CN107970972B - A kind of catalytic cracking catalyst and preparation method thereof - Google Patents

A kind of catalytic cracking catalyst and preparation method thereof Download PDF

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CN107970972B
CN107970972B CN201610921557.8A CN201610921557A CN107970972B CN 107970972 B CN107970972 B CN 107970972B CN 201610921557 A CN201610921557 A CN 201610921557A CN 107970972 B CN107970972 B CN 107970972B
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molecular sieve
acid
treatment
inorganic
ratio
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CN107970972A (en
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罗一斌
朱玉霞
刘建强
陈振宇
庄立
任飞
欧阳颖
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petrochemical Corp
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China Petrochemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves

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  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
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Abstract

The present invention provides a kind of catalytic cracking catalysts and preparation method thereof, and with dry basis, the catalyst contains the natural mineral matter of the Y molecular sieve of 25-75 weight %, the inorganic oxide binder of 10-30 weight % and 15-65 weight %；Wherein, the cell parameter of the Y molecular sieve is 24.35-24.55 angstroms；The Al distribution parameter D of the molecular sieve meets: 0.3≤D≤0.8；The mesopore volume of the molecular sieve is 0.15-1.0 mls/g；The ratio that the mesopore volume of the molecular sieve accounts for total pore volume is 30%-70%；The ratio that the strong acid acid amount of the molecular sieve accounts for total acid content is 30-60%, and the ratio between B acid acid amount and L acid acid amount are 20-100.With excellent heavy oil conversion performance, higher midbarrel oil yield, lower coke yield when catalytic cracking catalyst provided by the invention is for heavy oil catalytic cracking.

Description

Catalytic cracking catalyst and preparation method thereof
Technical Field
The invention relates to a catalytic cracking catalyst and a preparation method thereof.
Background
Catalytic Cracking (FCC) is an important secondary processing of crude oil and plays a significant role in the oil refining industry. In the catalytic cracking process, heavy fractions such as vacuum distillates or residues of heavier components are reacted in the presence of a catalyst to be converted into high value-added products such as liquefied gas, gasoline, diesel oil and the like, and catalytic materials with high cracking activity are generally required to be used in the process. Molecular sieves are widely used in the petroleum refining and processing industry due to their shape-selective properties, high specific surface area and strong acidity. The Y-type molecular sieve (HY, REY, USY) is the main active component of catalytic cracking and hydrocracking catalyst since its first use in the last 60 years. However, as the crude oil heavies are increased, the content of polycyclic compounds in the raw material is increased significantly, the pore size of the Y-type molecular sieve as a main cracking member is only 0.74nm, and the Y-type molecular sieve is used for processing heavy fractions such as residual oil, and the accessibility of the active center of the catalyst is a main obstacle for cracking the polycyclic compounds (such as polycyclic aromatic hydrocarbon and polycyclic naphthenic hydrocarbon) contained in the Y-type molecular sieve; the existence of the acidity on the surface of the molecular sieve enables heavy oil molecules which cannot enter the pore channel to have nonselective reaction on the outer surface of the molecular sieve, so that the product distribution is influenced.
In order to overcome the defects that the pore diameter of the microporous material is small and the surface of the microporous material has more acidity, the synthesis of the mesoporous-rich catalytic material is increasingly paid attention by people.
U.S. Pat. Nos. 5069890 and 5087348 disclose a method for preparing mesoporous Y-type molecular sieve, which comprises treating commercially available USY at 760 deg.C for 24h in 100% steam atmosphere. The mesoporous volume of the Y-type molecular sieve obtained by the method is increased from 0.02mL/g to 0.14mL/g, but the crystallinity is reduced from 100 percent to 70 percent, and the specific surface area is 683m2The/g is reduced to 456m2The acid density is reduced from 28.9% to 6%.
In the method for preparing the mesoporous-containing Y-type molecular sieve disclosed in the U.S. Pat. No. 4, 5601798, HY or USY is used as a raw material and is put into an autoclave to react with NH4NO3Solution or NH4NO3With HNO3The obtained Y-type molecular sieve has a mesoporous volume of 0.2-0.6 mL/g, but the crystallinity and the specific surface area are obviously reduced.
Chinese patent CN101722022 discloses an alkali treatment modification method of Y-type molecular sieve, which comprises the following steps: strong base: distilled water (0.1-2): (0.05-2): (4-15) beating and uniformly mixing the Y-type molecular sieve with aqueous solution of strong alkali in a mass ratio, and treating the mixture for 0.1-24 h at 0-120 ℃ with alkali to obtain the molecular sieve with higher N than the parent Y-type molecular sieve2The amount of adsorption.
The method for preparing the framework silicon-rich Y-type molecular sieve disclosed in Chinese patent CN 101723399 is to firstly use alkali liquor to carry out desiliconization pretreatment on a NaY molecular sieve, and then carry out ammonium exchange and dealumination silicon supplementation treatment on the molecular sieve after the alkali treatment, so that the mesopores of the obtained Y-type molecular sieve are increased but are not obvious.
Chinese patent CN103172082 discloses a preparation method of a mesoporous-containing Y-type molecular sieve, which comprises the steps of firstly carrying out ammonium exchange on a sodium-type Y-type molecular sieve, then utilizing an organic acid aqueous solution to treat, carrying out NaOH treatment on the acid-treated molecular sieve, and finally utilizing an ammonium nitrate aqueous solution to treat, so as to obtain the mesoporous-containing Y-type molecular sieve. The obtained Y-type molecular sieve contains abundant micropores, and the volume of the mesoporous pores can reach 0.5 mL/g-1.5 mL/g.
