CN112209401B - Modification method and rare earth Y-type molecular sieve - Google Patents

Modification method and rare earth Y-type molecular sieve Download PDF

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CN112209401B
CN112209401B CN201910612796.9A CN201910612796A CN112209401B CN 112209401 B CN112209401 B CN 112209401B CN 201910612796 A CN201910612796 A CN 201910612796A CN 112209401 B CN112209401 B CN 112209401B
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rare earth
molecular sieve
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ammonium
water
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CN112209401A (en
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王成强
罗一斌
郑金玉
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Priority to EP20837442.1A priority patent/EP3998118A4/en
Priority to US17/626,087 priority patent/US20220259055A1/en
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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Abstract

A method for modifying a Y-type molecular sieve comprises the following steps: the method comprises the step of contacting a rare earth NaY molecular sieve with an alkaline substance to obtain the rare earth NaY molecular sieve containing the alkaline substance, and carrying out hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, wherein the apparent pressure of the atmosphere environment is 0.01-1 Mpa and the atmosphere environment contains 1-100% of water vapor.

Description

Modification method and rare earth Y-type molecular sieve
Technical Field
The invention relates to a modification method and a rare earth Y-type molecular sieve obtained by the modification method.
Background
Catalytic cracking is the most important production technology in oil refineries today, and catalytic cracking units are used to convert heavy oils and residues into gasoline, diesel, and light gas components. In the industry, a catalytic cracking unit must comprise two parts of reaction and high-temperature regeneration of a catalyst, so that the catalyst needs to consider the factors of catalytic activity, selectivity and the like, and compared with other types of molecular sieves, the Y-type molecular sieve is more used in a cracking reaction and has the main function of producing gasoline-range molecular products in a catalytic cracking catalyst as an active component of the catalytic cracking catalyst.
The rare earth exchanged rare earth Y molecular sieve is a high-activity component of the catalytic cracking catalyst. Rare earth ions in the rare earth Y molecular sieve migrate from the supercage to the sodalite cage and form an oxygen-bridge-containing multi-core cation structure, so that the stability of an acid center of the molecular sieve in a high-temperature hydrothermal environment is improved, the cracking activity and the activity stability of the molecular sieve catalyst are improved, and the heavy oil conversion activity and the selectivity of the catalyst are improved. But when the NaY molecular sieve is ion-exchanged with the aqueous solution of rare-earth saltAlternatively, hydrated rare earth ions having a diameter of about 0.79nm are difficult to enter the sodalite cage through the six-membered ring window of the Y molecular sieve (having a diameter of about 0.26 nm). Therefore, during the preparation of the rare earth Y molecular sieve, the hydrated layer around the rare earth ions must be removed by calcination, so that the rare earth ions can enter into the sodalite cages and the hexagonal prisms, and the sodium ions in the cages are moved out to the supercages by the calcination process, in short, the calcination accelerates the intracrystalline exchange between solid ions, and the molecular sieve is mixed with other cations such as NH in the aqueous solution4 +、RE3+Exchange of (2) and reduction of Na of molecular sieves+Conditions for content creation (USP 3402996). Therefore, how to promote the migration of rare earth ions and improve the occupancy of rare earth ions on the position (in a small cage) of a lockable cation directly relates to the performance of the rare earth Y molecular sieve and influences the activity stability of the catalyst taking the rare earth Y molecular sieve as an active component. In order to promote the migration of rare earth ions into sodalite cages, high-temperature roasting or high-temperature hydrothermal roasting is generally adopted in the industry, however, in addition to the more severe requirements on the material of the industrial roasting furnace, the rare earth ions which are locked have the tendency to return to large cages (Zeolite, 6(4), 235, 1986). The current technical situation of industrial roasting is as follows: NaY and RE3+The rare earth NaY (sodium oxide content is 4.5-6.0%) molecular sieve filter cake obtained after exchange needs to be subjected to solid ion exchange at high temperature roasting (550-580 ℃), and then the sodium is removed by aqueous solution exchange.
The current major problem is that the degree of solid-state ion exchange needs to be further improved. Therefore, how to make as many rare earth ions migrate to the small cage position as possible at a limited calcination temperature to further improve the stability of the molecular sieve becomes a great technical problem to be solved industrially.
