CN108452833B - Catalytic cracking catalyst - Google Patents
Catalytic cracking catalyst Download PDFInfo
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- CN108452833B CN108452833B CN201710096449.6A CN201710096449A CN108452833B CN 108452833 B CN108452833 B CN 108452833B CN 201710096449 A CN201710096449 A CN 201710096449A CN 108452833 B CN108452833 B CN 108452833B
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- molecular sieve
- rare earth
- acid
- phosphorus
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- 239000003054 catalyst Substances 0.000 title claims abstract description 124
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 76
- 239000002808 molecular sieve Substances 0.000 claims abstract description 343
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- 239000011148 porous material Substances 0.000 claims abstract description 109
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 103
- 239000011574 phosphorus Substances 0.000 claims abstract description 103
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 100
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- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
Classifications
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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
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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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- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
A catalytic cracking catalyst comprises a phosphorus-containing and rare earth-modified Y-type molecular sieve, an alumina binder containing an additive and clay, wherein the content of rare earth oxide in the phosphorus-containing and rare earth-modified Y-type molecular sieve is 4-11 wt%, the content of phosphorus is 0.05-10 wt%, the content of sodium oxide is not more than 0.5 wt%, the total pore volume is 0.4-0.48 mL/g, the pore volume of secondary pores accounts for 20-38% of the total pore volume, the unit cell constant is 2.440-2.455 nm, the content of non-framework aluminum accounts for not more than 10% of the total aluminum content, the lattice collapse temperature is not lower than 1060 ℃, and the ratio of the B acid content to the L acid content is not lower than 3.50. The catalyst has higher heavy oil conversion activity, lower coke selectivity, higher gasoline yield, liquefied gas yield, light oil yield and total liquid yield.
Description
Technical Field
The invention relates to a catalytic cracking catalyst and a preparation method thereof.
Background
The Y-type molecular sieve has been the main active component of catalytic cracking (FCC) catalysts since its first use in the last 60 th century. However, as crude oil heavies increase, the content of polycyclic compounds in the FCC feedstock increases significantly, and their ability to diffuse through the zeolite channels decreases significantly. The aperture of the Y-type molecular sieve as the main active component is only 0.74nm, and the Y-type molecular sieve is directly used for processing heavy fractions such as residual oil and the like, and the accessibility of the active center of the catalyst can become a main obstacle for cracking polycyclic compounds contained in the Y-type molecular sieve.
The molecular sieve pore structure has close relation with the cracking reaction performance, especially for a residual oil cracking catalyst, the secondary pores of the molecular sieve can increase the accessibility of residual oil macromolecules and active centers thereof, and further improve the cracking capability of residual oil. The hydrothermal dealumination process is one of the most widely used in industry, and includes the first exchange of NaY zeolite with water solution of ammonium ion to reduce the sodium ion content in zeolite, and the subsequent roasting of the ammonium ion exchanged zeolite at 600-825 deg.c in water vapor atmosphere to stabilize the zeolite. The method has low cost and is easy for industrialized mass production, and the obtained ultrastable Y-type zeolite has rich secondary pores, but has serious loss of crystallinity and poor thermal stability.
At present, the industrial production of the ultrastable Y-type zeolite is generally an improvement on the hydrothermal roasting process, and the method of twice exchanging and twice roasting is adopted, so that the prepared ultrastable Y-type zeolite also has a certain amount of secondary pores, but the proportion of the secondary pores with larger pore diameters in the total secondary pores is lower, and the specific surface and the crystallinity of the ultrastable zeolite are still required to be further improved.
US5,069,890 and US5,087,348 disclose a method for preparing a mesoporous Y-type molecular sieve, which mainly comprises the following steps: commercially available USY was used as a starting material and treated at 760 ℃ for 24 hours in an atmosphere of 100% steam. 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 surface area is 683m2The/g is reduced to 456m2The acid density drops sharply from 28.9% to 6% even more.
In the method for preparing the mesoporous-containing Y-shaped molecular sieve disclosed in US5,601,798, HY or USY is taken as a raw material and is put into an autoclave to react with NH4NO3Solution or NH4NO3With HNO3The mixed solution is mixed and treated for 2 to 20 hours at the temperature of 115 to 250 ℃ higher than the boiling point, the volume of the mesoporous of the obtained Y-shaped molecular sieve can reach 0.2 to 0.6ml/g, but the crystallinity and the surface area are obviously reduced.
CN201310240740.8 discloses a combined modification method of a rich-mesoporous ultrastable Y molecular sieve, which is characterized in that organic acid and inorganic salt dealuminization reagents are added simultaneously in the modification process to carry out combined modification of organic acid and inorganic salt, and the optimal process conditions of optimal concentration, volume ratio, reaction time, reaction temperature and the like of organic acid and inorganic salt solution are determined through orthogonal experiments. Compared with industrial USY molecular sieve, the USY obtained by the method has obviously improved secondary pore content, and is suitable for high and medium oil type hydrocracking catalyst carriers. CN1388064 discloses a method for preparing high-silicon Y zeolite with a unit cell constant of 2.420-2.440 nanometers, which comprises the steps of carrying out ammonium exchange, hydrothermal treatment and/or chemical dealumination on NaY zeolite or Y-type zeolite subjected to hyperstabilization treatment for one or more times; characterized in that at least the first ammonium exchange in the ammonium exchange before the hydrothermal treatment and/or chemical dealumination is a low-temperature selective ammonium exchange at room temperature to below 60 ℃, and the rest of the ammonium exchanges are either low-temperature selective ammonium exchanges at room temperature to below 60 ℃ or conventional ammonium exchanges at 60-90 ℃. The high-silicon Y zeolite prepared by the patent still has higher crystal retention degree when the unit cell constant is smaller, and simultaneously has more secondary holes, and is suitable for being used as a middle distillate oil hydrocracking catalyst. The ultrastable Y molecular sieve prepared by the method disclosed by the patent contains a certain amount of secondary pores, has a small unit cell constant, is high in silicon-aluminum ratio, does not contain rare earth, and is suitable for hydrogenation catalysts which are difficult to meet the requirement of high catalytic cracking activity required by processing heavy oil.
CN1629258 discloses a preparation method of a cracking catalyst containing a rare earth ultrastable Y-type molecular sieve, which is characterized in that the method comprises the step of contacting a NaY molecular sieve with an ammonium salt aqueous solution containing 6-94 wt% of ammonium salt twice or more according to the weight ratio of ammonium salt to molecular sieve of 0.1-24 under the conditions of normal pressure and the temperature of more than 90 ℃ to no more than the boiling point temperature of the ammonium salt aqueous solution, so that Na in the molecular sieve is obtained2Reducing the O content to below 1.5 weight percent, and then contacting the molecular sieve with an aqueous solution with the rare earth salt content of 2-10 weight percent at the temperature of 70-95 ℃ to ensure that the rare earth in the molecular sieve is RE2O30.5-18 wt%, and mixing with carrier and drying. The molecular sieve has low superstability, low Si/Al ratio and less secondary pores.
CN1127161 discloses a rare earth-containingA process for preparing silicon-rich ultrastable Y-type molecular sieve from NaY as raw material in solid RECl3In the presence of SiCl4And carrying out gas-phase dealuminization and silicon supplementation reaction to complete the ultra-stabilization of NaY and the rare earth ion exchange in one step. The unit cell constant a of the molecular sieve prepared by the methodo2.430-2.460 nm, rare earth content of 0.15-10.0 wt%, and Na2The O content is less than 1.0 wt%. However, the molecular sieve is prepared only by a gas phase ultrastable method, and although the ultrastable Y molecular sieve containing rare earth can be prepared, the prepared molecular sieve is lack of secondary pores.
The gas-phase chemical method enables silicon in gas-phase silicon tetrachloride and aluminum in a molecular sieve framework to directly generate isomorphous substitution under the gas-phase ultrastable reaction condition, so that dealuminization and silicon supplement are carried out simultaneously, dealuminization is uniform, and the gas-phase ultrastable molecular sieve does not have secondary pores.
CN1031030 discloses a preparation method of an ultrastable Y-type molecular sieve with low rare earth content, which is used for hydrocarbon cracking and is prepared by using a NaY-type molecular sieve as a raw material through the steps of primary mixed exchange of ammonium ions and rare earth ions, stabilization treatment, removal of part of framework aluminum atoms, thermal or hydrothermal treatment and the like. Rare earth content (RE) of the molecular sieve2O3) 0.5 to 6 wt% of SiO2/Al2O3Up to 9 to 50, unit cell constant a02.425 to 2.440 nm. The ultrastable molecular sieve prepared by the method has high silicon-aluminum ratio, small unit cell constant and a certain amount of rare earth, but the prepared molecular sieve heavy oil has low catalytic cracking activity and poor coke selectivity.
CN1330981A discloses a phosphorus-containing Y-type zeolite and a preparation method thereof. The said P-containing Y-type zeolite contains P, a Si component and rare-earth component, and the Si component is loaded by impregnating zeolite with solution of Si compound and is SiO2The content of the silicon component is 1-15 wt% calculated by P2O5The content of the phosphorus component is 0.1-15 wt%, and the content of the rare earth component is 0.2-15 wt% calculated by rare earth oxide. The molecular sieve is prepared by mixing rare earth-containing Y-type zeolite with rare earth-containing zeoliteThe solution of silicon and phosphorus is soaked together, and is obtained by hydrothermal roasting at 550-850 ℃ after being dried. However, the heavy oil containing phosphorus Y-type zeolite has low cracking activity and low light oil yield.
CN1353086A discloses a method for preparing Y-type molecular sieve containing phosphorus and rare earth, which comprises the steps of firstly mixing and exchanging NaY molecular sieve with ammonium ions and rare earth ions, carrying out hydrothermal roasting, and then reacting and combining the NaY molecular sieve with phosphorus compounds by 0.2-10 wt% (based on P)2O5Calculated), and then carrying out hydrothermal roasting. However, the heavy oil containing phosphorus Y-type zeolite has low cracking activity and low light oil yield.
CN1506161 discloses an active component of a rare earth ultrastable Y molecular sieve, wherein the modified molecular sieve contains 8-25 wt% of rare earth oxide and 0.1-3.0 wt% of phosphorus; 0.3 to 2.5 wt% of sodium oxide, 30 to 55% of crystallinity and 2.455 to 2.472nm of unit cell constant. The molecular sieve is prepared by using NaY zeolite as a raw material, performing rare earth exchange and first roasting to obtain 'once-exchanged once-roasted' rare earth NaY, reacting with rare earth, phosphorus-containing substances and ammonium salt, and performing second roasting treatment to obtain modified Y zeolite modified by phosphorus and rare earth. The molecular sieve prepared by the method has high rare earth content, large unit cell constant, poor thermal stability and poor selectivity of molecular sieve coke.
CN1317547A discloses a phosphorus and rare earth compound modified Y zeolite and a preparation method thereof, the molecular sieve is prepared by mixing and exchanging NaY zeolite with rare earth and ammonium salt, then carrying out hydrothermal roasting treatment, reacting with phosphorus compound, and then carrying out secondary roasting treatment, wherein RE is RE2O3The weight ratio of the ammonium salt to the Y zeolite is 0.02-0.18, the weight ratio of the ammonium salt to the Y zeolite is 0.1-1.0, the weight ratio of the P to the Y zeolite is 0.003-0.05, the roasting temperature is 250-750 ℃, the water vapor condition is 5-100%, and the time is 0.2-3.5 hours. The modified Y zeolite obtained by the method has poor thermal stability and low heavy oil cracking activity.