Chinese patent CN104760973 discloses a Y-type molecular sieve with ultrahigh mesoporous content and a preparation method thereof, firstly, pretreating Y-type zeolite at 300-600 ℃ for 1-5 h; cooling to 200-600 ℃; in an anhydrous drying environment, introducing a drying gas saturated by dealumination and silicon supplementation into the pretreated Y-type zeolite, and reacting for 0.5-7 h to obtain a crude product; or in an anhydrous drying environment, raising the temperature to 250-700 ℃ at a constant speed, introducing a drying gas saturated by dealumination and silicon supplementation into the pretreated Y-type zeolite, and reacting for 0.5-7 h to obtain a crude product; carrying out acid treatment on the crude product; and (4) carrying out alkali treatment on the crude product after the acid treatment to obtain the Y-type molecular sieve. The Y-type molecular sieve prepared by the method has ultrahigh mesoporous content, but the micropore volume is lower.
Disclosure of Invention
The catalytic cracking catalyst provided by the invention has excellent heavy oil conversion capability, higher yield of middle distillate oil and lower yield of coke when being used for heavy oil catalytic cracking.
In order to achieve the above object, the present invention provides a catalytic cracking catalyst comprising, on a dry basis, 25 to 75 wt% of a Y molecular sieve, 10 to 30 wt% of an inorganic oxide binder, and 15 to 65 wt% of a natural mineral; wherein the unit cell parameter of the Y molecular sieve is 24.35-24.55 angstrom; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.3 and less than or equal to 0.8, wherein D is Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the inward H distance of the crystal face edge of the molecular sieve crystal grain measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the outward H distance of the geometric center of the crystal face of the molecular sieve crystal grain measured by the TEM-EDS method, wherein H is 10 percent of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the mesoporous volume of the molecular sieve is 0.15-1.0 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 30-70%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 30-60%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-100.
Preferably, the molecular sieve has a unit cell parameter of from 24.40 to 24.52 angstroms; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.35 and less than or equal to 0.75; the mesoporous volume of the molecular sieve is 0.2-0.8 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 35-65%; the strong acid amount of the molecular sieve accounts for 35-55% of the total acid amount, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 60-80.
Preferably, the natural minerals include at least one selected from kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite, and the inorganic oxide binder includes at least one selected from silica, alumina, zirconia, titania, and amorphous silica-alumina.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following steps: mixing raw materials for preparing a catalytic cracking catalyst with water, pulping and spray drying; wherein the raw material comprises 25-75 wt% of Y molecular sieve, 10-30 wt% of precursor of inorganic oxide binder and 15-65 wt% of natural mineral substance based on dry weight; the unit cell parameter of the Y molecular sieve is 24.35-24.55 angstrom; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.3 and less than or equal to 0.8, wherein D is Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the inward H distance of the crystal face edge of the molecular sieve crystal grain measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the outward H distance of the geometric center of the crystal face of the molecular sieve crystal grain measured by the TEM-EDS method, wherein H is 10 percent of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the mesoporous volume of the molecular sieve is 0.15-1.0 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 30-70%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 30-60%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-100.
Preferably, the preparation step of the Y molecular sieve comprises: a. carrying out ammonium exchange treatment on the NaY molecular sieve, and filtering and washing to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium oxide content of less than 5 weight percent, calculated as sodium oxide and based on the weight of the ammonium exchanged molecular sieve on a dry basis; b. b, carrying out hydrothermal roasting treatment on the ammonium exchange molecular sieve obtained in the step a in a steam atmosphere to obtain a water roasted molecular sieve; c. c, performing first dealumination treatment on the water-baked molecular sieve obtained in the step b in an acid solution consisting of organic acid and inorganic acid, and filtering and washing to obtain a first dealumination molecular sieve; d. c, performing alkali treatment on the first dealuminized molecular sieve obtained in the step c in an inorganic alkali solution, and filtering and washing to obtain an alkali-treated molecular sieve; e. and d, carrying out secondary dealumination treatment on the alkali-treated molecular sieve obtained in the step d in a composite acid dealumination agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain the Y molecular sieve.
Preferably, the organic acid in the acid solution in step c is at least one selected from the group consisting of ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the conditions of the first dealumination treatment in step c include: the weight ratio of the molecular sieve, the organic acid and the inorganic acid on a dry basis is 1: (0.03-0.3): 0.02-0.4); the first dealuminization treatment temperature is 25-100 ℃, and the first dealuminization treatment time is 0.5-6 hours.
Preferably, the conditions of the first dealumination treatment in step c include: the weight ratio of the molecular sieve, the organic acid and the inorganic acid on a dry basis is 1: (0.05-0.25):(0.05-0.25).
Preferably, the inorganic base solution in step d is at least one selected from the group consisting of a sodium hydroxide solution, a potassium hydroxide solution, a lithium hydroxide solution and ammonia water.
Preferably, the conditions of the alkali treatment in step d include: the weight ratio of the molecular sieve to the inorganic base on a dry basis is 1: (0.02-0.6); the alkali treatment temperature is 25-100 ℃, and the alkali treatment time is 0.5-6 hours.
Preferably, the organic acid in the composite acid dealuminating agent solution in the step e is at least one selected from ethylenediamine tetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the conditions of the second dealumination treatment in step e comprise: the weight ratio of the molecular sieve, the fluosilicic acid, the organic acid and the inorganic acid is 1: (0.03-0.3): (0.05-0.3): 0.05-0.25); the second dealuminization treatment temperature is 25-100 ℃, and the second dealuminization treatment time is 0.5-6 hours.
Preferably, the conditions of the second dealumination treatment in step e comprise: the weight ratio of the molecular sieve, the fluosilicic acid, the organic acid and the inorganic acid is 1: (0.035-0.2):(0.06-0.2):(0.1-0.2).