CN1026225C discloses a method for preparing rare earth Y molecular sieve, which comprises the following steps of mixing NaY molecular sieve with RE3+After ion exchange in water solution, roasting in 100% flowing water vapor at 450-600 deg.c for 1-3 hr.
The method comprises the steps of carrying out contact treatment on a NaY molecular sieve and a rare earth salt solution or a mixed solution of ammonium salt and a rare earth salt solution, filtering, washing, drying and then carrying out roasting treatment to obtain a rare earth sodium Y molecular sieve; then pulping the rare earth sodium Y molecular sieve, contacting with an ammonium salt solution, then not filtering, mixing with a rare earth salt solution, and adjusting the pH value of the slurry by using an alkaline liquid to perform rare earth deposition, or pulping the rare earth sodium Y molecular sieve, then performing contact treatment with a mixed solution of the ammonium salt solution and the rare earth salt solution, adjusting the pH value of the slurry by using the alkaline liquid to perform rare earth deposition, filtering and drying, and performing secondary roasting treatment to obtain the rare earth Y molecular sieve. The method needs to pass through the processes of two-phase exchange and two-baking and combined deposition of rare earth.
Disclosure of Invention
The invention aims to provide a simpler and low-cost modification method for improving the solid state ion exchange degree of REY.
Therefore, the modification method of the Y-type molecular sieve provided by the invention comprises the following steps: the method comprises the step of contacting a rare earth NaY molecular sieve with an alkaline substance to obtain the rare earth NaY molecular sieve containing the alkaline substance, and carrying out hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, wherein the apparent pressure of the atmosphere environment is 0.01-1 MPa and the atmosphere environment contains 1-100% of water vapor.
The modification method of the invention, wherein the rare earth NaY molecular sieve is preferably obtained by the steps A of carrying out contact treatment on the NaY molecular sieve and a rare earth salt solution or a mixed solution of the rare earth salt solution and an ammonium salt, and carrying out filtration, water washing and drying treatment; the rare earth salt solution in the step A contains chloride aqueous solution containing one or more of lanthanum, cerium, praseodymium and neodymium ions. The ammonium salt in the step A is selected from any one or a mixture of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate. The contact treatment of the NaY molecular sieve and the rare earth salt solution or the mixed solution of the ammonium salt and the rare earth salt solution is generally carried out in the step A, wherein the NaY molecular sieve and the rare earth salt solution or the mixed solution of the ammonium salt and the rare earth salt solution are exchanged for at least 0.3 hour at the temperature of room temperature to 100 ℃ under the conditions that the pH of slurry is 3.0-5.0, the weight ratio of water sieve is 5-30.
The modification method of the invention, wherein the alkaline substance is selected from one or more of ammonia water, a buffer solution of ammonia water and ammonium chloride, sodium hydroxide, sodium metaaluminate, sodium carbonate, sodium bicarbonate and the like; the contact with the basic substance may be carried out by a conventional method such as impregnation or supporting.
In the modification method of the present invention, the hydrothermal calcination treatment is performed under an atmosphere environment in which external pressure is applied and water is added to the outside. The atmosphere is obtained by applying external pressure and water, preferably apparent pressure is 0.1-0.8 MPa, more preferably apparent pressure is 0.3-0.6 MPa, preferably 30-100% water vapor, more preferably 60-100% water vapor. The external pressure application refers to applying a certain pressure to the preparation material in the hydrothermal roasting treatment process from the outside, and for example, the external pressure application may be performed by introducing an inert gas from the outside to maintain a certain back pressure. The amount of water applied to the outside is based on the condition that the atmosphere contains 1-100% of water vapor. The hydrothermal roasting temperature is 300-800 ℃, and preferably 400-600 ℃; the calcination time is at least 0.1 hour, preferably 0.5 to 3 hours.
The rare earth Y-type molecular sieve obtained by the modification method has the rare earth content of 2-18 wt%, preferably 8-15 wt%, the unit cell constant of 2.440-2.470 nm and the crystallinity of 30-60% calculated by rare earth oxide, and the rare earth Y-type molecular sieve has at least two mesoporous pore size distributions at 2-3 nm and 3-4 nm, and the mesoporous volume of the rare earth Y-type molecular sieve is more than 0.031cc/g, preferably 0.031 cc/g-0.057 cc/g (shown in the fact that a hysteresis ring shown by a C curve in fig. 2 has a larger area). The mesoporous pores are pores with the pore diameter of 2-50 nm.