CN02103910.0 provides a method for preparing 'one-exchange one-baking' modified faujasite, which is obtained by carrying out primary exchange reaction on faujasite, a phosphorus compound and an ammonium compound, then introducing a rare earth solution into the exchange slurry for further reaction, and carrying out filtration, washing and water vapor roasting treatment. The zeolite has low cracking activity and low heavy oil conversion rate.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a catalytic cracking catalyst suitable for heavy oil catalytic cracking processing, which contains a modified Y-type molecular sieve (the Y-type molecular sieve is also called Y-type zeolite), and the catalyst has higher heavy oil cracking activity and better coke selectivity. The second technical problem to be solved by the invention is to provide a preparation method of the catalyst.
The invention provides a catalytic cracking catalyst, which comprises 10-50 wt% of phosphorus-containing and rare earth-containing modified Y-type molecular sieve (modified Y-type molecular sieve for short) based on the weight of the catalytic cracking catalyst, 2-40 wt% of alumina containing additives based on the weight of the catalyst, and 10-80 wt% of clay based on the weight of the catalyst; the additive-containing alumina contains 60-99.5 wt% of alumina and 0.5-40 wt% of additive by dry basis, wherein the additive is selected from one or more of compounds containing alkaline earth metal, lanthanide metal, silicon, gallium, boron or phosphorus; the content of the rare earth oxide of the phosphorus-containing and rare earth-modified Y-shaped molecular sieve is 4 to 11 weight percent, and the phosphorus content is P2O50.05 to 10 wt%, sodium oxide content (Na)2O content) of not more than 0.5% by weight, for example, 0.05 to 0.5% by weight, and a total pore volume of 0.36 to 0.48mL/g, the pore volume of secondary pores having a pore diameter of 2 to 100nm of the phosphorus-and rare earth-modified Y-type molecular sieve is 20 to 40% by volume of the total pore volume, the unit cell constant is 2.440 to 2.455nm, the content of non-framework aluminum in the phosphorus-and rare earth-modified Y-type molecular sieve is not more than 10% by volume of the total aluminum content, the lattice collapse temperature is not less than 1060 ℃, and the ratio of the amount of B acid to the amount of L acid in the total amount of the phosphorus-and rare earth-modified Y-type molecular sieve measured at 200 ℃ by pyridine adsorption infrared method is not less than 3.5.
In the catalytic cracking catalyst provided by the invention, the lattice collapse temperature of the phosphorus-containing and rare earth-modified Y-type molecular sieve is not lower than 1060 ℃, preferably, the lattice collapse temperature of the molecular sieve is 1065-1085 ℃, for example, 1067-1080 ℃.
In the catalytic cracking catalyst provided by the invention, the ratio of the B acid amount to the L acid amount in the total acid amount of the modified Y-type molecular sieve determined by a pyridine adsorption infrared method at 200 ℃ is preferably 3.5-6, for example 3.5-5.5 or 3.5-4.6.
In the catalytic cracking catalyst provided by the invention, the unit cell constant of the phosphorus-containing and rare earth-modified Y-type molecular sieve is 2.440-2.455 nm, such as 2.442-2.453 nm or 2.442-2.451 nm.
In the catalytic cracking catalyst provided by the invention, the phosphorus-containing and rare earth-containing modified Y-type molecular sieve is a high-silicon Y-type molecular sieve, and the framework silicon-aluminum ratio (SiO) of the high-silicon Y-type molecular sieve2/Al2O3Molar ratio) of 7 to 14, for example 8.5 to 12.6 or 9.2 to 11.4 or 7.8 to 12.6.
In the catalytic cracking catalyst provided by the invention, the percentage of the non-framework aluminum content in the phosphorus-containing and rare earth-modified Y-type molecular sieve in the total aluminum content is not higher than 10%, for example, 5-9.5 wt% or 6-9.5 wt%.
In the catalytic cracking catalyst provided by the invention, the crystal retention of the phosphorus-containing and rare earth-modified Y-shaped molecular sieve after aging for 17 hours at 800 ℃ under normal pressure and in a 100 volume percent steam atmosphere is 38-60 percent or 50-60 percent or 46-58 percent, for example. The normal pressure is 1 atm.
In the catalytic cracking catalyst provided by the invention, the relative crystallinity of the phosphorus-containing and rare earth-modified Y-type molecular sieve is not less than 70%, for example, 70-80%, and further for example, 70-76%.
In the catalytic cracking catalyst provided by the invention, the phosphorus-containing and rare earth-containing modified Y-type molecular sieve has an implementation mode that the specific surface area is 600-670 m2The number of grams of the additive is, for example, 610 to 670 or 640 to 670 or 646 to 667m2/g。
In the catalytic cracking catalyst provided by the invention, the total pore volume of the phosphorus-containing and rare earth-modified Y-type molecular sieve is 0.36-0.48 mL/g, preferably, the total pore volume is 0.38-0.42 or 0.4-0.48 mL/g, for example. The pore volume of the secondary pores of 2.0 to 100nm is 0.08 to 0.18mL/g, for example, 0.1 to 0.16 mL/g.
In the catalytic cracking catalyst provided by the invention, the pore volume of the secondary pores with the pore diameter (diameter) of 2.0-100 nm accounts for 20-40% of the total pore volume, preferably 28-38%, for example 25-35%. The ratio of the pore volume of secondary pores with the pore diameter of 8-100 nm (the total volume of the pores with the pore diameter of 2-100 nm)/the pore volume of total secondary pores (the total volume of the pores with the pore diameter of 2-100 nm) in the modified Y-type molecular sieve is 40-80%, for example, 45-75% or 55-77%.
In the catalytic cracking catalyst provided by the invention, the phosphorus-containing and rare earth-containing modified Y-shaped molecular sieve contains rare earth elements, and RE is used in the modified Y-shaped molecular sieve2O3The rare earth oxide content is preferably 4.5 to 10 wt%, for example 5 to 9 wt%, in the range of 4 to 11 wt%.
In the catalytic cracking catalyst provided by the invention, the phosphorus-containing and rare earth-containing modified Y-shaped molecular sieve contains phosphorus modified elements, and P in the modified Y-shaped molecular sieve2O5(i.e. with P)2O5Phosphorus content) of 0.05 to 10 wt.%, preferably 0.1 to 6 wt.%, for example 1 to 4 wt.%.
In the catalytic cracking catalyst provided by the invention, the content of sodium oxide in the phosphorus-containing and rare earth-modified Y-type molecular sieve is not more than 0.5%, and can be 0.05-0.5 wt%, for example, 0.1-0.4 wt% or 0.05-0.3 wt%.
In the catalytic cracking catalyst provided by the invention, the content of the phosphorus-containing and rare earth-modified Y-type molecular sieve is 10-50 wt% on a dry basis, preferably 15-45 wt%, for example 25-40 wt%.
The catalytic cracking catalyst provided by the invention contains 10-50 wt% of phosphorus-containing and rare earth-modified Y-shaped molecular sieve on a dry basis, preferably, the content of the phosphorus-containing and rare earth-modified Y-shaped molecular sieve is 15-45 wt%, for example, 20-40 wt% or 25-35 wt%.
The catalytic cracking catalyst provided by the invention can also contain clay, and the content of the clay is not more than 70 wt%, preferably 10-70 wt% based on the weight of the catalytic cracking catalyst. The clay is selected from one or more of clays used as cracking catalyst component, such as one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, and bentonite. These clays are well known to those of ordinary skill in the art. The content of the clay in the catalytic cracking catalyst provided by the invention can be 20-55 wt% or 30-50 wt% on a dry basis.
The catalyst of the invention contains alumina containing additive, and the content of the alumina containing additive is 2-40 wt%, preferably 2-20 wt% on a dry basis based on the weight of the catalyst. The alumina containing additives can be prepared according to the methods described in patents CN1915486A, CN1915485A and CN 1916116A. Preferably, the additive-containing alumina contains 70 wt% to 95 wt% of alumina based on the dry weight of the additive-containing alumina, and 5 wt% to 30 wt% of the additive based on the dry weight of the additive-containing alumina. Wherein said additive is preferably a phosphorus and/or magnesium containing compound.
The dry weight is the weight of the solid product obtained by calcining the material at 800 ℃ for 1 hour.
Preferably, the preparation method of the alumina containing the additive comprises the following steps:
(1) mixing pseudoboehmite with water and acid sufficient to cause slurrification thereof under agitation, wherein the acid is used in an amount such that the weight ratio of the acid to alumina in the pseudoboehmite is 0.01 to 0.5;
(2) aging the mixed slurry obtained in the step (1) at room temperature to 90 ℃ for 0 to 24 hours;
(3) mixing the product of step (2) with additives, optionally drying and optionally calcining.
In the method for preparing alumina containing additive, the acid in the step (1) is used in an amount that the weight ratio of the acid to the alumina in the pseudo-boehmite is 0.05-0.3. The slurrying in the step (1) enables the solid content of the slurry formed by the pseudo-boehmite and the water to be 10-50 wt%, and preferably 15-30 wt%. The acid is selected from one or more of inorganic acid and organic acid, for example, the inorganic acid can be one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid, the organic acid can be one or more of formic acid, acetic acid, oxalic acid or itaconic acid, and hydrochloric acid or nitric acid is preferred.
In the preparation method of the alumina containing the additive, preferably, the aging temperature in the step (2) is between room temperature and 80 ℃, the room temperature is, for example, between 15 and 40 ℃, and the aging time is between 0.5 and 4 hours. The mixture formed by the product of step (2) and the additive in step (3) can be directly used for preparing the catalytic cracking catalyst, namely, the formed mixture is mixed with other components forming the catalytic cracking catalyst, and can also be dried and calcined for preparing the catalyst. Such as drying, spray drying.
In one embodiment of the method for preparing the additive-containing alumina, the calcination temperature in the step (3) is 350 to 800 ℃, for example, 400 to 600 ℃, and the calcination time is, for example, 0.5 to 8 hours. The additive is selected from one or more of compounds containing alkaline earth metal, lanthanide metal, silicon, gallium, sheds or phosphorus elements, the compounds containing the alkaline earth metal, copper metal, silicon, gallium, sheds or phosphorus elements can be oxides and hydrated oxides of the elements, such as magnesium oxide and magnesium hydroxide in the alkaline earth metal, rare earth oxide in the lanthanide metal, silicon oxide, silica sol and phosphorus oxide, and also can be salts containing the elements, such as nitrate in the alkaline earth metal, rare earth chloride in the lanthanide metal, silicate and phosphate. When the additive is an oxide of the element and/or a water-containing oxide, the mixing is to directly mix the product obtained in the step 2 with the additive; when the additive is one or more of salts containing the elements, the mixing is preferably performed by firstly preparing the salts into an aqueous solution and then mixing the aqueous solution with the product obtained in the step (2). The mixing in each step can be accomplished by any of a variety of methods known in the art, preferably under conditions sufficient to slurry the material (e.g., pseudoboehmite, additives), which are well known to those skilled in the art, including the introduction of water in an amount sufficient to slurry the material, typically in an amount of from 10 to 50 weight percent, preferably from 15 to 30 weight percent, of the slurry solids.