Preferably, the conditions of the hydrothermal roasting treatment in step b include: the temperature is 450 ℃ and 750 ℃, the time is 0.5-6 hours, and the water vapor atmosphere is 100 percent of the water vapor atmosphere.
Preferably, the natural mineral includes at least one selected from kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite, and rectorite, and the precursor of the inorganic oxide binder includes at least one selected from silica sol, alumina sol, peptized pseudo-boehmite, silica-alumina sol, and phospho-alumina sol.
The catalytic cracking catalyst provided by the invention has excellent heavy oil conversion capability, higher yield of middle distillate oil and lower yield of coke when being used for heavy oil catalytic cracking.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a catalytic cracking catalyst, which comprises 25-75 wt% of Y molecular sieve, 10-30 wt% of inorganic oxide binder and 15-65 wt% of natural mineral substance by dry weight, preferably 30-70 wt% of Y molecular sieve, 12-28 wt% of inorganic oxide binder and 20-55 wt% of natural mineral substance by dry weight; wherein the unit cell parameter of the Y molecular sieve is 24.35-24.55 angstrom; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.3 and less than or equal to 0.8, wherein D is Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the inward H distance of the crystal face edge of the molecular sieve crystal grain measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the outward H distance of the geometric center of the crystal face of the molecular sieve crystal grain measured by the TEM-EDS method, wherein H is 10 percent of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the mesoporous volume of the molecular sieve is 0.15-1.0 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 30-70%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 30-60%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-100. Preferably, the molecular sieve has a unit cell parameter of from 24.40 to 24.52 angstroms; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.35 and less than or equal to 0.75; the mesoporous volume of the molecular sieve is 0.2-0.8 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 35-65%; the strong acid amount of the molecular sieve accounts for 35-55% of the total acid amount, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 60-80.
According to the invention, the method for measuring the aluminum content of the molecular sieve by using the TEM-EDS method is well known by the technicians in the field, wherein the geometric center is also well known by the technicians in the field and can be obtained by calculation according to a formula, the invention is not repeated, the geometric center of a general symmetrical graph is the intersection point of connecting lines of all opposite vertexes, the crystal plane is one plane of a regular crystal grain, and the inward and outward directions are both inward and outward directions on the crystal plane.
According to the invention, the proportion of the mesoporous volume of the molecular sieve in the total pore volume is measured by a nitrogen adsorption and desorption method, and the mesopores are molecular sieve pore passages with the pore diameter of more than 2 nanometers and less than 100 nanometers; the strong acid amount of the molecular sieve is NH in proportion to the total acid amount3The TPD method, the acid centre of which is NH3Desorbing the corresponding acid center at the temperature of more than 300 ℃; and the ratio of the acid amount of the B acid to the acid amount of the L acid is measured by adopting a pyridine adsorption infrared acidity method.
According to the present invention, the natural mineral substance means a natural simple substance or compound formed under the combined action of various substances of the earth's crust (referred to as geological action) and having a specific chemical composition expressed by a chemical formula and a relatively fixed chemical composition, and may include, for example, at least one selected from kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite, and the inorganic oxide binder means an inorganic oxide serving to bind the respective components in the catalyst, and may include, for example, at least one selected from silica, alumina, zirconia, titania and amorphous silica-alumina.
The invention also provides a preparation method of the catalytic cracking catalyst, which comprises the following steps: mixing raw materials for preparing a catalytic cracking catalyst with water, pulping and spray drying; wherein the raw material comprises 25-75 wt% of Y molecular sieve, 10-30 wt% of precursor of inorganic oxide binder and 15-65 wt% of natural mineral substance based on dry weight; the unit cell parameter of the Y molecular sieve is 24.35-24.55 angstrom; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.3 and less than or equal to 0.8, wherein D is Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the inward H distance of the crystal face edge of the molecular sieve crystal grain measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the outward H distance of the geometric center of the crystal face of the molecular sieve crystal grain measured by the TEM-EDS method, wherein H is 10 percent of the distance from a certain point of the crystal face edge to the geometric center of the crystal face; the mesoporous volume of the molecular sieve is 0.15-1.0 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 30-70%; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 30-60%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-100.
According to the present invention, the preparation step of the Y molecular sieve may comprise: a. carrying out ammonium exchange treatment on the NaY molecular sieve, and filtering and washing to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium oxide content of less than 5 weight percent, calculated as sodium oxide and based on the weight of the ammonium exchanged molecular sieve on a dry basis; b. b, carrying out hydrothermal roasting treatment on the ammonium exchange molecular sieve obtained in the step a in a steam atmosphere to obtain a water roasted molecular sieve; c. c, performing first dealumination treatment on the water-baked molecular sieve obtained in the step b in an acid solution consisting of organic acid and inorganic acid, and filtering and washing to obtain a first dealumination molecular sieve; d. c, performing alkali treatment on the first dealuminized molecular sieve obtained in the step c in an inorganic alkali solution, and filtering and washing to obtain an alkali-treated molecular sieve; e. and d, carrying out secondary dealumination treatment on the alkali-treated molecular sieve obtained in the step d in a composite acid dealumination agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain the Y molecular sieve.
According to the invention, the ammonium exchange treatment described in step a is well known to the person skilled in the art, for example, NaY molecular sieves can be used according to the molecular sieve: ammonium salt: h2O is 1: (0.1-1): (5-10) the weight ratio is exchanged at room temperature to 100 ℃ for 0.5-2 hoursPost-filtration, the exchange process can be repeated 1-4 times to make Na on the molecular sieve2The O content is less than 5 wt%. The ammonium salt may be a commonly used inorganic ammonium salt, for example, at least one selected from the group consisting of ammonium chloride, ammonium sulfate and ammonium nitrate.