For the Y-type molecular sieve containing rare earth, in the X-ray diffraction pattern, the peak with 2 theta of 11.8 +/-0.1 degrees can be used for characterizing the distribution condition of the rare earth in a small cage, I1Represents the peak intensity thereof; the peak 2 theta of 12.3 +/-0.1 degrees can be used for characterizing the rare earth distribution in a supercage, I2Represents the peak intensity thereof, I1And I2The ratio of (A) can be used for representing the migration degree of the rare earth ions from the super cage to the small cage, and the higher the ratio is, the better the migration degree is, otherwise, the worse the migration degree is. In the prior art, if the rare earth Y-type molecular sieve is obtained by conventional normal-pressure steam roasting, X is adoptedIntensity I of peak at 11.8 ± 0.1 ° 2 θ in ray diffraction pattern1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) is generally < 4.
The modified molecular sieve obtained by the method has the intensity I of a peak with the 2 theta being 11.8 +/-0.1 degrees in an X-ray diffraction pattern1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is more than or equal to 4.0; preferably, the intensity I of the peak with 2 θ of 11.8 ± 0.1 ° in the X-ray diffraction pattern is described1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.5-6.0.
The modification method is simple to implement, not only is the REY solid-state ion exchange degree improved, but also the modified rare earth Y-type molecular sieve has unique pore size distribution characteristics, at least 2 (2-3 nm and 3-4 nm) mesoporous pore size distributions exist, the richness of the Y molecular sieve mesopores is obviously increased, and the mesopore volume is more than 0.031 cc/g.
The modification method is a novel method for expanding pores of the rare earth Y-shaped molecular sieve with low cost and low emission, the proximity of the rare earth Y-shaped molecular sieve modified by the method is improved, the utilization rate of an active center is improved, and the modified rare earth Y-shaped molecular sieve has higher cracking activity stability and reduced coke selectivity when being applied to a catalytic cracking process, and particularly has wide application prospect in the field of heavy oil catalysis.
Drawings
FIG. 1 is a BJH pore size distribution diagram of a modified rare earth Y-type molecular sieve, wherein a curve A represents a sample PCY-1, and a curve B represents a comparative sample DBY-1.
FIG. 2 is a diagram showing the adsorption and desorption distribution of the modified rare earth Y-type molecular sieve, wherein the C curve represents a sample PCY-1, and the D curve represents a comparative sample DBY-1.
Fig. 3 is an X-ray diffraction (XRD) pattern of the rare earth Y-type molecular sieve.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In each example, the product unit cell constant and crystallinity were determined by X-ray diffraction (XRD) and the product BJH pore size distribution curve was measured by low temperature nitrogen desorption.
Example 1
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding 20ml 357gRE2O3And (3) mixing the rare earth chloride salt solution and 2g of ammonium chloride solid, heating to 70 ℃ after uniform stirring, adjusting the pH value of the slurry to 4.5 by using dilute hydrochloric acid, and stirring for 1 hour at constant temperature. Filtering, washing with water, drying, loading 7g of ammonia water by an immersion method, drying, and then carrying out pressurized hydrothermal roasting treatment for 2 hours at 500 ℃ and 0.3Mpa in a 100% water vapor atmosphere to obtain the rare earth sodium Y molecular sieve which is marked as PCY-1.
In the chemical composition of PCY-1, the rare earth oxide was 10.1% by weight.
In FIG. 1, the curve A is the pore size distribution curve calculated by sample PCY-1 according to BJH model. As can be seen from the curve A in FIG. 1, at least 2 mesoporous pore size distributions exist, which are respectively at 2-3 nm and 3-4 nm.
The C curve in FIG. 2 is the adsorption/desorption curve of sample PCY-1. As can be seen from the C curve, the absorption and desorption curve of the sample PCY-1 has a hysteresis loop with a large area, which indicates that the PCY-1 sample has a rich mesoporous structure.
FIG. 3 is an XRD spectrum of sample PCY-1, showing that it has a phase-pure FAU crystal structure without the formation of heterocrystals. The XRD results and the pore parameters are shown in Table 1.
Comparative example 1
This comparative example illustrates the process and results of conventional non-pressurized calcination of the resulting rare earth Y-type molecular sieve.
The same as example 1 except that the firing in an atmosphere of 100% steam was performed under a condition of zero apparent pressure and the supported aqueous ammonia was not impregnated.