The catalytic cracking catalyst of the present invention preferably further comprises an alumina binder, wherein the content of the alumina binder is not more than 32 wt%, preferably 5 to 32 wt%, based on the weight of the catalyst, and the alumina binder is selected from one or more of alumina, hydrated alumina and alumina sol of various forms commonly used in cracking catalysts, for example, one or more selected from gamma-alumina, η -alumina, theta-alumina, chi-alumina, pseudoboehmite (pseudoboehmite), Boehmite (Boehmite), Gibbsite (Gibbsite), Bayerite (bayer) or alumina sol, preferably pseudoboehmite and/or alumina sol, and the catalytic cracking catalyst preferably comprises 2 to 15 wt%, preferably 3 to 10 wt%, based on the dry basis, of alumina sol binder, and 10 to 30 wt%, preferably 15 to 25 wt%, based on the dry basis, of pseudoboehmite binder.
Preferably, the total content of the alumina binder and the alumina containing additive in the catalyst of the present invention is 10 wt% to 40 wt%, for example 20 to 35 wt%, and the content of the alumina containing additive is 2 wt% to 20 wt%, based on the weight of the catalyst.
The catalytic cracking catalyst of the present invention preferably comprises, based on the weight of the catalytic cracking catalyst: 10 to 50 wt% on a dry basis, such as 15 to 45 wt% or 25 to 40 wt% of the phosphorus-and rare earth-modified Y-type molecular sieve, and 50 to 90 wt% on a dry basis, such as 55 to 85 wt% or 60 to 75 wt% of a matrix. The matrix comprises the additive-containing alumina, clay and optionally a binder, preferably an alumina binder.
The catalyst provided by the invention can also contain other molecular sieves besides the phosphorus-containing and rare earth-modified Y-type molecular sieve, wherein the other molecular sieves are selected from the molecular sieves used in the catalytic cracking catalyst, such as one or more of zeolite with MFI structure, Beta zeolite, other Y-type zeolite and non-zeolite molecular sieve, the content of the other molecular sieves can be 0-40 wt% such as 0-30 wt% or 1-20 wt%, preferably, the content of the other Y-type molecular sieves is not more than 40 wt% such as 1-40 wt% or 0-20 wt% on a dry basis, the content of the other Y-type zeolites such as one or more of REY, REHY, DASY, SOY and PSRY, the MFI structure zeolite such as one or more of H5, ZRP and ZSP, the Beta zeolite such as H β, the non-zeolite molecular sieves such as aluminum phosphate molecular sieves (AlPO molecular sieves), and silicoaluminophosphate molecular sieves (ZSM), and the content of the other molecular sieves is not more than 20 wt% based on the weight of the catalyst.
The preparation methods of the catalyst of the present invention are the existing methods, and the preparation methods are described in detail in patents CN1916116A, CN1362472A, CN1727442A, CN1132898C, CN1727445A and CN1098130A, which are incorporated herein by reference. Typically comprising the steps of forming a slurry comprising the modified Y-type molecular sieve, a binder, clay and water, spray drying, optionally washing and drying. Spray drying, washing and drying are the prior art, and the invention has no special requirements. For example, a preparation method comprises the steps of mixing and pulping the modified Y-type molecular sieve, alumina containing additives, clay, optional alumina binder and water, spray drying, washing, filtering and drying.
One embodiment of the present invention provides a method for preparing a catalytic cracking catalyst comprising the steps of preparing a phosphorus and rare earth modified Y-type molecular sieve, forming a slurry comprising the phosphorus and rare earth modified Y-type molecular sieve, an additive-containing alumina, a clay, water, and optionally an alumina binder, spray drying, wherein,
the method for preparing the phosphorus-containing and rare earth-modified Y-type molecular sieve comprises the following steps:
(1) contacting the NaY molecular sieve with a rare earth solution to perform an ion exchange reaction, filtering and washing to obtain a Y-type molecular sieve containing rare earth with a conventional unit cell size and reduced sodium oxide content; wherein the rare earth solution is also called rare earth salt solution;
(2) modifying the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size, and optionally drying to obtain a Y-type molecular sieve with a reduced unit cell constant, wherein the modifying is to roast the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content and the conventional unit cell size at the temperature of 350-480 ℃ in an atmosphere containing 30-90 vol% of water vapor (also called 30-90 vol% of water vapor atmosphere or 30-90 vol% of water vapor) for 4.5-7 hours;
(3) mixing the Y-type molecular sieve sample with SiCl, wherein the unit cell constant is reduced4Carrying out gas contact reaction; wherein the preferable contact reaction temperature is 200-650 ℃, SiCl4: the weight ratio of the Y-type molecular sieve with reduced unit cell constant obtained in the step (2) on a dry basis is 0.1-0.7: 1, reacting for 10 minutes to 5 hours, and then washing and filtering to obtain the gas-phase ultra-stable modified Y-type molecular sieve. Wherein the water content of the Y-type molecular sieve sample with reduced unit cell constant is preferably not more than 1 wt%; if the water content in the Y-type molecular sieve sample obtained by modification treatment in the step (2) (in the Y-type molecular sieve sample obtained by roasting) is not more than 1 wt%, the Y-type molecular sieve sample can be directly used for contacting silicon tetrachloride to carry out the reaction, and if the water content in the Y-type molecular sieve sample obtained by roasting in the step (2) exceeds 1 wt%, the Y-type molecular sieve sample with the reduced unit cell constant obtained by roasting in the step (2) is dried to enable the water content to be lower than 1 wt%;
(4) contacting the gas-phase ultra-stable modified Y-shaped molecular sieve obtained in the step (3) with an acid solution for modification to obtain an acid-treated modified Y-shaped molecular sieve;
(5) and (4) contacting the acid-treated modified Y-shaped molecular sieve obtained in the step (4) with a phosphorus compound for phosphorus modification treatment.
The catalytic cracking catalyst provided by the invention has high thermal and hydrothermal stability, higher activity and hydrothermal stability, is used for heavy oil catalytic cracking, has strong heavy oil cracking capability, excellent coke selectivity, and higher gasoline yield, light oil yield and total liquid yield. For example, phosphorus and rare earth containing compounds prepared by the process of the present invention have high crystallinity, high thermal and hydrothermal stabilityAn ultrastable molecular sieve SZ2 with secondary pore structure is prepared through preparing the catalytic cracking catalyst SC2 with high-Si ultrastable Y molecular sieve content of 30.0 wt% by using SZ2 as active component, ageing, and loading the aged catalyst in the fixed fluidized bed ACE evaluating apparatus with heavy oil at 500 deg.C and 16 hr－1The catalyst oil ratio (weight ratio) 4 was evaluated, the conversion of heavy oil was 77.23 wt%, the gasoline yield was 55.91 wt%, the light oil yield was 72.37 wt%, the total liquid yield was 88.89 wt%, the coke selectivity was 4.52%, and the catalyst DC4 prepared by the prior art and having the same content of high-silicon molecular sieve components was aged and then heavy oil was used on a stationary fluidized bed ACE evaluation apparatus at 500 ℃ and a weight hourly space velocity of 16h－1When the catalyst composition is evaluated under the condition of a catalyst-to-oil ratio (weight ratio) of 5, the heavy oil conversion rate of the DC4 catalyst is 75.73 wt%, the gasoline yield is 52.05 wt%, the light oil yield is 68.48 wt%, the total liquid yield is 85.02 wt%, and the coke selectivity is 7.59%; therefore, the catalyst has higher heavy oil conversion capacity, better coke selectivity, higher gasoline yield, light oil yield and total liquid yield.
The preparation method of the catalytic cracking catalyst provided by the invention can prepare the high-silicon Y-type molecular sieve which has high crystallinity, high thermal stability and high hydrothermal stability and is rich in secondary pores, can ensure that the molecular sieve has higher crystallinity under the condition of greatly improving the hyperstabilization degree, and the prepared modified Y-type molecular sieve has uniform aluminum distribution, less non-framework aluminum content and smooth secondary pore channels.
The catalyst of the present invention is suitable for catalytic cracking of hydrocarbon oil, especially heavy oil. Such as one or more of atmospheric residue, vacuum gas oil, atmospheric gas oil, straight run gas oil, propane light/heavy deasphalted oil, and coker gas oil.
Detailed Description
The catalytic cracking catalyst provided by the invention contains 10-50 wt% of the modified Y-type molecular sieve containing phosphorus and rare earth on a dry basis, 2-40 wt% of alumina containing an additive on a dry basis, 0-40 wt% of alumina binder on a dry basis and 10-80 wt% of clay on a dry basis on a weight basis of the catalyst. Preferably, the catalytic cracking catalyst contains 25 to 40 wt% of the phosphorus-and rare earth-modified Y-type molecular sieve on a dry basis, 2 to 20 wt% of the additive-containing alumina on a dry basis, 5 to 30 wt% of an alumina binder on a dry basis, and 30 to 50 wt% of clay on a dry basis, and the total content of the alumina binder and the additive-containing alumina is 20 to 35 wt%.
In one embodiment of the catalytic cracking catalyst provided by the invention, the content of the rare earth oxide in the phosphorus-containing and rare earth-modified Y-type molecular sieve is 4-11 wt%, preferably 4.5-10 wt%; p in the modified Y-shaped molecular sieve2O5(i.e. with P)2O5The phosphorus content) is 0.05 to 10 wt.%, for example 0.1 to 6 wt.%, preferably 0.1 to 5 wt.%; the sodium oxide content is 0.05 to 0.5 wt.%, for example 0.1 to 0.4 wt.% or 0.05 to 0.3 wt.%, preferably less than 0.2 wt.%; the total pore volume is 0.36-0.48 mL/g, the percentage of the pore volume of the secondary pores with the pore diameter of 2-100 nm in the total pore volume is preferably 28-38%, preferably 25-35%, the unit cell constant is 2.440-2.455 nm, preferably 2.441-2.453 nm or 2.442-2.451 nm, and the framework silicon-aluminum ratio (SiO 22/Al2O3Molar ratio) is: 7 to 14 is, for example, 8.5 to 12.6 or 9.2 to 11.4, the percentage of non-framework aluminum content in the molecular sieve to the total aluminum content is not higher than 10%, preferably 6 to 9.5%, the relative crystallinity is not lower than 60%, preferably not lower than 70%, for example 70 to 80%, the lattice collapse temperature is 1065 to 1080 ℃, and the ratio of the amount of B acid to the amount of L acid in the total acid amount of the modified Y-type molecular sieve measured at 200 ℃ by a pyridine adsorption infrared method is not lower than 3.50, for example 3.5 to 6, preferably 3.5 to 4.6.
In the catalytic cracking catalyst provided by the invention, the modified Y-type molecular sieve is a phosphorus-containing and rare earth ultrastable Y-type molecular sieve rich in secondary poresThe secondary pore distribution curve with the medium pore diameter of 2 nm-100 nm is in double-variable pore distribution, wherein the most variable pore diameter of the secondary pore with the smaller pore diameter is 2-5 nm, and the most variable pore diameter of the secondary pore with the larger pore diameter is 6 nm-20 nm, preferably 8 nm-18 nm. Preferably, the proportion of secondary pores with a pore diameter of 8nm to 100nm to the total secondary pores (2nm to 100nm) is 40% to 80%, preferably 45% to 75%, for example, 45% to 55% or 55% to 77%. SiO of the zeolite2/Al2O3Is 7 to 14, preferably 7.8 to 13, more preferably 8.5 to 12.6, and has a cell constant of 2.440 to 2.455nm, preferably 2.441 to 2.453 nm.