According to the present invention, both the organic acid and the inorganic acid in the acid solution in step c are well known to those skilled in the art, for example, the organic acid in the acid solution may be at least one selected from the group consisting of ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably citric acid; the inorganic acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid, and hydrochloric acid is preferred.
The dealumination treatment according to the present invention is well known to those skilled in the art, and the first dealumination treatment may be performed once or in several times by mixing an organic acid with the water-calcined molecular sieve and then mixing an inorganic acid with the water-calcined molecular sieve; or mixing inorganic acid with the water baked molecular sieve, and then mixing organic acid with the water baked molecular sieve; inorganic acid, organic acid and water baked molecular sieve can also be mixed at the same time. The conditions of the first dealumination treatment may be: the weight ratio of the molecular sieve, the organic acid and the inorganic acid on a dry basis is 1: (0.03-0.3): (0.02-0.4), preferably 1: (0.05-0.25): (0.05-0.25); the first dealuminization treatment temperature is 25-100 ℃, and the first dealuminization treatment time is 0.5-6 hours.
According to the present invention, the inorganic base solution in step d is well known to those skilled in the art, and may be, for example, at least one selected from the group consisting of a sodium hydroxide solution, a potassium hydroxide solution, a lithium hydroxide solution and ammonia water, and is preferably a sodium hydroxide solution. The conditions of the alkali treatment in step d may include: the weight ratio of the molecular sieve to the inorganic base on a dry basis is 1: (0.02-0.6), preferably 1: (0.05-0.4); the alkali treatment temperature is 25-100 ℃, and the alkali treatment time is 0.5-6 hours.
According to the present invention, although dealumination treatment is well known to those skilled in the art, the use of an inorganic acid, an organic acid and fluorosilicic acid together for dealumination treatment has not been reported. The second dealumination treatment may be performed once or in multiple times, and the organic acid may be first mixed with the alkali-treated molecular sieve, and then the fluorosilicic acid and the inorganic acid are mixed with the alkali-treated molecular sieve, that is, the organic acid is first added into the alkali-treated molecular sieve, and then the fluorosilicic acid and the inorganic acid are slowly added in parallel, or the fluorosilicic acid is first added and then the inorganic acid is added, preferably the fluorosilicic acid and the inorganic acid are slowly added in parallel. The organic acid in the composite acid dealuminating agent solution in the step e may be at least one selected from ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, preferably oxalic acid or citric acid, and more preferably citric acid, and the inorganic acid may be at least one selected from hydrochloric acid, sulfuric acid and nitric acid, preferably hydrochloric acid or sulfuric acid, and more preferably hydrochloric acid. The conditions of the second dealumination treatment may be: the weight ratio of the molecular sieve, the fluosilicic acid, the organic acid and the inorganic acid is 1: (0.03-0.3): (0.05-0.3): 0.05-0.25), preferably 1: (0.035-0.2): (0.06-0.2): 0.1-0.2); the second dealuminization treatment temperature is 25-100 ℃, and the second dealuminization treatment time is 0.5-6 hours.
According to the present invention, hydrothermal calcination is well known to those skilled in the art for stabilizing the molecular sieve, and the hydrothermal calcination treatment conditions in step b may be: the temperature is 450-750 ℃, preferably 550-700 ℃, the time is 0.5-6 hours, preferably 1-2 hours, the water vapor atmosphere is 100 percent of the water vapor atmosphere, the hydrothermal roasting treatment also has the function of deammoniation, so that the ammonium exchange molecular sieve (NH) after the ammonium exchange treatment4NaY) is treated as a water-calcined molecular sieve (HNaY), preferably under the conditions: the temperature is 500-600 deg.C, the water vapor atmosphere is 100% by volume, the time is 1-3 hr, and the treatment is preferably carried out with flowing water vapor, and the weight of water vapor consumed per hour can be 1-2 times of the weight of ammonium exchange molecular sieve.
The washing according to the invention is well known to the person skilled in the art and is generally referred to as water washing, for example, the molecular sieve may be rinsed with water at 30-60 ℃ in an amount of 5-10 times the weight of the molecular sieve.
According to the present invention, the precursor of the inorganic oxide binder refers to a raw material for preparing a catalytic cracking catalyst for forming the inorganic oxide binder in the catalytic cracking catalyst, and may include at least one selected from the group consisting of pseudo-boehmite, alumina sol, silica-alumina sol, and water glass, for example.
The present invention will be further illustrated by the following examples, but the present invention is not limited thereto, and the instruments and reagents used in the examples of the present invention are those commonly used by those skilled in the art unless otherwise specified.
The cell constants of the present invention were determined by RIPP145-90 standard method, which is published in 1990, in "analytical methods in petrochemical industry (RIPP test method)", Yangro custom, scientific Press.
The TEM-EDS determination method of the invention is described in the research methods of solid catalysts, petrochemical industry, 29(3), 2000: 227.
the measuring method of the mesoporous pore volume and the total pore volume of the invention is as follows:
the measurement was carried out by using AS-3, AS-6 static nitrogen adsorption apparatus manufactured by Quantachrome instruments.
The instrument parameters are as follows: the sample was placed in a sample handling system and evacuated to 1.33X 10 at 300 deg.C-2Pa, keeping the temperature and the pressure for 4h, and purifying the sample. Testing the purified samples at different specific pressures P/P at a liquid nitrogen temperature of-196 DEG C0The adsorption quantity and the desorption quantity of the nitrogen under the condition are obtained to obtain N2Adsorption-desorption isotherm curve. Then, the total specific surface area, the micropore specific surface area and the mesopore specific surface area are calculated by utilizing a two-parameter BET formula, and the specific pressure P/P is taken0The adsorption capacity below 0.98 is the total pore volume of the sample, the pore size distribution of the mesoporous part is calculated by using BJH formula, and the mesoporous pore volume (2-100 nm) and the mesoporous pore volume of 2-20 nm are calculated by adopting an integration method.