100g of NaY molecular sieve and 1800g of deionized water are mixed and beaten, and 20ml of 357gRE is added2O3And (3) mixing the rare earth chloride salt solution and 2g of ammonium chloride solid, heating to 70 ℃ after uniform stirring, adjusting the pH value of the slurry to 4.5 by using dilute hydrochloric acid, and stirring for 1 hour at constant temperature. And after filtering, washing and drying, carrying out pressurized hydrothermal roasting treatment for 2 hours at 500 ℃ under the apparent pressure of 0Mpa and in the atmosphere of 100% water vapor to obtain a rare earth NaY molecular sieve comparison sample, which is marked as DBY-1.
The chemical composition of DBY-1 was 10.0% by weight of rare earth oxide.
In FIG. 1, curve B is the pore size distribution curve calculated by the BJH model for the comparative sample DBY-1. As can be seen from the curve B in FIG. 1, there are mainly 1 kind of mesoporous pore size distributions, that is, there is mesoporous pore size distribution at 3-4 nm, and there is no mesoporous pore size distribution at 2-3 nm.
The D curve in FIG. 2 is the adsorption/desorption curve of the comparative sample DBY-1. As can be seen from the D curve of fig. 2, the hysteresis loop area is smaller, indicating that the mesopore volume is smaller.
The XRD spectrum of comparative sample DBY-1 is characterized by FIG. 3.
The XRD results and the pore parameters are shown in Table 1.
Comparative example 2
This comparative example illustrates the process and results of conventional non-pressurized calcination of a rare earth Y-type molecular sieve obtained by non-pressurized hydrothermal calcination (i.e., atmospheric hydrothermal calcination).
The same as example 2 except that the calcination condition was atmospheric pressure, and the ammonia-supported catalyst was impregnated.
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding 20ml 357gRE2O3The rare earth chloride solution and 2g of ammonium chloride solid are stirred evenly, the temperature is raised to 70 ℃, the PH value of the slurry is adjusted to 4.5 by dilute hydrochloric acid, and the slurry is stirred for 1 hour at constant temperature. Filtering, washing, drying, loading 7g of ammonia water by adopting an immersion method, drying, and then carrying out pressurized hydrothermal roasting treatment for 2 hours at 500 ℃ and 0Mpa in a 100% water vapor atmosphere to obtain the rare earth NaY molecular sieve which is marked as DBY-1, wherein the chemical composition of the DBY-1 molecular sieve is 9.7 wt% of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram respectively have the characteristics of the curve in figure 1B, the curve in figure 2D and the curve in figure 3.
The XRD results and the pore parameters are shown in Table 1.
Example 2
100g of NaY molecular sieve (Changling division, China petrochemical catalyst Co., Ltd., caustic soda 74.1 wt%, crystallinity 89.3%, the same applies below) and 1000g of deionized water were mixed and beaten, and 16ml of 357gRE was added2O3L rare earth chloride solution and 8g ammonium chloride solid, stirring, heating to 60 deg.C, and diluting with waterAdjusting the pH value of the slurry to 4.0 by hydrochloric acid, and stirring for 1.5h at constant temperature.
Filtering, washing, drying, loading 10g of ammonium chloride by adopting an impregnation method, drying, and roasting at 430 ℃ and an apparent pressure of 0.8Mpa for 0.5h in a 100% water vapor atmosphere to obtain the NaY molecular sieve containing the rare earth, wherein the sample number is marked as PCY-2.
The chemical composition of the PCY-2 molecular sieve is 8.0 weight percent of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of PCY-2 have the characteristics of the curve in figure 1A, the curve in figure 2C and the curve in figure 3 respectively.
The XRD results and the pore parameters are shown in Table 1.
Example 3
100g of NaY molecular sieve and 2200g of deionized water are mixed and beaten, and 24ml of 357gRE is added2O3The temperature is raised to 70 ℃ after the mixture is evenly stirred, the PH value of the serous fluid is adjusted to 3.5 by using dilute hydrochloric acid, and the mixture is stirred for 1 hour at constant temperature. Filtering, washing with water, drying, loading 12g ammonium bicarbonate by impregnation, drying, and performing pressurized hydrothermal roasting treatment at 520 ℃ and 0.4Mpa for 1.5h in 100% steam atmosphere to obtain the rare earth NaY molecular sieve PCY-3.