In the catalytic cracking catalyst provided by the invention, the preparation process of the phosphorus and rare earth containing modified Y-shaped molecular sieve comprises the step of contacting the Y-shaped molecular sieve with silicon tetrachloride to carry out dealuminization and silicon supplementation reaction.
In the preparation method of the phosphorus and rare earth modified Y-shaped molecular sieve, the NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction in the step (1) to obtain the Y-shaped molecular sieve with the normal unit cell size and the reduced sodium oxide content and containing rare earth. The NaY molecular sieve can be purchased commercially or prepared according to the existing method, and in one embodiment, the unit cell constant of the NaY molecular sieve is 2.465-2.472 nm, and the framework silicon-aluminum ratio (SiO)2/Al2O3Molar ratio) of 4.5 to 5.2, a relative crystallinity of 85% or more, for example, 85 to 95%, and a sodium oxide content of 13.0 to 13.8% by weight. The NaY molecular sieve and the rare earth solution are subjected to ion exchange reaction, the exchange temperature is preferably 15-95 ℃, for example 65-95 ℃, and the exchange time is preferably 30-120 minutes, for example 45-90 minutes. NaY molecular sieve (dry basis) rare earth salt (RE)2O3Meter) H2O is 1:0.01 to 0.18:5 to 20 by weight. In one embodiment, the ion exchange reaction of the NaY molecular sieve and the rare earth solution comprises the following steps of mixing the NaY molecular sieve, rare earth salt and H2The exchange between rare earth ions and sodium ions is carried out by stirring a mixture of NaY molecular sieve (also called NaY zeolite), rare earth salt and water at a weight ratio of 1:0.01 to 0.18:5 to 15, for example, at room temperature to 60 ℃ or 65 to 95 ℃, preferably for 30 to 120 minutes. In one embodiment, the method comprises the following steps of,the weight ratio of the NaY molecular sieve to water is as follows: 1: 6-20, preferably: 7-15. The NaY molecular sieve, rare earth salt and water are mixed to form a mixture, the NaY molecular sieve and the water can be formed into slurry, and then rare earth salt and/or aqueous solution of rare earth salt are added into the slurry, wherein the rare earth solution is solution of rare earth salt, and the rare earth salt is preferably rare earth chloride and/or rare earth nitrate. The rare earth such as one or more of La, Ce, Pr, Nd and misch metal, preferably, the misch metal contains one or more of La, Ce, Pr and Nd, or further contains at least one of rare earth other than La, Ce, Pr and Nd. The washing in step (1) is intended to wash out exchanged sodium ions, and for example, deionized water or decationized water may be used for washing. Preferably, the rare earth content of the rare earth-containing Y-type molecular sieve with the reduced sodium oxide content obtained in step (1) and the conventional unit cell size is calculated as RE2O34.5 to 13 wt%, for example 5.5 to 13 wt% or 5.5 to 12 wt%, and sodium oxide content of not more than 9.5 wt%, for example 5.5 to 9.5 wt%, and a cell constant of 2.465nm to 2.472 nm.
In the preparation method of the phosphorus and rare earth modified Y-shaped molecular sieve, the Y-shaped molecular sieve with the conventional unit cell size containing rare earth is roasted for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere of 30-90 vol% of water vapor in step (2) for treatment, preferably, the roasting temperature in step (2) is 380-460 ℃, the roasting atmosphere is 40-80 vol% of water vapor, and the roasting time is 5-6 hours. The water vapor atmosphere contains 30-90% by volume of water vapor and also contains other gases, such as one or more of air, helium or nitrogen. The Y-type molecular sieve with the reduced unit cell constant in the step (2) has the unit cell constant of 2.450 nm-2.462 nm. Preferably, the calcined molecular sieve is also dried in step (2) so that the water content in the Y-type molecular sieve having a reduced unit cell constant is preferably not more than 1 wt%. The solid content of the Y-type molecular sieve sample with reduced unit cell constant obtained in the step (2) is preferably not less than 99% by weight.
The invention provides a preparation method of a catalytic cracking catalyst containing phosphorus and rare earthIn the preparation method of the modified Y-type molecular sieve, SiCl is adopted in the step (3)4: the weight ratio of the Y-type zeolite (on a dry basis) is preferably 0.3-0.6: 1, the reaction temperature is preferably 350-500 ℃, and the washing method in the step (3) can adopt a conventional washing method, and can be washed by water, such as decationized water or deionized water, so as to remove Na remained in the zeolite+，Cl-And Al3+Etc. soluble by-products, for example the washing conditions may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieve: h2The weight ratio of O is 1: 6-15, the pH value is preferably 2.5-5.0, and the washing temperature is 30-60 ℃. Preferably, the washing is performed such that no free Na is detected in the washing solution after washing+，Cl-And Al3+Plasma, usually Na in washed molecular sieve samples+，Cl-And Al3+The respective contents of ions do not exceed 0.05 wt.%.
In the preparation method of the phosphorus-and rare earth-containing modified Y-shaped molecular sieve, in the step (4), the gas-phase ultrastable modified Y-shaped molecular sieve obtained in the step (3) is contacted with an acid solution to react (the method is called channel cleaning modification, which is called channel cleaning for short, or called acid treatment modification). In one embodiment, the gas phase ultrastable modified Y-type molecular sieve obtained in step (3) is contacted with an acid solution for reaction, the gas phase ultrastable modified molecular sieve, that is, the gas phase ultrastable modified Y-type molecular sieve, is mixed with the acid solution and reacted for a period of time, and then the reacted molecular sieve is separated from the acid solution, for example, by filtration, and then optionally washed (the washing is to remove Na remaining in the zeolite)+，Cl-And Al3+Etc. soluble by-products, for example the washing conditions may be: the weight ratio of the washing water to the molecular sieve can be 5-20: 1, typically molecular sieve: h2The weight ratio of O is 1: 6-15, the pH value is preferably 2.5-5.0, the washing temperature is 30-60 ℃), and the modified Y-type molecular sieve provided by the invention is obtained by optional drying. Contacting the gas-phase ultra-stable modified Y-shaped molecular sieve obtained in the step (3) with an acid solution, wherein the weight ratio of the acid to the molecular sieve (calculated on a dry basis) is 0.001-0.15: 1 is, for example, 0.002 to 0.1: 1 or 0.01 to 0.05: 1, the weight ratio of water to the molecular sieve calculated on a dry basis is 5-20: 1 is, for example, 8 to 15: 1, the temperature for the contact reaction is 60-100 ℃, for example 80-99 ℃, preferably 88-98 ℃.
Preferably, the acid in the acid solution (aqueous acid solution) is at least one organic acid and at least one inorganic acid of medium or higher strength. The organic acid can be one or more of oxalic acid, malonic acid, succinic acid (succinic acid), methylsuccinic acid, malic acid, tartaric acid, citric acid and salicylic acid, and the inorganic acid with medium strength or higher can be one or more of phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid. Preferably, the temperature for cleaning and modifying the pore passage is 80-99 ℃, such as 85-98 ℃, and the time for treating and modifying is more than 60 minutes, such as 60-240 minutes or 90-180 minutes. The weight ratio of the organic acid to the molecular sieve is 0.02-0.10: 1, the weight ratio of the inorganic acid with the medium strength to the molecular sieve is 0.01-0.05: 1 is, for example, 0.02 to 0.05: 1, the weight ratio of water to the molecular sieve is preferably 5-20: 1 is, for example, 8 to 15: 1.
preferably, the pore cleaning modification is carried out in two steps, and firstly, inorganic acid with the strength higher than medium is contacted with the molecular sieve, wherein the weight ratio of the inorganic acid with the strength higher than medium to the molecular sieve is 0.01-0.06: 1 is, for example, 0.02 to 0.05: 1, the weight ratio of water to the molecular sieve is preferably 5-20: 1 is, for example, 8 to 15: 1, the temperature of the contact reaction is 80-99 ℃, preferably 90-98 ℃, and the reaction time is 60-120 minutes; and then contacting the treated molecular sieve with organic acid, wherein the weight ratio of the organic acid to the molecular sieve is (0.02-0.10): 1 is, for example, 0.02 to 0.10: 1 or 0.05-0.08: 1, the weight ratio of water to the molecular sieve is preferably 5-20: 1 is, for example, 8 to 15: 1, the temperature of the contact reaction is 80-99 ℃, preferably 90-98 ℃, and the reaction time is 60-120 minutes. Wherein in the weight ratio, the molecular sieve is on a dry basis.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps of (5) carrying out phosphorus modification treatment on the acid-treated modified Y-shaped molecular sieve obtained in the step (4),to introduce phosphorus into the molecular sieve, said phosphorus modification treatment generally comprising contacting the acid-treated modified Y-type molecular sieve obtained in step (4) with an exchange liquid containing a phosphorus compound. The contacting is typically at 15 to 100 ℃, preferably 30 to 95 ℃ for 10 to 100 minutes, followed by filtration, and optionally washing. Wherein the weight ratio of water to molecular sieve in the exchange liquid is 2-5, preferably 3-4, phosphorus (as P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.0005 to 0.10, preferably 0.001 to 0.06. The phosphorus compound can be one or more of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate and diammonium hydrogen phosphate. The washing is performed by using water with the weight 5-15 times of that of the molecular sieve, such as decationized or deionized water.
In one embodiment, the phosphorus modification treatment conditions are: adding the acid-treated modified Y-shaped molecular sieve into an exchange solution containing a phosphorus compound, carrying out exchange reaction for 10-100 minutes at 15-100 ℃, filtering and washing; wherein, in the mixture formed by the exchange liquid containing the phosphorus compound and the molecular sieve, the weight ratio of water to the molecular sieve is 2-5, preferably 3-4, phosphorus (expressed as P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.0005 to 0.10, preferably 0.001 to 0.06.
The preparation method of the catalytic cracking catalyst provided by the invention comprises the following steps of mixing and pulping the phosphorus-containing and rare earth-modified Y-shaped molecular sieve, an alumina binder, clay and water to form slurry, spray drying, and optionally washing and drying, wherein the preparation method of the phosphorus-containing and rare earth-modified Y-shaped molecular sieve comprises the following steps:
(1) carrying out ion exchange reaction on a NaY molecular sieve (also called NaY zeolite) and a rare earth solution, filtering and washing to obtain a Y-type molecular sieve containing rare earth and having a conventional unit cell size and reduced sodium oxide content; the ion exchange is carried out for 30-120 minutes under the conditions of stirring and the temperature of 15-95 ℃, preferably 65-95 ℃;
(2) roasting the rare earth-containing Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere containing 30-90 vol% of water vapor, and drying to obtain the Y-type molecular sieve with the reduced unit cell constant and the water content of less than 1 wt%; the unit cell constant of the Y-type molecular sieve with the reduced unit cell constant is 2.450 nm-2.462 nm;
(3) mixing said reduced unit cell constant Y-type molecular sieve sample having a water content of less than 1 wt% with heat vaporized SiCl4Gas contact of SiCl4: the weight ratio of the Y-type molecular sieve with the water content lower than 1 wt% and the reduced unit cell constant (calculated by dry basis) is 0.1-0.7: 1, carrying out contact reaction for 10 minutes to 5 hours at the temperature of 200-650 ℃, optionally washing and filtering to obtain a gas-phase ultra-stable modified Y-type molecular sieve;
(4) carrying out acid treatment modification on the gas-phase superstable modified Y-type molecular sieve obtained in the step (3); mixing the gas-phase ultra-stable modified Y-type molecular sieve obtained in the step (3) with inorganic acid with medium strength or higher and water, contacting at 80-99 ℃, preferably 90-98 ℃, for at least 30 minutes, such as 60-120 minutes, then adding organic acid, contacting at 80-99 ℃, preferably 90-98 ℃, for at least 30 minutes, such as 60-120 minutes, filtering, optionally washing and optionally drying to obtain the acid-treated modified Y-type molecular sieve; wherein the preferable weight ratio of the organic acid to the molecular sieve on a dry basis is 0.02-0.10: 1, the weight ratio of the inorganic acid with the medium strength or more to the molecular sieve based on a dry basis is 0.01-0.05: 1, the weight ratio of water to the molecular sieve is 5-20: 1.