The method for measuring the amount of the B acid and the amount of the L acid is as follows:
an FTS3000 Fourier Infrared spectrometer manufactured by BIO-RAD of America was used.
And (3) testing conditions are as follows: pressing the sample into tablet, sealing in an in-situ cell of an infrared spectrometer, and vacuumizing to 10 deg.C at 350 deg.C-3Pa, keeping for 1h to enable gas molecules on the surface of the sample to be desorbed completely, and cooling to room temperature. The pressure was introduced into the in-situ cell at 2.Balancing pyridine vapor with pressure of 67Pa for 30min, heating to 200 deg.C, and vacuumizing to 10 deg.C-3Pa, keeping for 30min, cooling to room temperature at 1400-1700cm-1Scanning in wave number range, and recording infrared spectrogram of pyridine adsorption at 200 ℃. Then the sample in the infrared absorption cell is moved to a heat treatment area, the temperature is raised to 350 ℃, and the vacuum is pumped to 10 DEG-3Pa, keeping for 30min, cooling to room temperature, and recording the infrared spectrogram of pyridine adsorption at 350 ℃. And automatically integrating by an instrument to obtain the acid content of the B acid and the acid content of the L acid.
The method for measuring the total acid amount and the strong acid amount of the present invention is as follows:
an Autochem II 2920 programmed temperature desorption instrument of Michman, USA, is adopted.
And (3) testing conditions are as follows: weighing 0.2g of a sample to be detected, putting the sample into a sample tube, putting the sample tube into a thermal conductivity cell heating furnace, taking He gas as carrier gas (50mL/min), heating the sample tube to 600 ℃ at the speed of 20 ℃/min, and purging the sample tube for 60min to remove impurities adsorbed on the surface of the catalyst. Then cooling to 100 ℃, keeping the temperature for 30min, and switching to NH3-He mixed gas (10.02% NH)3+ 89.98% He) for 30min, and then continuing to purge with He gas for 90min until the baseline is stable, so as to desorb the physically adsorbed ammonia gas. And (4) heating to 600 ℃ at the heating rate of 10 ℃/min for desorption, keeping for 30min, and finishing desorption. Detecting gas component change by TCD detector, automatically integrating by instrument to obtain total acid amount and strong acid amount, wherein acid center of strong acid is NH3The desorption temperature is higher than 300 ℃ of the corresponding acid center.
The D value is calculated as follows: selecting a crystal grain and a certain crystal face of the crystal grain in a transmission electron mirror to form a polygon, wherein the polygon has a geometric center, an edge and a 10% distance H (different edge points and different H values) from the geometric center to a certain point of the edge, any one of regions in the inward H distance of the edge of the crystal face which is larger than 100 square nanometers and any one of regions in the outward H distance of the geometric center of the crystal face which is larger than 100 square nanometers are respectively selected, measuring the aluminum content, namely Al (S1) and Al (C1), calculating D1 to Al (S1)/Al (C1), respectively selecting different crystal grains to measure for 5 times, and calculating the average value to be D.
Preparation of example 1
Subjecting Y molecular sieve (catalysis)Crystal cell constant 24.63 angstroms, manufactured by agent Qilu division) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 3g of citric acid while stirring, then adding 400g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 5g of oxalic acid while stirring, slowly dropwise adding 50g of hydrochloric acid (the mass fraction is 10%) and 15g of fluosilicic acid (the concentration is 20%), heating to 50 ℃, stirring at constant temperature for 1h, filtering, washing and drying to obtain a molecular sieve sample A, wherein the physicochemical properties of the molecular sieve sample A are shown in Table 1.
Preparation of comparative example 1
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 wt%; the molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis weight) of the roasted molecular sieve, pulping to obtain molecular sieve pulp with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, stirring for 0.5h at constant temperature, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, slowly dropwise adding 127g of fluosilicic acid (the concentration is 20%), heating to 50 ℃, stirring for 1 hour at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB1, wherein the physicochemical properties of the molecular sieve sample DB1 are shown in Table 1.
Preparation of comparative example 2
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing at a ratio of 1:10, pulping, ammonium exchanging at 70 deg.C for 1 hr, filtering, washing,Drying, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 5g of oxalic acid while stirring, then adding 400g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 146g of fluosilicic acid (the concentration is 20%) while stirring, heating to 50 ℃, stirring for 1h at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB2, wherein the physicochemical properties of the molecular sieve sample DB2 are shown in Table 1.
Preparation of comparative example 3
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 5g of oxalic acid while stirring, then adding 400g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 12g of oxalic acid while stirring, then adding 178g of hydrochloric acid (the mass fraction is 10%), heating to 50 ℃, stirring for 1 hour at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB3, wherein the physicochemical properties of the molecular sieve sample DB3 are shown in Table 1.
Preparation of comparative example 4
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing at a ratio of 1:10, pulping, ammonium exchanging at 70 deg.C for 1 hr, passing the sampleFiltering, washing, drying, and determining that the sodium content of the molecular sieve is less than 5 wt%. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 15g of oxalic acid while stirring, then adding 200g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 29g of oxalic acid while stirring, heating to 50 ℃, stirring for 1h at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB4, wherein the physicochemical properties of the molecular sieve sample DB4 are shown in Table 1.
Preparation of comparative example 5
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 3g of oxalic acid while stirring, then adding 400g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, and stirring at constant temperature for 0.5 h; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 245g of hydrochloric acid (mass fraction of 10%) while stirring, heating to 50 ℃, stirring for 1h at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB5, wherein the physicochemical properties of the molecular sieve sample DB5 are shown in Table 1.