The chemical composition of the PCY-3 molecular sieve is 10.7 percent by weight of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of PCY-3 have the characteristics of the curve in figure 1A, the curve in figure 2C and the curve in figure 3 respectively.
The XRD results and the pore parameters are shown in Table 1.
Example 4
100g of NaY molecular sieve and 2800g of deionized water are mixed and beaten, and 28ml of 357gRE2O3The temperature is raised to 80 ℃ after the mixture is evenly stirred, the PH value of the slurry is adjusted to 3.8 by using dilute hydrochloric acid, and the mixture is stirred for 1 hour at constant temperature. Filtering, washing with water, drying, loading 9g of sodium carbonate by an immersion method, drying, and then carrying out pressurized hydrothermal roasting treatment for 2 hours at 580 ℃, 0.5Mpa and 100% steam atmosphere to obtain the rare earth NaY molecular sieve which is marked as PCY-4.
The chemical composition of the PCY-4 molecular sieve is 12.3 weight percent of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of PCY-4 are respectively characterized by the curves in figure 1A, figure 2C and figure 3.
The XRD results and the pore parameters are shown in Table 1.
Example 5
Mixing 100g NaY molecular sieve and 2000g deionized water, pulping, adding 32ml 357gRE2O3The temperature is raised to 70 ℃ after the mixture is evenly stirred, the PH value of the serous fluid is adjusted to 4.0 by using dilute hydrochloric acid, and the mixture is stirred for 1 hour at constant temperature. Filtering, washing with water, drying, loading 10g of buffer solution of ammonium chloride and ammonia water by an immersion method, drying, and then carrying out pressurized hydrothermal roasting treatment for 1.5h at 550 ℃ under 0.4Mpa in the atmosphere of 100% water vapor to obtain the rare earth NaY molecular sieve PCY-5.
The chemical composition of the PCY-5 molecular sieve is 12.6 weight percent of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of PCY-5 have the characteristics of the curve in figure 1A, the curve in figure 2C and the curve in figure 3 respectively.
The XRD results and the pore parameters are shown in Table 1.
Example 6
100g of NaY molecular sieve and 1800g of deionized water are mixed and beaten, and 20ml of 357gRE is added2O3The rare earth chloride solution and 2g of ammonium chloride solid are stirred evenly, the temperature is raised to 70 ℃, the PH value of the slurry is adjusted to 4.5 by dilute hydrochloric acid, and the slurry is stirred for 1 hour at constant temperature. Filtering, washing with water, drying, loading 2g hydrochloric acid solution by adopting an immersion method, drying, and then carrying out pressurized hydrothermal roasting treatment for 2 hours at 430 ℃ under 0.6Mpa in a 100% water vapor atmosphere to obtain the rare earth NaY molecular sieve which is marked as PCY-6.
The chemical composition of the PCY-6 molecular sieve is 10.0 weight percent of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of PCY-6 have the characteristics of the curve in figure 1A, the curve in figure 2C and the curve in figure 3 respectively.
The XRD results and the pore parameters are shown in Table 1.
Comparative example 3
This comparative example illustrates the process and results of a rare earth Y-type molecular sieve obtained without a pressurized hydrothermal calcination treatment (i.e., atmospheric hydrothermal calcination).
The same as example 6, except that the calcination conditions were atmospheric pressure and the supported hydrochloric acid was not impregnated.
100g of NaY molecular sieve and 1800g of deionized water are mixed and beaten, and 20ml of 357gRE is added2O3And (3) mixing the rare earth chloride salt solution and 2g of ammonium chloride solid, heating to 70 ℃ after uniform stirring, adjusting the pH value of the slurry to 4.5 by using dilute hydrochloric acid, and stirring for 1 hour at constant temperature. Filtering, washing, drying, and performing pressurized hydrothermal roasting treatment at 430 ℃ and 0Mpa for 2h in 100% steam atmosphere to obtain the rare earth NaY molecular sieve DBY-3.
The chemical composition of the DBY-3 molecular sieve is 10.0 percent by weight of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of DBY-3 have the characteristics of the curve in figure 1B, the curve in figure 2D and the curve in figure 3 respectively.
The XRD results and the pore parameters are shown in Table 1.