(5) adding the acid-treated modified Y-type molecular sieve into an exchange solution containing a phosphorus compound, carrying out exchange reaction for 10-100 minutes at 15-100 ℃, filtering, washing and optionally drying; wherein the weight ratio of water to molecular sieve in the exchange liquid is 2-5, preferably 3-4, phosphorus (as P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.005 to 0.10, preferably 0.01 to 0.05.
The following examples further illustrate the invention but are not intended to limit the invention thereto.
In the examples and comparative examples, the NaY molecular sieve (also called NaY zeolite) was supplied by the chinese petrochemical catalyst co, zeuginese, inc, and had a sodium oxide content of 13.5 wt% and a framework silica to alumina ratio (SiO) of2/Al2O3Molar ratio) of 4.6, unit cell constant of 2.470nm, relative crystallinity of 90%; the chlorinated rare earth and the nitric acid rare earth are chemical pure reagents produced by Beijing chemical plants. The pseudoboehmite is an industrial product produced by Shandong aluminum factories, and has the solid content of 61 percent by weight; the kaolin is kaolin specially used for a cracking catalyst produced by Suzhou China kaolin company, and has the solid content of 76 weight percent; the alumina sol is provided by the company Qilu, China petrochemical catalyst, Inc.
The analysis method comprises the following steps: in each comparative example and example, the elemental content of the zeolite was determined by X-ray fluorescence spectroscopy; the unit cell constants and relative crystallinity of the zeolite were measured by X-ray powder diffraction (XRD) using RIPP 145-90 and RIPP146-90 standard methods (compiled by petrochemical analysis method (RIPP test method), Yankee et al, scientific Press, published in 1990), and the framework silica-alumina ratio of the zeolite was calculated from the following formula: SiO 22/Al2O3＝(2.5858-a0)×2/(a0-2.4191)]Wherein, a0Is the unit cell constant in nm; the total silicon-aluminum ratio of the zeolite is calculated according to the content of Si and Al elements measured by an X-ray fluorescence spectrometry, and the ratio of the framework Al to the total Al can be calculated by the framework silicon-aluminum ratio measured by an XRD method and the total silicon-aluminum ratio measured by an XRF method, so that the ratio of non-framework Al to the total Al can be calculated. The crystal structure collapse temperature was determined by Differential Thermal Analysis (DTA).
In each comparative example and example, the acid center type of the molecular sieve and its acid amount were determined by infrared analysis using pyridine adsorption. An experimental instrument: model Bruker IFS113V FT-IR (fourier transform infrared) spectrometer, usa. An experimental method for measuring the amount of B acid and the amount of L acid in total acid at 200 ℃ by using a pyridine adsorption infrared method comprises the following steps: and (3) carrying out self-supporting tabletting on the sample, and placing the sample in an in-situ cell of an infrared spectrometer for sealing. Heating to 400 deg.C, and vacuumizing to 10 deg.C-3And Pa, keeping the temperature for 2h, and removing gas molecules adsorbed by the sample. The temperature is reduced to room temperature, pyridine vapor with the pressure of 2.67Pa is introduced to keep the adsorption equilibrium for 30 min. Then heating to 200 ℃, and vacuumizing to 10 DEG C-3Desorbing for 30min under Pa, reducing to room temperature for spectrography, scanning wave number range: 1400cm-1～1700cm-1And obtaining the pyridine absorption infrared spectrogram of the sample desorbed at 200 ℃. According to the pyridine absorption1540cm in attached infrared spectrogram-1And 1450cm-1The strength of the adsorption peak is characterized to obtain the total content in the molecular sieve
Relative amount of acid center (B acid center) to Lewis acid center (L acid center).
In each of the comparative examples and examples, the secondary pore volume was determined as follows: measuring total pore volume of the molecular sieve according to adsorption isotherm, measuring micropore volume of the molecular sieve according to T mapping method from adsorption isotherm, subtracting micropore volume from total pore volume to obtain secondary pore volume,
the chemical reagents used in the comparative examples and examples are not specifically noted, and are specified to be chemically pure.
Example 1
2000Kg (dry basis) of SiO skeleton2/Al2O34.6 NaY zeolite (sodium oxide content 13.5 wt%, available from the Kikukushi company, China petrochemical catalyst, Qilu division) was charged in a vessel containing 20m3Stirring the mixture evenly at 25 ℃ in a primary exchange tank of water, and then adding 600L of RECl3Solutions (RECl)3Rare earth concentration in solution as RE2O3319g/L), stirring for 60 minutes, filtering, washing, and continuously feeding a filter cake into a flash evaporation drying furnace for drying; obtaining the rare earth-containing Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content, wherein the sodium oxide content is 7.0 weight percent, the unit cell constant is 2.471nm, and then sending the molecular sieve into a roasting furnace for modification: controlling the temperature of the material atmosphere at 390 ℃, and roasting for 6 hours under 50% of water vapor (the atmosphere contains 50% of water vapor by volume); then, introducing the molecular sieve material into a roasting furnace for roasting and drying, controlling the temperature of the material atmosphere at 500 ℃, and roasting for 2.5 hours in a dry air atmosphere (the water vapor content is lower than 1 volume percent) to ensure that the water content is lower than 1 weight percent; obtaining the Y-type molecular sieve with reduced unit cell constant, wherein the unit cell constant is 2.455nm, and then directly feeding the Y-type molecular sieve material with reduced unit cell constant into a continuous gas-phase ultrastable reactionThe gas phase ultra-stable reaction is carried out in the reactor, the gas phase ultra-stable reaction process of the molecular sieve in the continuous gas phase ultra-stable reactor and the subsequent tail gas absorption process are carried out according to the method disclosed in embodiment 1 of the CN103787352A patent, and the process conditions are as follows: SiCl4: weight ratio of Y-type zeolite 0.5: 1, the feed rate of the molecular sieve is 800 kg/h, and the reaction temperature is 400 ℃. Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3The water (2) was added to the molecular sieve material in the secondary exchange tank in an amount of 2000Kg (dry basis) by weight, stirred well, and then, 0.6m hydrochloric acid was added thereto in a concentration of 10% by weight3Heating to 90 ℃, continuing to stir for 60 minutes, then adding 140Kg of citric acid, continuing to stir for 60 minutes at 90 ℃, filtering, washing, and then directly adding the molecular sieve filter cake into an exchange solution containing ammonium phosphate, wherein the adding amount of the molecular sieve is as follows: phosphorus (in P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.04, wherein the weight ratio of water to the molecular sieve is 2.5, the exchange reaction is carried out for 60 minutes at the temperature of 50 ℃, the filtration and the washing are carried out, the rare earth and phosphorus-containing modified Y molecular sieve which is rich in secondary pores is obtained, the sampling and the drying are carried out, and the sample is recorded as SZ-1. Table 1 shows the composition of SZ-1, the unit cell constant, the relative crystallinity, the framework Si/Al ratio, the structural collapse temperature, the specific surface area, the percentage of the secondary pores with larger pore diameter (8 nm-100 nm) in the total secondary pores (2-100 nm), and the total secondary pore volume.
After SZ-1 is aged for 17 hours at 800 ℃, 1atm and 100 percent of water vapor in a naked state, the relative crystallinity of the molecular sieve before and after the SZ-1 is aged is analyzed by an XRD method and the relative crystallinity retention after the aging is calculated, and the result is shown in a table 2, wherein:
1048 g of pseudo-boehmite containing 61 wt% of alumina is taken and added into 5212 g of decationized water, 130ml of chemically pure hydrochloric acid (containing 36 wt% of HCl) is added under the stirring state, the mixture is aged for 1 hour at 70 ℃, then, 110ml of phosphoric acid (produced by Beijing chemical plant, the concentration of which is 85 percent and analytically pure) and 260 g of magnesium chloride hexahydrate (produced by Beijing bicyclic reagent plant, analytically pure) aqueous solution (wherein, 136 g of magnesium chloride hexahydrate) are added, and the slurry of alumina containing the additive is obtained after pulping.
3332 g of an alumina sol having an alumina content of 21% by weight was taken and added to 7300 g of decationized water, and 5395 g of kaolin having a solid content of 76% by weight was added under stirring and slurried for 60 minutes to obtain kaolin slurry. Adding 1574 g of pseudoboehmite containing 61 wt% of alumina into 6254 g of decationized water, pulping, adding 154ml of chemically pure hydrochloric acid (containing 36 wt% of HCl) under stirring, aging for 60 minutes, adding the prepared kaolin slurry, adding the prepared alumina slurry containing additive, pulping, adding 2400 g (dry basis) of SZ-1 molecular sieve and REY molecular sieve (produced by Zilu, Inc. of China petrochemical catalyst Co., Ltd.), and rare earth (as RE)2O3Calculated) 18 wt%, silicon to aluminum ratio (SiO)2/Al2O3Molar ratio 4.6)]400 g (dry basis), pulping, spray-drying at an inlet temperature of 650 ℃ and a tail gas temperature of 180 ℃, washing with deionized water, and drying to obtain the catalyst, which is marked as SC-1.