Preparation of comparative example 6
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing at a ratio of 1:10, pulping, ammonium exchanging at 70 deg.C for 1h, filtering, washing, oven drying, and determining sodium content of molecular sieveThe amount is less than 5 wt%. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 3g of oxalic acid while stirring, then adding 400g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, and stirring at constant temperature for 0.5 h; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 30g of oxalic acid while stirring, slowly dropwise adding 100g of fluosilicic acid (the concentration is 20%), heating to 50 ℃, stirring for 1 hour at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB6, wherein the physicochemical properties of the molecular sieve sample DB6 are shown in Table 1.
Preparation of comparative example 7
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 3g of oxalic acid while stirring, then adding 400g of hydrochloric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 10.42g of NaOH (the purity is 96 percent), heating to 50 ℃, and stirring at constant temperature for 0.5 h; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 188g of hydrochloric acid (mass fraction of 10%) while stirring, slowly dropwise adding 100g of fluosilicic acid (concentration of 20%), heating to 50 ℃, stirring for 1h at constant temperature, filtering, washing and drying to obtain a molecular sieve sample DB7, wherein the physicochemical properties of the molecular sieve sample DB7 are shown in Table 1.
Preparation of example 2
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing at a ratio of 1:10, pulping, ammonium exchanging at 70 deg.C for 1 hr, filtering, washing, oven drying, measuringThe sodium content of the molecular sieve is less than 5 wt%. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 5g of oxalic acid while stirring, then adding 200g of sulfuric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 30 ℃, stirring for 2h at constant temperature, filtering and washing with water until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 31.25g of KOH (the purity is 96 percent), heating to 70 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 15g of ethylene diamine tetraacetic acid while stirring, slowly dropwise adding 100g of hydrochloric acid (the mass fraction is 10%) and 15g of fluosilicic acid (the concentration is 20%), heating to 50 ℃, stirring for 1h at constant temperature, filtering, washing and drying to obtain a molecular sieve sample B, wherein the physicochemical properties of the molecular sieve sample B are shown in Table 2.
Preparation of example 3
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the calcined molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 25g of oxalic acid while stirring, then adding 250g of nitric acid (the mass fraction is 10 percent), and adding for 30 min; heating to 90 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 35g of NaOH (the purity is 96 percent), heating to 80 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 20g of oxalic acid while stirring, slowly dropwise adding 105g of hydrochloric acid (the mass fraction is 10%) and 49g of fluosilicic acid (the concentration is 20%), heating to 70 ℃, stirring at constant temperature for 1h, filtering, washing and drying to obtain a molecular sieve sample C, wherein the physicochemical properties of the molecular sieve sample C are shown in Table 2.
Preparation of example 4
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl anddistilled water was mixed according to a ratio of 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange at 70 ℃ for 1h, filtering, washing and drying a sample. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 30g of oxalic acid while stirring, then adding 100g of sulfuric acid (the mass fraction is 10 percent), and adding for 1 min; heating to 55 ℃, stirring for 2h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 wt%, adding 41g of NaOH (the purity is 96%), heating to 50 ℃, stirring at constant temperature for 0.5h, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 30g of sulfosalicylic acid while stirring, slowly dropwise adding 100g of hydrochloric acid (the mass fraction is 10%) and 62g of fluosilicic acid (the concentration is 20%), heating to 50 ℃, stirring at constant temperature for 1h, filtering, washing and drying to obtain a molecular sieve sample D, wherein the physicochemical properties of the molecular sieve sample D are listed in Table 2.
Preparation of example 5
Mixing Y molecular sieve (produced by catalyst Qilu division, unit cell constant 24.63 angstrom) and NH4Cl and distilled water as 1: mixing and pulping uniformly at a ratio of 1:10, performing ammonium exchange for 1h at 70 ℃, filtering, washing and drying a sample, and determining that the sodium content of the molecular sieve is less than 5 weight percent. The molecular sieve is roasted for 2 hours at 600 ℃ under 100 percent of water vapor. Adding water into 100g (dry basis mass) of the roasted molecular sieve to prepare molecular sieve slurry with the solid content of 10 weight percent, adding 20g of citric acid while stirring, then adding 10 percent of 220g of nitric acid by mass percent, and adding for 30 min; heating to 75 ℃, stirring for 1h at constant temperature, filtering and washing until the filtrate is neutral; adding water into a sample, pulping to obtain molecular sieve slurry with the solid content of 10 weight percent, adding 23g of LiOH, heating to 400 ℃, stirring for 2 hours at constant temperature, filtering and washing to be neutral; adding water into the filter cake, pulping to obtain molecular sieve slurry with the solid content of 20 wt%, adding 5g of ethylenediamine tetraacetic acid while stirring, slowly dropwise adding 148g of sulfuric acid (the mass fraction is 10%) and 125g of fluosilicic acid (the concentration is 20%), heating to 80 ℃, stirring for 1h at constant temperature, filtering, washing and drying to obtain a molecular sieve sample E, wherein the physicochemical properties of the molecular sieve sample E are listed in Table 2.
As can be seen from the data in Table 1, for the Y molecular sieve after the alkali treatment and the desilication, the Al in the molecular sieve can not be effectively removed by adopting single organic acid oxalic acid for dealumination (DB4), single inorganic acid hydrochloric acid for dealumination (DB5) and the composite acid of the organic acid oxalic acid and the inorganic acid hydrochloric acid (DB3), and a good dealumination effect can be obtained only after the fluosilicic acid is used. When the fluosilicic acid is used alone for dealumination (DB2), the mesopores are relatively less, the proportion of strong acid in the total acid is lower, and the proportion of B acid/L acid is lower. The dealumination of the fluosilicic acid composite organic acid oxalic acid (DB6) and the dealumination of the fluosilicic acid composite inorganic acid salt acid (DB7) increase the volume of mesoporous, but the proportion of strong acid in total acid and the proportion of B acid/L acid are not as high as those of the molecular sieve provided by the invention. The invention adopts a composite acid system, can effectively adjust the aluminum distribution and improve the acid distribution on the premise of ensuring the integrity of the crystal structure and the mesoporous pore canal structure of the molecular sieve under the synergistic action of three acids, has rich silicon on the surface of the molecular sieve, can inhibit the occurrence of surface non-selective side reaction, has rich mesopores and is beneficial to the implementation of heavy oil cracking reaction.