Comparative example 4
This comparative example illustrates the process and results of a rare earth Y-type molecular sieve obtained without pressurized hydrothermal calcination treatment (i.e., atmospheric hydrothermal calcination).
The same as example 6, but under atmospheric calcination conditions, hydrochloric acid was impregnated.
100g of NaY molecular sieve and 1800g of deionized water are mixed and beaten, and 20ml of 357gRE is added2O3The rare earth chloride solution and 2g of ammonium chloride solid are stirred evenly, the temperature is raised to 70 ℃, the PH value of the slurry is adjusted to 4.5 by dilute hydrochloric acid, and the slurry is stirred for 1 hour at constant temperature. Filtering, washing with water, drying, loading 2g hydrochloric acid solution by adopting a dipping method, drying, and then carrying out pressurized hydrothermal roasting treatment for 2 hours at 430 ℃ and 0Mpa in a 100% water vapor atmosphere to obtain the rare earth NaY molecular sieve which is marked as DBY-2.
The chemical composition of the DBY-2 molecular sieve is 9.7 percent by weight of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of DBY-4 have the characteristics of the curve in figure 1B, the curve in figure 2D and the curve in figure 3 respectively.
The XRD results and the pore parameters are shown in Table 1.
Example 7
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding20ml of 357gRE2O3The rare earth chloride solution and 2g of ammonium chloride solid are stirred evenly, the temperature is raised to 70 ℃, the PH value of the slurry is adjusted to 4.5 by dilute hydrochloric acid, and the slurry is stirred for 1 hour at constant temperature. Filtering, washing with water, drying, loading 3g of sodium hydroxide solid by adopting an immersion method, drying, and then carrying out pressurized hydrothermal roasting treatment for 2 hours at 400 ℃ under 0.8Mpa in the atmosphere of 100% water vapor to obtain the rare earth NaY molecular sieve which is marked as PCY-7.
The chemical composition of the PCY-7 molecular sieve is 9.7 percent by weight of rare earth oxide.
The BJH pore size distribution curve, the adsorption and desorption curve and the XRD spectrogram of PCY-7 are respectively characterized by the curves in figure 1A, figure 2C and figure 3.
The XRD results and the pore parameters are shown in Table 1.
TABLE 1
Figure BDA0002122845420000091
As can be seen from table 1, the mesoporous area and the mesoporous volume of the rare earth Y-type molecular sieve prepared in embodiments 1 to 7 of the method of the present invention are significantly higher than those of the samples in comparative examples 1 to 4, wherein the sample in embodiment 1 is more preferable, which shows that the sample has a more significant mesoporous characteristic and a higher crystallinity, which indicates that the enrichment of mesopores of the Y-type molecular sieve is significantly increased by pressurized hydrothermal calcination after loading ammonia water by an impregnation method, and a certain degree of mesopores of the molecular sieve are formed.
Example 8
This example illustrates the cracking performance of heavy oil after the rare earth Y-type molecular sieve is subjected to hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17 h.
The rare earth Y-type molecular sieve PCY-1 of example 1 and the rare earth Y-type molecular sieve DBY-2 of comparative example 2 were mixed with ammonium chloride solution for exchange, and Na contained therein was added2Washing to below 0.3 wt% with O%, filtering, drying, and performing hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17 hr to perform micro-reverse evaluation on heavy oil.
Heavy oil micro-inverse evaluation conditions: the molecular sieve loading is 2g, the raw oil is Wu-MI-Sanqiao heavy oil (physicochemical properties are shown in Table 2), the oil inlet quantity is 1.384g, the reaction temperature is 500 ℃, and the regeneration temperature is 600 ℃.
The results are shown in Table 3.