Example 2
2000Kg (dry basis) of SiO skeleton2/Al2O34.6 NaY zeolite (sodium oxide content 13.5 wt%, available from the Kikukushi company, China petrochemical catalyst, Qilu division) was charged in a vessel containing 20m3In a primary exchange tank for removing the cationic water, stirring uniformly at 90 ℃, and then adding 800L RECl3Solutions (RECl)3Rare earth concentration in solution as RE2O3319g/L) is counted, and stirring is carried out for 60 minutes; filtering, washing, and drying the filter cake in a flash drying furnace to obtain the rare earth-containing Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content, wherein the sodium oxide content is 5.5 weight percent, and the unit cell constant is 2.471 nm; then, the mixture is sent into a roasting furnace and roasted for 5.5 hours at the temperature (atmosphere temperature) of 450 ℃ under the atmosphere of 80 percent of water vapor; then, the molecular sieve material enters a roasting furnace to be roasted and dried, the roasting temperature is controlled to be 500 ℃, the atmosphere is dry air atmosphere, the roasting time is 2 hours, so that the water content is lower than 1 weight percent,obtaining the Y-type molecular sieve with reduced unit cell constant, wherein the unit cell constant is 2.461 nm; then, the Y-type molecular sieve material with the reduced unit cell constant is directly sent into a continuous gas phase hyperstable reactor for gas phase hyperstable reaction, the gas phase hyperstable reaction process of the molecular sieve in the continuous gas phase hyperstable reactor and the subsequent tail gas absorption process are carried out according to the method of embodiment 1 disclosed in the CN103787352A patent, and the process conditions are as follows: SiCl4: weight ratio of Y-type zeolite 0.25: 1, the feed rate of the molecular sieve was 800 kg/hour, and the reaction temperature was 490 ℃. Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3Adding the decationized water into a molecular sieve material in a secondary exchange tank, wherein the weight of the molecular sieve material is 2000Kg (dry basis), uniformly stirring, and then adding a sulfuric acid solution with the concentration of 7 weight percent, and the concentration of the sulfuric acid solution is 0.9m3Heating to 93 ℃, stirring for 80 minutes, adding 70Kg of citric acid and 50Kg of tartaric acid, stirring for 70 minutes at 93 ℃, filtering, washing, and directly adding the molecular sieve filter cake into an exchange solution containing diammonium hydrogen phosphate, wherein the adding amount of the molecular sieve is as follows: phosphorus (in P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.03, and the weight ratio of water to the molecular sieve is 3.0, the exchange reaction is carried out for 50 minutes at the temperature of 60 ℃, the filtration and the washing are carried out, the ultrastable Y molecular sieve which is rich in secondary pores and contains rare earth and phosphorus modification is obtained, the sampling and the drying are carried out, and the sample is recorded as SZ-2. Table 1 shows the composition of SZ-2, the percentage of the total secondary pores (2-100 nm) occupied by the unit cell constant, the relative crystallinity, the framework Si/Al ratio, the structural collapse temperature, the specific surface area and the secondary pores with larger pore diameter (8-100 nm), and the total secondary pore volume.
After aging SZ-2 in a naked state at 800 ℃ for 17 hours by 100% steam, the crystallinity of the zeolite before and after aging of the SZ-2 is analyzed by an XRD method and the relative crystal retention after aging is calculated, and the result is shown in Table 2.
984 g of pseudoboehmite containing 61 wt% of alumina was added to 4896 g of decationized water, 123ml of chemically pure hydrochloric acid (containing 36 wt% of HCl) was added under stirring, followed by aging at 70 ℃ for 1 hour, and thereafter 720 g of aqueous solution of magnesium chloride hexahydrate (411 g of magnesium chloride hexahydrate, analytical grade, available from beijing bicycnic reagent works) was added and slurried to obtain a slurry of alumina containing additives.
2856 g of an alumina sol having an alumina content of 21% by weight was added to 2502 g of decationized water, 5263 g of kaolin having a solid content of 76% by weight was added with stirring, and the mixture was pulped for 60 minutes to obtain kaolin slurry. 2949 g of pseudo-boehmite containing 61 wt% of alumina is added to 14691 g of decationized water, 321ml of hydrochloric acid (chemical purity, concentration 36 wt%) is added under stirring, after aging for 60 minutes, the prepared kaolin slurry is added and pulped, the prepared alumina slurry containing the additive is added and pulped, 3000 g (dry basis) of an SZ-2 molecular sieve is added, pulping is carried out, spray drying and washing treatment (same as example 1) are carried out, and the catalyst SC-2 is obtained after drying.
Example 3
2000Kg (dry basis) of SiO skeleton2/Al2O34.6 NaY zeolite (sodium oxide content 13.5 wt%, available from the Kikukushi company, China petrochemical catalyst, Qilu division) was charged in a vessel containing 20m3Stirring in a first exchange tank for removing cationic water at 95 deg.C, and adding 570L RECl3Solutions (RECl)3Rare earth concentration in solution as RE2O3319g/L), stirring for 60 minutes, filtering, washing, continuously feeding filter cakes into a flash drying furnace for drying to obtain the rare earth-containing Y-type molecular sieve with the normal unit cell size and the reduced sodium oxide content, wherein the sodium oxide content is 7.5 weight percent, and the unit cell constant is 2.471 nm; then, the mixture is sent into a roasting furnace for hydrothermal modification, and the hydrothermal modification conditions are as follows: roasting at 470 ℃ for 5 hours in an atmosphere containing 70 volume percent of water vapor; then, the molecular sieve material enters a roasting furnace to be roasted and dried, the roasting temperature is controlled to be 500 ℃, the roasting atmosphere is a dry air atmosphere, the roasting time is 1.5 hours, the water content is enabled to be lower than 1 weight percent, and the Y-type molecular sieve with the reduced unit cell constant is obtained, wherein the unit cell constant is 2.458 nm; then, the Y-shaped molecular sieve material with the reduced unit cell constant is sent into a continuous gas-phase ultra-stable reactor to carry out gas-phase ultra-stable reaction. Gas phase superstable reaction process of molecular sieve in continuous gas phase superstable reactor and its follow-upThe tail gas absorption process is carried out according to the method disclosed in embodiment 1 of the CN103787352A patent, and the process conditions are as follows: SiCl4: weight ratio of Y-type zeolite 0.45: 1, the feed rate of the molecular sieve is 800 kg/h, and the reaction temperature is 400 ℃. Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3Adding the decationized water into a molecular sieve material in a secondary exchange tank, wherein the weight of the molecular sieve material is 2000Kg (dry basis weight), uniformly stirring, and slowly adding a nitric acid solution with the concentration of 5 weight percent, namely 1.2m3Heating to 95 ℃, stirring for 90 minutes, then adding 90Kg of citric acid and 40Kg of oxalic acid, stirring for 70 minutes at 93 ℃, filtering, washing, and directly adding the molecular sieve filter cake into an exchange solution containing ammonium phosphate, wherein the adding amount of the molecular sieve is as follows: phosphorus (in P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.015, the weight ratio of water to the molecular sieve is 2.8, the exchange reaction is carried out for 30 minutes at the temperature of 70 ℃, the filtration and the washing are carried out, the ultrastable Y molecular sieve which is rich in secondary pores and contains rare earth and phosphorus modification is obtained, the sampling and the drying are carried out, and the sample is marked as SZ-3. Table 1 shows the composition of SZ-3, the percentage of the total secondary pores (2-100 nm) occupied by the unit cell constant, the relative crystallinity, the framework Si/Al ratio, the structural collapse temperature, the specific surface area and the secondary pores with larger pore diameter (80-100 nm), and the total secondary pore volume. After aging SZ-3 in a naked state at 800 ℃ for 17 hours by 100% steam, the crystallinity of the zeolite before and after aging of SZ-3 is analyzed by an XRD method and the relative crystal retention after aging is calculated, and the result is shown in Table 2.
1312 g of pseudo-boehmite containing 61 wt.% of alumina was taken and added to 6528 g of decationized water, 164ml of chemically pure hydrochloric acid (HCl content 36 wt.%) was added with stirring and aged at 70 ℃ for 1 hour, then 392ml of phosphoric acid (85% strength, analytical purity, manufactured by Beijing chemical plant) was added and slurried to obtain an additive-containing alumina slurry.
3808 g of alumina sol having an alumina content of 21 wt% was added to 6088 g of decationized water, 9123 g of kaolin having a solid content of 76 wt% was added under stirring, and the mixture was slurried for 60 minutes to obtain kaolin slurry. 5244 g of pseudo-boehmite containing 61 wt% of alumina is added into 16931 g of decationized water, 568ml of chemically pure hydrochloric acid (concentration: 36 wt%) is added under stirring, after aging for 60 minutes, the prepared kaolin slurry is added, and then the prepared alumina slurry containing the additive is added, and then the slurry is added, and then 4000 g (dry basis) of SZ-3 molecular sieve, 539 g (dry basis) of REY molecular sieve (same as example 1) and 500 g (dry basis) of ZRP-5 molecular sieve (produced by china petrochemical catalyst company, ltd., rare earth content: 0.5 wt%, silica-alumina ratio: 45) are added, and the slurry is subjected to spray drying and washing treatment (same as example 1), and dried to obtain the catalyst, which is marked as SC-3.
Comparative example 1
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 deg.C, holding for 1 hr, filtering, washing, drying at 120 deg.C, performing hydrothermal modification treatment (at 650 deg.C, roasting with 100% water vapor for 5 hr), adding into 20L of decationized water solution, stirring, mixing, adding 1000 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out second hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours) to obtain the rare earth-free hydrothermal ultrastable Y-type molecular sieve which is subjected to twice ion exchange and twice hydrothermal ultrastable, and is marked as DZ-1. Table 1 shows the composition of DZ-1, the percentage of the total secondary pores (2-100 nm) occupied by the unit cell constant, the relative crystallinity, the framework Si/Al ratio, the structural collapse temperature, the specific surface area, and the secondary pores with larger pore diameters (8-100 nm), and the total secondary pore volume. After aging DZ-1 in the bare state at 800 ℃ for 17 hours with 100% steam, the crystallinity of the zeolite before and after aging DZ-1 was analyzed by XRD and the relative crystal retention after aging was calculated, the results are shown in Table 2.
714.5 g of an alumina sol having an alumina content of 21% by weight were added to 1565.5 g of decationized water, stirring was started, and 2763 g of kaolin having a solids content of 76% by weight were added and dispersed for 60 minutes. 2049 g of pseudo-boehmite with the alumina content of 61 wt% is taken and added into 8146 g of decationized water, 210ml of hydrochloric acid with the mass concentration of 36% is added under the stirring state, dispersed kaolin slurry is added after acidification is carried out for 60 minutes, 1500 g (dry basis) of finely ground DZ-1 molecular sieve is added, after uniform stirring, spray drying and washing treatment are carried out, and the catalytic cracking catalyst is obtained by drying and is recorded as DC-1. Wherein, the obtained DC-1 catalyst contains 30 weight percent of DZ-1 molecular sieve, 42 weight percent of kaolin, 25 weight percent of pseudo-boehmite and 3 weight percent of alumina sol.
Comparative example 2
2000 g of NaY molecular sieve (dry basis) is added into 20L of decationized aqueous solution, stirred to be uniformly mixed, and 1000 g of (NH) is added4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, drying a filter cake at 120 ℃, and then carrying out hydrothermal modification treatment, wherein the conditions of the hydrothermal modification treatment are as follows: roasting with 100% steam at 650 deg.C for 5 hr, adding into 20L of decationized water solution, stirring, adding 200ml of RE (NO)3)3Solutions (with RE)2O3The concentration of the rare earth solution is measured as follows: 319g/L) and 900 g (NH)4)2SO4Stirring, heating to 90-95 ℃, keeping for 1 hour, filtering, washing, drying a filter cake at 120 ℃, and then performing second hydrothermal modification treatment (roasting at 650 ℃ under 100% of water vapor for 5 hours) to obtain the rare earth-containing hydrothermal ultrastable Y-type molecular sieve marked as DZ2, wherein the hydrothermal ultrastable Y-type molecular sieve is hydrothermally ultrastable twice through ion exchange twice. Table 1 shows the composition of DZ-2, the percentage of the total secondary pores (2-100 nm) occupied by the unit cell constant, the relative crystallinity, the framework Si/Al ratio, the structural collapse temperature, the specific surface area, and the secondary pores with larger pore diameters (8-100 nm), and the total secondary pore volume. After aging DZ-2 in the bare state at 800 ℃ for 17 hours with 100% steam, the crystallinity of the zeolite before and after aging DZ-2 was analyzed by XRD and the relative crystal retention after aging was calculated, the results are shown in Table 2.
DZ-2 molecular sieve, kaolin, water, pseudo-boehmite binder and alumina sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as DC-2 (refer to the preparation method of comparative example 1). Wherein the obtained DC-2 catalyst contains 30 wt% of DZ-2 molecular sieve, 42 wt% of kaolin, 25 wt% of pseudo-boehmite and 3 wt% of alumina sol on a dry basis.
Comparative example 3
2000kg of NaY molecular sieve (dry basis) was added to 20m3Stirring in water to mix well, adding 650L RE (NO)3)3Stirring the solution (319g/L), heating to 90-95 ℃, keeping for 1 hour, then filtering, washing, continuously feeding the filter cake into a flash evaporation and roasting furnace for roasting and drying, controlling the roasting temperature to be 500 ℃, the roasting atmosphere to be a dry air atmosphere, roasting for 2 hours to enable the water content to be lower than 1 weight percent, and then feeding the dried molecular sieve material into a continuous gas-phase ultrastable reactor for gas-phase ultrastable reaction. The gas phase hyperstable reaction process of the molecular sieve in the continuous gas phase hyperstable reactor and the subsequent tail gas absorption process are carried out according to the method disclosed in embodiment 1 of the CN103787352A patent, and the process conditions are as follows: SiCl4: weight ratio of Y-type zeolite 0.4: 1, the feed rate of the molecular sieve is 800 kg/h, and the reaction temperature is 580 ℃. Separating the molecular sieve material after gas phase superstable reaction by a gas-solid separator, and feeding into a secondary exchange tank, wherein 20m is added in advance in the secondary exchange tank3The water (2) is added into a molecular sieve material in a secondary exchange tank, the weight of the molecular sieve material is 2000Kg (dry basis), the mixture is stirred evenly, and then 5 weight percent of nitric acid with the weight of 1.2m is slowly added3Heating to 95 ℃, continuing to stir for 90 minutes, then adding 90Kg of citric acid and 40Kg of oxalic acid, continuing to stir for 70 minutes at 93 ℃, filtering, washing, and then directly adding the molecular sieve filter cake into an exchange solution containing ammonium phosphate, wherein the adding amount of the molecular sieve is as follows: phosphorus (in P)2O5Calculated) and the weight ratio of the molecular sieve is as follows: 0.015, the weight ratio of water to molecular sieve is 2.8, exchange reaction is carried out for 30 minutes under the condition of 70 ℃, filtration, washing, sampling and drying are carried out, and the sample is marked as DZ-3. Table 1 shows the composition of DZ-3, the cell constant, the relative crystallinity, the framework Si/Al ratio, the structural collapse temperature, the specific surface area and the total secondary pores (2-100 nm) occupied by the secondary pores with larger pore diameter (8-100 nm)Percent, total secondary pore volume. After aging DZ-3 in the bare state at 800 ℃ for 17 hours with 100% steam, the crystallinity of the zeolite before and after aging DZ-3 was analyzed by XRD and the relative crystal retention after aging was calculated, the results are shown in Table 2.
DZ-3 molecular sieve, kaolin, water, pseudo-boehmite binder and alumina sol are formed into slurry according to a conventional preparation method of a catalytic cracking catalyst, the slurry is spray-dried to prepare a microspherical catalyst, and the prepared catalytic cracking catalyst is marked as DC-3 (refer to the preparation method of comparative example 1). Wherein, the obtained DC-3 catalyst contains 30 weight percent of DZ-3 molecular sieve, 42 weight percent of kaolin, 25 weight percent of pseudo-boehmite and 3 weight percent of alumina sol.
Comparative example 4
A catalyst was prepared by following the procedure of example 2 except that the molecular sieve SZ2 was replaced with the molecular sieve DZ3 prepared in comparative example 3 to obtain catalyst DC-4.
Examples 4 to 6
The catalysts prepared in examples 1 to 3 were evaluated for light oil microreflection. The catalysts SC-1, SC-2 and SC-3 prepared in examples 1 to 3 were subjected to 100% steam aging at 800 ℃ for 4 hours or 17 hours, respectively, and then the light oil micro-reactivities of the catalysts were evaluated, and the evaluation results are shown in Table 3. Evaluation method of light oil micro-inverse activity:
the light oil micro-reverse activity of the sample is evaluated by adopting a standard method of RIPP92-90 (see the edition of petrochemical analysis method (RIPP test method), Yangcui et al, scientific publishing company, published in 1990), the catalyst loading is 5.0g, the reaction temperature is 460 ℃, the raw oil is Hongkong light diesel oil with the distillation range of 235-337 ℃, the product composition is analyzed by gas chromatography, and the light oil micro-reverse activity is calculated according to the product composition.
Light oil Microreactivity (MA) (gasoline production at less than 216 ℃ in product + gas production + coke production)/total feed × 100%.
Comparative examples 5 to 8
Comparative examples 5-8 illustrate the catalytic cracking activity and stability of the ultrastable Y-type molecular sieves prepared by the methods provided in comparative examples 1-4.
The light oil micro-reactivities of DC-1, DC-2, DC-3 and DC-4 catalysts were evaluated after 100% steam aging at 800 ℃ for 4 hours or 17 hours. See example 6 for evaluation, and the results are shown in Table 3.
TABLE 1
As can be seen from table 1, the high-stability modified Y-type molecular sieve provided by the present invention has the following advantages: the content of sodium oxide is low, the non-framework aluminum content is low when the silicon-aluminum content of the molecular sieve is high, the pore volume of 2.0-100 nm secondary pores in the molecular sieve accounts for the volume percentage of the total pores, the ratio of B acid/L acid (the total amount of B acid to the amount of L acid) is high, the crystallinity value measured when the content of rare earth is high when the unit cell constant of the molecular sieve is small is high, and the thermal stability is high.
TABLE 2
As can be seen from Table 2, the modified Y-type molecular sieve provided by the invention has higher relative crystal retention after being aged under the harsh conditions of 800 ℃ and 17 hours in the exposed state of the molecular sieve sample, which indicates that the modified Y-type molecular sieve provided by the invention has high hydrothermal stability.
Examples 7 to 9
Examples 7-9 illustrate the catalytic cracking reaction performance of the modified Y-type molecular sieve provided by the invention.
After the SC-1, SC-2 and SC-3 catalysts are aged for 17 hours at 800 ℃ under the atmosphere of 100 percent of water vapor, the catalytic cracking reaction performance of the catalysts is evaluated on a small-sized fixed fluidized bed reactor (ACE), and cracked gas and product oil are respectively collected and analyzed by gas chromatography. The catalyst loading is 9g, the reaction temperature is 500 ℃, and the weight hourly space velocity is 16h－1The weight ratio of the base oil is shown in Table 5, the properties of the raw materials for the ACE test are shown in Table 4, and the evaluation results are shown in Table 5.
TABLE 3 catalyst microreactivity
TABLE 4 ACE evaluation of raw oil Properties
Comparative examples 9 to 12
Comparative examples 7-9 illustrate the catalytic cracking reaction performance of the catalytic cracking catalysts prepared by the methods provided in comparative examples 1-4.
After aging DC-1, DC-2, DC-3 and DC-4 catalysts with 100% steam at 800 deg.C for 17 hours, the catalytic cracking reaction performance was evaluated in a small fixed fluidized bed reactor (ACE), the evaluation method was the same as example 7, the raw material properties of the ACE experiment are shown in Table 4, and the evaluation results are shown in Table 5.
TABLE 5
As can be seen from the results shown in tables 3 and 5, the catalytic cracking catalyst provided by the present invention has high hydrothermal stability, significantly lower coke selectivity, significantly higher liquid yield, significantly higher light oil yield, higher gasoline yield, and higher heavy oil conversion activity.
Claims (30)
1. A catalytic cracking catalyst comprises 10-50 wt% of phosphorus-containing and rare earth-modified Y-type molecular sieve, 2-40 wt% of alumina containing an additive and 10-80 wt% of clay on a dry basis, wherein the weight of the Y-type molecular sieve is calculated on a dry basis; wherein, the alumina containing the additive contains 60 to 99.5 weight percent of alumina and 0.5 to 40 weight percent of additive on a dry basis, and the additive is selected from one or more compounds containing alkaline earth metal, lanthanide metal, silicon, gallium, boron or phosphorus; the content of the rare earth oxide of the phosphorus-containing and rare earth-modified Y-type molecular sieve is 4-11 wt%, and the phosphorus content is P2O50.05 to 10 wt% of sodium oxideThe weight of the molecular sieve is not more than 0.5 percent, the total pore volume is 0.36 mL/g-0.48 mL/g, the pore volume of secondary pores with the pore diameter of 2 nm-100 nm of the phosphorus-containing and rare earth modified Y-shaped molecular sieve accounts for 20 percent-40 percent of the total pore volume, the unit cell constant is 2.440 nm-2.455 nm, the non-framework aluminum content of the phosphorus-containing and rare earth modified Y-shaped molecular sieve accounts for not more than 10 percent of the total aluminum content, the lattice collapse temperature is not lower than 1060 ℃, and the ratio of the B acid amount to the L acid amount in the total acid amount of the phosphorus-containing and rare earth modified Y-shaped molecular sieve measured by a pyridine adsorption infrared method at 200 ℃ is not lower than 3.5.
2. The catalytic cracking catalyst of claim 1, wherein the pore volume of the secondary pores with the pore diameter of 2nm to 100nm in the phosphorus-containing and rare earth-modified Y-type molecular sieve accounts for 28% to 38% of the total pore volume.
3. The catalytic cracking catalyst of claim 1, wherein the phosphorus-containing and rare earth-modified Y-type molecular sieve has a non-framework aluminum content of 5-9.5 wt% of total aluminum content, and a framework silicon-aluminum ratio of SiO2/Al2O3The molar ratio is 7-14.
4. The catalytic cracking catalyst of claim 1, wherein the phosphorus-containing and rare earth-modified Y-type molecular sieve has a lattice collapse temperature of 1065-1085 ℃.
5. The catalytic cracking catalyst of claim 1, wherein the ratio of the amount of B acid to the amount of L acid in the total acid amount of the phosphorus-and rare earth-modified Y-type molecular sieve measured at 200 ℃ by pyridine adsorption infrared method is 3.5 to 6.
6. The catalytic cracking catalyst of claim 1, wherein the phosphorus-containing and rare earth-modified Y-type molecular sieve has a relative crystal retention of 38% or more after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
7. The catalytic cracking catalyst of claim 6, wherein the relative crystal retention of the phosphorus-containing and rare earth-modified Y-type molecular sieve is 38-60% after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
8. The catalytic cracking catalyst of claim 6, wherein the relative crystal retention of the phosphorus-containing and rare earth-modified Y-type molecular sieve is 50-60% after aging at 800 ℃ under normal pressure in a 100% steam atmosphere for 17 hours.
9. The catalytic cracking catalyst of claim 1, wherein the phosphorus-containing and rare earth-modified Y-type molecular sieve has a relative crystallinity of 70-80%.
10. The catalytic cracking catalyst of any one of claims 1 to 9, wherein the phosphorus-and rare earth-containing modified Y-type molecular sieve has a rare earth oxide content of 4.5 to 10 wt%, and the phosphorus content is P2O50.1 to 6 wt%, sodium oxide content of 0.05 to 0.3 wt%, cell constant of 2.442 to 2.451nm, and framework Si/Al ratio of SiO2/Al2O3The molar ratio is 8.5-12.6.
11. The catalytic cracking catalyst of claim 1, wherein the ratio of the pore volume of secondary pores with a pore diameter of 8-100 nm to the pore volume of total secondary pores with a pore diameter of 2-100 nm in the phosphorus-containing and rare earth-modified Y-type molecular sieve is 40-80%.
12. The catalytic cracking catalyst of claim 1, wherein the catalyst comprises 25 wt% to 40 wt% of the phosphorus-containing and rare earth-modified Y-type molecular sieve on a dry basis, 2 wt% to 20 wt% of the additive-containing alumina on a dry basis, 5 wt% to 30 wt% of an alumina binder on a dry basis, and 30 wt% to 50 wt% of clay on a dry basis.
13. The catalytic cracking catalyst of claim 1, wherein the clay is selected from one or more of kaolin, montmorillonite, diatomaceous earth, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, bentonite;
the preparation method of the alumina containing the additive comprises the following steps:
(1) mixing the pseudoboehmite with water and acid sufficient to slurry the pseudoboehmite under agitation, wherein the acid is used in an amount such that the weight ratio of the acid to the alumina in the pseudoboehmite is from 0.01 to 0.5;
(2) aging the mixed slurry obtained in the step (1) at room temperature to 90 ℃ for 0 to 24 hours;
(3) mixing the product of step (2) with additives, optionally drying and optionally calcining.
14. A preparation method of the catalytic cracking catalyst of any one of claims 1 to 13, comprising the steps of preparing a phosphorus-containing and rare earth-modified Y-type molecular sieve, forming a slurry comprising the phosphorus-containing and rare earth-modified Y-type molecular sieve, additive-containing alumina, clay and water, and spray-drying, wherein the additive-containing alumina contains 60 wt% to 99.5 wt% of alumina and 0.5 wt% to 40 wt% of an additive, based on the weight of the additive-containing alumina, and the additive is one or more selected from compounds containing alkaline earth metals, lanthanide metals, silicon, gallium, boron or phosphorus elements; the preparation method of the phosphorus-containing and rare earth-modified Y-type molecular sieve comprises the following steps:
(1) contacting the NaY molecular sieve with a rare earth salt solution to perform an ion exchange reaction, filtering, washing, and optionally drying to obtain a rare earth-containing Y-type molecular sieve with a conventional unit cell size and reduced sodium oxide content;
(2) roasting the rare earth-containing Y-type molecular sieve with the conventional unit cell size and the reduced sodium oxide content for 4.5-7 hours at the temperature of 350-480 ℃ in the atmosphere of 30-90 vol% of water vapor, and optionally drying to obtain the Y-type molecular sieve with the reduced unit cell constant;
(3) according to SiCl4: reduced Y of the unit cell constant on a dry basisThe type molecular sieve is 0.1-0.7: 1, carrying out contact reaction on the Y-type molecular sieve with the reduced unit cell constant and silicon tetrachloride gas at the reaction temperature of 200-650 ℃ for 10 minutes to 5 hours, and optionally washing and filtering to obtain a gas-phase ultrastable modified Y-type molecular sieve;
(4) contacting the gas-phase ultra-stable modified Y-shaped molecular sieve obtained in the step (3) with an acid solution;
(5) and (4) contacting the molecular sieve obtained in the step (4) and the acid solution with a phosphorus compound for phosphorus modification treatment.
15. The process of claim 14, wherein the rare earth-containing Y-type molecular sieve having a conventional unit cell size and a reduced sodium oxide content in step (1) has a unit cell constant of 2.465 to 2.472nm and a sodium oxide content of not more than 9.0 wt.%.
16. The process of claim 14, wherein in step (1), the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content and a conventional unit cell size contains rare earth in an amount of RE2O34.5 to 13 wt%, sodium oxide content 4.5 to 9.5 wt%, and unit cell constant 2.465nm to 2.472 nm.
17. The method of claim 16, wherein the rare earth-containing Y-type molecular sieve having a reduced sodium oxide content comprises from 5.5 to 8.5 wt% of sodium oxide in the rare earth-containing Y-type molecular sieve.
18. The method of claim 14, wherein the step (1) of contacting the NaY molecular sieve with the rare earth salt solution for ion exchange reaction is: according to the NaY molecular sieve: rare earth salt: h2O is 1: 0.01-0.18: 5-20, mixing NaY molecular sieve, rare earth salt and water, and stirring.
19. The method of claim 14 or 18, wherein the step (1) of contacting the NaY molecular sieve with the rare earth solution for an ion exchange reaction comprises: mixing NaY molecular sieve with decationized water, stirring, adding rare earth salt and/or rare earth salt solution to perform ion exchange reaction, filtering, and washing; the conditions of the ion exchange reaction are as follows: the exchange temperature is 15-95 ℃, the exchange time is 30-120 minutes, and the rare earth salt solution is a rare earth salt water solution.
20. The method of claim 14, wherein the rare earth salt is a rare earth chloride or a rare earth nitrate and the phosphorus compound is one or more selected from the group consisting of phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.
21. The method as claimed in claim 14, wherein the roasting temperature in step (2) is 380-460 ℃, the roasting atmosphere is 40-80% steam atmosphere, and the roasting time is 5-6 hours.
22. The method according to claim 14, wherein the unit cell constant of the Y-type molecular sieve with reduced unit cell constant obtained in step (2) is 2.450nm to 2.462nm, and the water content of the Y-type molecular sieve with reduced unit cell constant is not more than 1 wt%.
23. The method according to claim 14, wherein the washing method in step (3) is washing with water under the following washing conditions: molecular sieve: h2The weight ratio of O =1: 6-15, the pH value is 2.5-5.0, and the washing temperature is 30-60 ℃.
24. The method according to claim 14, wherein the gas phase ultrastable modified Y-type molecular sieve obtained in step (3) is contacted with an acid solution in the weight ratio of acid to molecular sieve of 0.001-0.15 in step (4): 1, the weight ratio of water to the molecular sieve is 5-20: 1, the acid is one or more of organic acid and inorganic acid, the contact time is more than 60 minutes, and the contact temperature is 80-99 ℃.
25. The method according to claim 24, wherein the gas phase ultrastable modified Y-type molecular sieve obtained in the step (3) is contacted with the acid solution in the step (4) for 1-4 hours.
26. The method according to claim 14, wherein the step (4) of contacting with the acid solution comprises an organic acid and an inorganic acid with a medium strength or higher, wherein the weight ratio of the inorganic acid with a medium strength or higher to the molecular sieve is 0.01-0.05: 1, the weight ratio of the organic acid to the molecular sieve is 0.02-0.10: 1, the weight ratio of water to the molecular sieve is 5-20: 1, the contact temperature is 80-99 ℃, and the contact time is 1-4 hours.
27. The method according to claim 14, wherein the contacting with the acid solution in step (4) comprises contacting with a medium-strength or higher inorganic acid, and then contacting with an organic acid, under the conditions of: the weight ratio of the inorganic acid with the medium strength to the molecular sieve is 0.01-0.05: 1, the weight ratio of water to the molecular sieve is 5-20: 1, the contact time is: the contact temperature is 90-98 ℃ for 60-120 minutes; the contact conditions with the organic acid are as follows: the weight ratio of the organic acid to the molecular sieve is 0.02-0.10: 1, the weight ratio of water to the molecular sieve is 5-20: 1, the contact time is: the contact temperature is 90-98 ℃ for 60-120 minutes.
28. The method of claim 26 or 27, wherein the organic acid is one or more of oxalic acid, malonic acid, succinic acid, methylsuccinic acid, malic acid, tartaric acid, citric acid, salicylic acid; the inorganic acid with the medium strength or more is one or more of phosphoric acid, hydrochloric acid, nitric acid and sulfuric acid.
29. The method of claim 14, wherein the phosphorus modification treatment conditions of step (5) are: contacting the molecular sieve obtained in the step (4) after contacting with the acid solution with an exchange liquid containing a phosphorus compound in the temperature of 15 DEG to 15 DEGCarrying out exchange reaction for 10-100 minutes at 100 ℃, filtering and washing; wherein in a mixture formed by contacting the exchange liquid with the molecular sieve, the weight ratio of water to the molecular sieve is 2-5, and P is used2O5The weight ratio of the phosphorus to the molecular sieve is 0.0005-0.10.
30. The method of claim 29, wherein the phosphorus modification treatment conditions of step (5) are such that the weight ratio of water to molecular sieve is 3 to 4, expressed as P2O5The weight ratio of the phosphorus to the molecular sieve is 0.001-0.06.
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| CN201710096449.6A CN108452833B (en) | 2017-02-22 | 2017-02-22 | Catalytic cracking catalyst |
| GB1911860.3A GB2573252B (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| US16/484,418 US10888848B2 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| RU2019126112A RU2755891C2 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and its preparation |
| JP2019565603A JP7083360B2 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and its production method |
| MYPI2019004689A MY191917A (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| PCT/CN2018/076430 WO2018153302A1 (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation method therefor |
| SG11201907656VA SG11201907656VA (en) | 2017-02-22 | 2018-02-12 | Catalytic cracking catalyst and preparation thereof |
| TW107105496A TWI760436B (en) | 2017-02-22 | 2018-02-14 | Catalytic cracking catalyst and preparation method thereof |
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| WO2020035016A1 (en) * | 2018-08-17 | 2020-02-20 | 中国石油化工股份有限公司 | Modified y-type molecular sieve, catalytic cracking catalyst comprising same, and preparation therefor and application thereof |
| WO2020038350A1 (en) * | 2018-08-20 | 2020-02-27 | 中国石油化工股份有限公司 | Modified y-shaped molecular sieve, catalytic cracking catalyst containing same, preparation method and application thereof |
| CN115703069B (en) * | 2021-08-11 | 2024-07-12 | 中国石油化工股份有限公司 | Phosphorus-containing catalytic cracking catalyst and preparation method thereof |
| CN115232643B (en) * | 2022-09-22 | 2022-11-25 | 潍坊弘润石化科技有限公司 | Hydrocracking method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388064A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
| CN1958452A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for raising content of rare earth of ultra stable Y type zeolite |
| CN101285001A (en) * | 2007-04-12 | 2008-10-15 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
-
2017
- 2017-02-22 CN CN201710096449.6A patent/CN108452833B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1388064A (en) * | 2001-05-30 | 2003-01-01 | 中国石油化工股份有限公司 | Prepn of high-silicon Y-Zeolite |
| CN1958452A (en) * | 2005-10-31 | 2007-05-09 | 中国石油化工股份有限公司 | Method for raising content of rare earth of ultra stable Y type zeolite |
| CN101285001A (en) * | 2007-04-12 | 2008-10-15 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
| CN101745418A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst, preparation and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 稀土改性 Y 型分子筛的研究;王栋等;《石化技术与应用》;20131130;第31卷(第6期);第489-492页 * |
| 超稳Y分子筛的化学改性研究;赵建辉;《齐鲁石油化工》;20000331;第28卷(第1期);第36-39页 * |
| 高硅铝比Y分子筛的制备与表征;韩宝斋等;《中国化学会第30届学术年会摘要集-第三十二分会： 多孔功能材料》;20160731;第43页 * |
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