The following examples illustrate the catalysts and the process for their preparation according to the invention, in which the raw materials used have the following properties: kaolin (Suzhou China Kaolin Corp, 75 wt% solids), alumina sol (Qilu catalyst division, 22.5 wt% alumina).
Examples 1 to 5
Kaolin is prepared into slurry with the solid content of 30 weight percent by using decationized water, the slurry is stirred uniformly, the pH value of the slurry is adjusted to 2.5 by using hydrochloric acid, the pH value is kept, aluminum sol is added after the slurry is kept for standing and aging for 1 hour at 50 ℃, the aluminum sol is stirred for 1 hour to form colloid, the Y molecular sieve prepared in the preparation example is added, and water is added or not added to form catalyst slurry (the solid content is 35 weight percent). Continuously stirring and then spray-drying to prepare the microsphere catalyst. The microspherical catalyst was then calcined at 500 ℃ for 1 hour, washed with ammonium sulfate (where ammonium sulfate: microspherical catalyst: water 0.5:1:10) at 60 ℃ to a sodium oxide content of less than 0.25 wt%, then rinsed with deionized water and filtered, and then dried at 110 ℃ to obtain catalyst CA-CE, the specific catalyst ratios on a dry basis are shown in table 4.
Comparative examples 1 to 7
A catalytic cracking catalyst was prepared according to the method of examples 1-5, except that the Y molecular sieves in examples 1-5 were replaced with the Y molecular sieves DB1-DB7 prepared in the comparative example to obtain catalysts CDB1-CDB7, the specific catalyst ratios on a dry basis are shown in Table 4.
Test examples
The catalytic cracking catalysts CA-CE prepared above were aged at 800 ℃ for 12 hours in an atmosphere of 100% steam, respectively, and then charged in a small-sized fixed fluidized bed ACE apparatus in respective charge amounts of 9 g. Then, the reaction temperature is 530 ℃ and the space velocity is 16h-1The feed oil shown in table 3 was subjected to catalytic cracking reaction at a feed oil weight ratio of 5:1, and the reaction results are shown in table 5.
Test comparative example
The raw oil was subjected to catalytic cracking reaction according to the method of test example except that the catalysts CA-CE were respectively replaced with the same parts by weight of catalytic cracking catalysts CDB1-CDB7, and the reaction results are shown in Table 5.
The results in table 5 show that the catalyst prepared by the present invention has excellent heavy oil conversion ability and higher gasoline yield.
TABLE 1
TABLE 2
Molecular sieves B C D E
Unit cell constant/A angstrom 24.48 24.43 24.39 24.35
Mesoporous volume/(mL/g) 0.27 0.34 0.68 0.21
VMesoporous structure/VGeneral hole 0.38 0.51 0.59 0.32
(amount of strong acid/total acid)/% 39 42 48 55
Acid amount of B acid/acid amount of L acid 40 51 86 74
D (Al distribution) 0.71 0.65 0.38 0.35
TABLE 3
Item Raw oil
Density (20 ℃ C.), g/cm3 0.9334
Dioptric light (70 degree) 1.5061
Four components, m%
Saturated hydrocarbons 55.6
Aromatic hydrocarbons 30
Glue 14.4
Asphaltenes <0.1
Freezing point, DEG C 34
Metal content, ppm
Ca 3.9
Fe 1.1
Mg <0.1
Na 0.9
Ni 3.1
Pb <0.1
V 0.5
C m％ 86.88
H m％ 11.94
S m％ 0.7
M% of carbon residue 1.77
TABLE 4
TABLE 5

Claims (15)

1. A catalytic cracking catalyst comprising, on a dry basis, 25 to 75 wt% of a Y molecular sieve, 10 to 30 wt% of an inorganic oxide binder, and 15 to 65 wt% of a natural mineral; wherein the unit cell parameter of the Y molecular sieve is 24.35-24.55 angstrom; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.3 and less than or equal to 0.8, wherein D = Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance H from the edge of the crystal face of the molecular sieve crystal grain to the inside measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance H from the geometric center of the crystal face of the molecular sieve crystal grain to the outside measured by a TEM-EDS method, wherein H is 10% of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face; the mesoporous volume of the molecular sieve is 0.15-1.0 ml/g; the proportion of the mesopore volume of the molecular sieve in the total pore volume is 30-70%, and the mesopores are molecular sieve pore passages with the pore diameter of more than 2 nanometers and less than 100 nanometers; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 30-60%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-100.
2. The catalytic cracking catalyst of claim 1, wherein the molecular sieve has a unit cell parameter of 24.40 to 24.52 angstroms; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.35 and less than or equal to 0.75; the mesoporous volume of the molecular sieve is 0.2-0.8 ml/g; the proportion of the mesoporous volume of the molecular sieve in the total pore volume is 35-65%; the strong acid amount of the molecular sieve accounts for 35-55% of the total acid amount, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 60-80.
3. The catalytic cracking catalyst of claim 1, wherein the natural minerals comprise at least one selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, hydrotalcite, bentonite, and rectorite, and the inorganic oxide binder comprises at least one selected from the group consisting of silica, alumina, zirconia, titania, and amorphous silica-alumina.
4. A method for preparing a catalytic cracking catalyst, the method comprising: mixing raw materials for preparing a catalytic cracking catalyst with water, pulping and spray drying; wherein,
the raw material comprises 25-75 wt% of Y molecular sieve, 10-30 wt% of precursor of inorganic oxide binder and 15-65 wt% of natural mineral substance based on dry weight;
the unit cell parameter of the Y molecular sieve is 24.35-24.55 angstrom; the Al distribution parameter D of the molecular sieve meets the following requirements: d is more than or equal to 0.3 and less than or equal to 0.8, wherein D = Al (S)/Al (C), Al (S) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance H from the edge of the crystal face of the molecular sieve crystal grain to the inside measured by a TEM-EDS method, Al (C) represents the aluminum content of a region which is arbitrarily more than 100 square nanometers in the distance H from the geometric center of the crystal face of the molecular sieve crystal grain to the outside measured by a TEM-EDS method, wherein H is 10% of the distance from a certain point of the edge of the crystal face to the geometric center of the crystal face; the mesoporous volume of the molecular sieve is 0.15-1.0 ml/g; the proportion of the mesopore volume of the molecular sieve in the total pore volume is 30-70%, and the mesopores are molecular sieve pore passages with the pore diameter of more than 2 nanometers and less than 100 nanometers; the ratio of the strong acid amount of the molecular sieve to the total acid amount is 30-60%, and the ratio of the acid amount of the B acid to the acid amount of the L acid is 20-100.
5. The method of claim 4, wherein the step of preparing the Y molecular sieve comprises:
a. carrying out ammonium exchange treatment on the NaY molecular sieve, and filtering and washing to obtain an ammonium exchange molecular sieve; wherein the ammonium exchanged molecular sieve has a sodium oxide content of less than 5 weight percent, calculated as sodium oxide and based on the weight of the ammonium exchanged molecular sieve on a dry basis;
b. b, carrying out hydrothermal roasting treatment on the ammonium exchange molecular sieve obtained in the step a in a steam atmosphere to obtain a water roasted molecular sieve;
c. c, performing first dealumination treatment on the water-baked molecular sieve obtained in the step b in an acid solution consisting of organic acid and inorganic acid, and filtering and washing to obtain a first dealumination molecular sieve;
d. c, performing alkali treatment on the first dealuminized molecular sieve obtained in the step c in an inorganic alkali solution, and filtering and washing to obtain an alkali-treated molecular sieve;
e. and d, carrying out secondary dealumination treatment on the alkali-treated molecular sieve obtained in the step d in a composite acid dealumination agent solution consisting of fluosilicic acid, organic acid and inorganic acid, and filtering and washing to obtain the Y molecular sieve, wherein the inorganic acid is at least one selected from hydrochloric acid, sulfuric acid and nitric acid.
6. The preparation method according to claim 5, wherein the organic acid in the acid solution in step c is at least one selected from the group consisting of ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid, and the inorganic acid is at least one selected from the group consisting of hydrochloric acid, sulfuric acid and nitric acid.
7. The preparation method according to claim 5, wherein the conditions of the first dealumination treatment in step c include: the weight ratio of the molecular sieve, the organic acid and the inorganic acid on a dry basis is 1: (0.03-0.3): 0.02-0.4); the first dealuminization treatment temperature is 25-100 ℃, and the first dealuminization treatment time is 0.5-6 hours.
8. The preparation method according to claim 5, wherein the conditions of the first dealumination treatment in step c include: the weight ratio of the molecular sieve, the organic acid and the inorganic acid on a dry basis is 1: (0.05-0.25):(0.05-0.25).
9. The production method according to claim 5, wherein the inorganic base solution in step d is at least one selected from the group consisting of a sodium hydroxide solution, a potassium hydroxide solution, a lithium hydroxide solution and ammonia water.
10. The production method according to claim 5, wherein the conditions of the alkali treatment in step d include: the weight ratio of the molecular sieve to the inorganic base on a dry basis is 1: (0.02-0.6); the alkali treatment temperature is 25-100 ℃, and the alkali treatment time is 0.5-6 hours.
11. The preparation method according to claim 5, wherein the organic acid in the composite acid dealuminating agent solution in the step e is at least one selected from the group consisting of ethylenediaminetetraacetic acid, oxalic acid, citric acid and sulfosalicylic acid.
12. The preparation method according to claim 5, wherein the conditions of the second dealumination treatment in step e include: the weight ratio of the molecular sieve, the fluosilicic acid, the organic acid and the inorganic acid is 1: (0.03-0.3): (0.05-0.3): 0.05-0.25); the second dealuminization treatment temperature is 25-100 ℃, and the second dealuminization treatment time is 0.5-6 hours.
13. The preparation method according to claim 5, wherein the conditions of the second dealumination treatment in step e include: the weight ratio of the molecular sieve, the fluosilicic acid, the organic acid and the inorganic acid is 1: (0.035-0.2):(0.06-0.2):(0.1-0.2).
14. The preparation method according to claim 5, wherein the conditions of the hydrothermal roasting treatment in step b include: the temperature is 450 ℃ and 750 ℃, the time is 0.5-6 hours, and the water vapor atmosphere is 100 percent of the water vapor atmosphere.
15. The method according to claim 4, wherein the natural mineral substance comprises at least one selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, hydrotalcite, bentonite and rectorite, and the precursor of the inorganic oxide binder comprises at least one selected from the group consisting of silica sol, alumina sol, peptoid boehmite, silica-alumina sol and phosphorus-containing alumina sol.
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CN105148985A (en) * 2014-06-10 2015-12-16 中国石油化工股份有限公司 Catalytic cracking catalyst, preparation method thereof and application
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CN102264643A (en) * 2008-12-22 2011-11-30 道达尔炼油与销售部 Modified y-type zeolites having a trimodal intracrystalline structure, method for making same, and use thereof
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