TABLE 2
Item VGO
Density (293K), g/cm3 0.904
Viscosity (373K), mPa.s 9.96
Carbon residue, wt. -%) 3.0
C,wt.％ 85.98
H,wt.％ 12.86
S,wt.％ 0.55
N,wt.％ 0.18
Saturated hydrocarbon, wt. -%) 56.56
Aromatic hydrocarbons, wt. -%) 24.75
Gum, wt. -%) 18.75
Asphaltenes, wt. -%) 0.44
Fe,μg/g 5.3
Ni,μg/g 5.0
V,μg/g 0.8
Cu,μg/g 0.04
Na,μg/g 1.2
TABLE 3
PCY-1 DBY-2 PCY-6 DBY-4
Ratio of agent to oil 1.45 1.45
Material balance/m%
Dry gas 1.18 1.41 1.20 1.06
Liquefied gas 8.67 9.63 8.45 7.01
Gasoline (R) and its preparation method 51.00 43.32 48.05 42.63
Diesel oil 18.68 17.90 19.97 20.74
Heavy oil 11.42 19.42 13.91 21.14
Coke 9.06 10.32 8.42 8.42
Conversion/m% 69.90 62.68 66.12 58.12
Yield of light oil/m% 69.67 61.22 68.03 63.37
Light harvesting plus liquefied gas/m% 78.34 70.85 76.48 70.38
Coke/conversion ratio 0.12 0.14 0.13 0.15
As can be seen from Table 3, compared with DBY-2 and DBY-4 molecular sieves, the molecular sieves PCY-1 and PCY-6 prepared by the method have excellent heavy oil cracking activity after being subjected to hydrothermal aging treatment at 800 ℃ under 100% of water vapor for 17 hours, the conversion rates are respectively increased by 7.22 percent and 8.00 percent, the gasoline yield is respectively increased by 6.68 percent and 5.42 percent, and the coke/conversion rates are respectively reduced by 0.02 and 0.02. This shows that the rare earth Y-type molecular sieve obtained by impregnating the loaded ammonia water and then performing pressure roasting treatment has higher cracking activity stability and reduced coke selectivity.

Claims (15)

1. A method for modifying a Y-type molecular sieve comprises the following steps: the method comprises the steps of contacting and drying a rare earth NaY molecular sieve with an alkaline substance to obtain the rare earth NaY molecular sieve containing the alkaline substance, and carrying out hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, wherein the alkaline substance is selected from one or more of ammonia water, a buffer solution of the ammonia water and ammonium chloride, sodium hydroxide, sodium carbonate and sodium bicarbonate, the apparent pressure of the atmosphere environment is 0.1-0.8 MPa and contains 1-100% of water vapor, and the hydrothermal roasting treatment temperature is 300-800 ℃.
2. The method according to claim 1, wherein the rare earth NaY molecular sieve is obtained by the steps of A, carrying out contact treatment on the NaY molecular sieve and a rare earth salt solution or a mixed solution of the rare earth salt solution and an ammonium salt, filtering, washing and drying.
3. The method of claim 2 wherein the rare earth salt solution in step a is an aqueous chloride solution comprising one or more selected from lanthanum, cerium, praseodymium, and neodymium.
4. The method according to claim 2, wherein the ammonium salt in step a is selected from any one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
5. The method according to claim 2, wherein the step a is performed at a pH =3.0 to 5.0, a water sieve weight ratio of 5 to 30, and a temperature of room temperature to 100 ℃.
6. The method according to claim 1, wherein the atmosphere has an apparent pressure of 0.3 to 0.6MPa and a hydrothermal calcination treatment temperature of 400 to 600 ℃.
7. The method according to claim 1 or 6, wherein said atmosphere contains 30 to 100% of water vapor.
8. The method of claim 7, wherein said atmosphere contains 60 to 100% water vapor.
9. A rare earth Y-type molecular sieve obtainable by the process of any one of claims 1 to 8.
10. The molecular sieve according to claim 9, wherein at least two mesoporous pore size distributions of 2 to 3nm and 3 to 4nm are present, and the mesoporous volume is 0.031cc/g or more.
11. The molecular sieve of claim 10, wherein said mesopore volume is 0.031cc/g to 0.057 cc/g.
12. A molecular sieve according to claim 9 having an X-ray diffraction pattern of 2θIntensity of the peak I of =11.8 ± 0.1 °1And 2θIntensity of peak I of =12.3 ± 0.1 °2The ratio of (A) to (B) is not less than 4.0.
13. The molecular sieve of claim 9 having an X-ray diffraction pattern of 2θIntensity of the peak I of =11.8 ± 0.1 °1And 2θIntensity of peak I of =12.3 ± 0.1 °2The ratio of (A) to (B) is 4.5-6.0.
14. The molecular sieve of claim 9 having a rare earth content of 2 to 18 wt.% based on rare earth oxide, a unit cell constant of 2.440 to 2.470nm, and a crystallinity of 30 to 60%.
15. The molecular sieve of claim 14 having a rare earth content of 8 to 15 wt.%, based on rare earth oxide.
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