is 0.5-2h.
22. The production method according to claim 1 or 2, wherein the frequency of the ultrasound is 35-200KHz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811033115.5A CN110876926B (en) | 2018-09-05 | 2018-09-05 | Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811033115.5A CN110876926B (en) | 2018-09-05 | 2018-09-05 | Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110876926A CN110876926A (en) | 2020-03-13 |
| CN110876926B true CN110876926B (en) | 2023-04-11 |
Family
ID=69727104
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811033115.5A Active CN110876926B (en) | 2018-09-05 | 2018-09-05 | Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110876926B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578299B (en) * | 2020-04-30 | 2023-11-10 | 中国石油化工股份有限公司 | Silicon-aluminum-zirconium composite oxide, catalytic cracking catalyst, and preparation methods and applications thereof |
| CN112845000A (en) * | 2020-12-31 | 2021-05-28 | 安徽百圣鑫金属科技有限公司 | Preparation method of heat-resistant coating for smelting high-purity aluminum ingot |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998009727A1 (en) * | 1996-09-05 | 1998-03-12 | Japan Energy Corporation | Solid acid catalyst and process for preparing the same |
| CN102451768A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Method for preparing zirconia-alumina composite oxide xerogel |
| CN102380362B (en) * | 2011-08-25 | 2014-03-12 | 太原理工大学 | Ordered zirconia-alumina mesoporous material and its preparation method |
| AU2013284234B2 (en) * | 2012-06-27 | 2018-03-01 | China Petroleum & Chemical Corporation | Catalytic cracking catalyst containing modified Y type molecular sieve and preparation method therefor |
| CN103949231A (en) * | 2014-04-17 | 2014-07-30 | 太原理工大学 | Preparation method of ultra-microporous aluminum oxide and zirconium oxide composite material with high specific surface area |
| WO2017146554A1 (en) * | 2016-02-25 | 2017-08-31 | 주식회사 에코프로 | Acid-resistant catalyst for decomposing perfluorinated compound and use thereof |
| CN107971018B (en) * | 2016-10-21 | 2019-12-27 | 中国石油化工股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN106881106B (en) * | 2017-04-14 | 2019-08-23 | 西南化工研究设计院有限公司 | A kind of conveying bed methanation catalyst and preparation method thereof |
-
2018
- 2018-09-05 CN CN201811033115.5A patent/CN110876926B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| 《化工百科全书》编辑委员会.《化工百科全书 （第8卷）》.《化工百科全书 （第8卷）》.化学工程出版社,1994,(第1版),第484-485页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110876926A (en) | 2020-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4704400B2 (en) | Method for increasing solid component content of catalytic cracking catalyst slurry | |
| CN101829592B (en) | Preparation method of fluidizing, catalyzing and cracking catalyst with high solid content | |
| CN107303502B (en) | Preparation method of high-solid-content catalytic cracking catalyst | |
| CN104549475B (en) | Preparation method of FCC gasoline desulfurization agent composition | |
| CN110876926B (en) | Zirconium-aluminum composite sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst | |
| JP2018103120A (en) | Metal scavenger, manufacturing method of metal scavenger, and fluid contact decomposition catalyst | |
| JP2022527909A (en) | Catalytic cracking catalyst and its preparation method | |
| JPH11564A (en) | Catalyst for catalytic cracking | |
| JP2019523705A (en) | FCC catalyst with alumina obtained from crystalline boehmite | |
| JP7064484B2 (en) | The process of degluing alumina for a flow catalyst | |
| CN116265108A (en) | Preparation method of catalytic cracking catalyst for producing more gasoline | |
| CN114425399A (en) | Catalytic cracking catalyst, preparation method and application thereof | |
| CN112569918B (en) | Improved zirconium-aluminum composite sol and preparation method and application thereof | |
| CN1234663C (en) | Alkylation process | |
| CN116265107A (en) | Preparation method of catalytic cracking catalyst for producing diesel oil in large quantity | |
| CN116265109A (en) | Preparation method of heavy oil efficient conversion catalyst | |
| CN112473731B (en) | Catalytic cracking catalyst containing Y and BEA structure molecular sieves, and preparation method and application method thereof | |
| JP2023523468A (en) | Modified Beta Zeolites, Catalytic Cracking Catalysts and Methods of Making and Using Them | |
| CN116265106A (en) | Preparation method of catalytic cracking catalyst for high yield of low carbon olefin | |
| CN112570017A (en) | Five-membered ring zeolite catalytic cracking catalyst | |
| CN112642472A (en) | Alumina sol binder catalyst for producing low-carbon olefin and BTX through hydrocarbon oil conversion, and preparation method and application thereof | |
| JP4541688B2 (en) | Isoparaffin-olefin alkylation process | |
| CN112892582A (en) | Light gasoline cracking catalyst containing all-silicon three-hole spherical mesoporous composite material and preparation method and application thereof | |
| CN112473732B (en) | Catalytic cracking catalyst for producing propylene and preparation method and application method thereof | |
| CN108355705A (en) | A kind of catalyst for heavy oil catalytic cracking and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |