CN112206809A - Rare earth-containing Y-type molecular sieve and preparation method thereof - Google Patents

Rare earth-containing Y-type molecular sieve and preparation method thereof Download PDF

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CN112206809A
CN112206809A CN201910612784.6A CN201910612784A CN112206809A CN 112206809 A CN112206809 A CN 112206809A CN 201910612784 A CN201910612784 A CN 201910612784A CN 112206809 A CN112206809 A CN 112206809A
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molecular sieve
rare earth
peak area
size distribution
pore size
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罗一斌
王成强
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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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Priority to CN201910612784.6A priority Critical patent/CN112206809A/en
Priority to TW109123253A priority patent/TW202104082A/en
Priority to JP2022501264A priority patent/JP2022540221A/en
Priority to US17/626,087 priority patent/US20220259055A1/en
Priority to KR1020227004443A priority patent/KR20220034193A/en
Priority to KR1020227004473A priority patent/KR20220025200A/en
Priority to PCT/CN2020/101051 priority patent/WO2021004503A1/en
Priority to EP20836459.6A priority patent/EP3998117A4/en
Priority to TW109123252A priority patent/TW202102439A/en
Priority to US17/626,059 priority patent/US20220250924A1/en
Priority to JP2022501268A priority patent/JP2022540629A/en
Priority to PCT/CN2020/101048 priority patent/WO2021004502A1/en
Priority to EP20837442.1A priority patent/EP3998118A4/en
Publication of CN112206809A publication Critical patent/CN112206809A/en
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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
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/66—Pore distribution
    • 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
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The Y-type molecular sieve containing rare earth is characterized in that a BJH pore size distribution spectrogram at least has mesoporous pore size distribution at 2-3nm, 3-4nm and 10-30nm positions, wherein the ratio of the peak area of the 2-3nm pore size distribution to the total pore peak area is more than 0.1, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area is more than 0.2.

Description

Rare earth-containing Y-type molecular sieve and preparation method thereof
Technical Field
The invention relates to a rare earth-containing Y-type molecular sieve and a preparation method thereof.
Background
Catalytic cracking is the most important production technology in today's refineries, and catalytic cracking units are used to convert heavy oils and resids into gasoline, diesel, and light gas components. In the industry, a catalytic cracking unit must comprise two parts of reaction and high-temperature catalyst regeneration, 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 the cracking reaction and is used as an active component of the catalytic cracking catalyst, and the main function of the Y-type molecular sieve in the catalytic cracking catalyst is responsible for producing gasoline range molecular products.
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. However, when the NaY molecular sieve is ion exchanged with an aqueous solution of a rare earth salt, hydrated rare earth ions having a diameter of about 0.79nm are difficult to enter the sodalite cage through the six-membered ring window (having a diameter of about 0.26nm) of the Y molecular sieve. 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+The content creates conditions (USP 3402996). Therefore, how to promote the migration of rare earth ions and increase the occupancy rate 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-.
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 in industry.
CN1026225C discloses a method for preparing rare earth Y molecular sieve, which comprises the 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 with water, 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, adjusting the pH value of the slurry by using alkaline liquid to perform rare earth deposition, or pulping the rare earth sodium Y molecular sieve, then performing contact treatment on the pulped rare earth sodium Y molecular sieve and 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 then 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 inventors of the present invention have surprisingly found, on the basis of extensive experiments, that partial ammonium exchange of NaY molecular sieves with ammonium salts is carried out first, followed by NH4The NaY molecular sieve is contacted with a rare earth salt solution or a mixed solution of the rare earth salt solution and ammonium salt to obtain a rare earth sodium Y molecular sieve, and then the rare earth sodium Y molecular sieve is roasted by adopting pressurized water and heat to obtain the molecular sieve which has unique mesoporous characteristics and higher activity and hydrothermal stability.
Therefore, the invention aims to solve the problem of complex process when the solid-state ion exchange degree is improved in the prior art, and aims to provide the rare earth-containing Y-type molecular sieve which is high in exchange degree and has unique pore size distribution characteristics; another object of the present invention is to provide a process for preparing the same, which is relatively simple and easy to operate. .
In order to achieve one of the purposes of the invention, the Y-type molecular sieve containing rare earth is characterized in that at least mesoporous pore size distributions of 2-3nm, 3-4nm and 10-30nm exist, in a BJH pore size distribution spectrogram, the ratio of the peak area of the 2-3nm pore size distribution to the total pore peak area is more than 0.1, and the ratio of the peak area of the 20nm pore size distribution to the total pore peak area is more than 0.2.
The intensity I of the peak with 2 theta of 11.8 +/-0.1 degrees in an X-ray diffraction pattern of the Y molecular sieve containing rare earth1Intensity of peak 12.3 + -0.1 DEG with 2 theta2Is greater than 4.0, preferably 2 theta is 11.8 + -0.1 DEG peak intensity I1Intensity of peak 12.3 + -0.1 DEG with 2 theta2A ratio of (a) to (b) of more than 4.3, more preferably an intensity I of a peak of 11.8 ± 0.1 ° 2 θ1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.8-6.0. In an X-ray diffraction pattern, a peak with 2 theta of 11.8 +/-0.1 degrees can be used for characterizing the distribution condition of rare earth in a small cage, and I1The peak intensity is shown, the 2 theta is 12.3 +/-0.1 DEG peak can be used for characterizing the rare earth distribution in the supercage, I2The ratio of the two 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. The molecular sieve of the invention has better migration degree of rare earth ions from the super cage to the small cage.
The rare earth-containing Y molecular sieve has the rare earth content of 2-18 wt%, preferably 8-15 wt%, calculated by rare earth oxide, a unit cell constant of 2.440-2.470 nm and the crystallinity of 30-60%. The rare earth-containing Y-type molecular sieve has at least 3 mesoporous pore size distributions, and has 3 mesoporous distributions at 2-3nm, 3-4nm and 10-30nm respectively. In a BJH diagram of the molecular sieve, the ratio of the peak area of 2-3nm pore size distribution to the total pore peak area is more than 0.1, and the ratio of the peak area of 10-30nm pore size distribution to the total pore peak area is more than 0.2; preferably, the ratio of the peak area of the pore size distribution of 2-3nm to the peak area of the total pore is more than 0.12, and the ratio of the peak area of the pore size distribution of 10-30nm to the peak area of the total pore is more than 0.22; more preferably, the ratio of the peak area of the pore size distribution of 2 to 3nm to the peak area of the total pores is more than 0.15, and the ratio of the peak area of the pore size distribution of 10 to 30nm to the peak area of the total pores is, for example, more than 0.25; most preferably, the ratio of the peak area of the pore size distribution of 2-3nm to the peak area of the total pores is 0.18-0.26, and the ratio of the peak area of the pore size distribution of 10-30nm to the peak area of the total pores is 0.27-0.32.
The invention further provides a preparation method of the rare earth-containing Y molecular sieve, which is characterized by comprising the following steps:
(1) partial ammonium exchange is carried out on the NaY molecular sieve and ammonium salt to remove 10-80% of sodium ions, and NH is obtained after filtration, washing and drying4A NaY molecular sieve;
(2) NH obtained in the step (1)4The method comprises the following steps of (1) carrying out contact treatment on a NaY molecular sieve and a rare earth salt solution or a mixed solution of the rare earth salt solution and ammonium salt, filtering, washing and drying to obtain a rare earth NaY molecular sieve;
(3) and (3) carrying out hydrothermal roasting treatment on the rare earth NaY molecular sieve obtained in the step (2) under an atmosphere environment of externally applied pressure and externally added water, wherein the atmosphere environment has an apparent pressure of 0.01-1 MPa and contains 1-100% of water vapor, and the hydrothermal roasting treatment temperature is 300-800 ℃, preferably 400-600 ℃.
In the preparation method of the invention, the ammonium salt in the step (1) and the step (2) is selected from any one or a mixture of more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
In the preparation method of the invention, in the step (1), the NaY molecular sieve and ammonium salt are subjected to partial ammonium exchange, so that 10 to 80 percent, preferably 20 to 60 percent of sodium ions are removed. The process can be, for example, exchanging NaY molecular sieve with ammonium salt solution at a weight ratio of water to sieve of 5-30, at a weight ratio of ammonium salt to ammonium salt of 0.01-3, at a temperature of room temperature to 100 ℃ for at least 0.3 hour.
In the preparation method of the invention, the rare earth salt solution in the step (2) is selected from a chloride aqueous solution containing one or more of lanthanum, cerium, praseodymium and neodymium ions.
In the preparation method, the NaY molecular sieve and the rare earth salt solution or the mixed solution of the rare earth salt solution and the ammonium salt are subjected to contact treatment in the step (2), and the process is to exchange the NaY molecular sieve and the rare earth salt solution or the mixed solution of the ammonium salt and the rare earth salt solution for at least 0.3 hour at the slurry pH of 3.0-5.0, the water-sieve weight ratio of 5-30 and the exchange temperature of room temperature-100 ℃. The contact treatment in step (2) is followed by conventional filtration, water washing and drying, which aims to remove, for example, chloride ions, prevent the subsequent roasting process from corroding equipment and also play a part in sodium removal.
In the preparation method of the present invention, the hydrothermal calcination treatment in step (3) is performed in an atmosphere environment in which pressure is externally applied and water is externally added. The atmosphere is obtained by externally applying 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 is applied to the hydrothermal roasting treatment of the prepared material from the outside, and for example, the external pressure may be applied 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 requirement that the atmosphere contains 1-100% of water vapor.
The preparation method of the invention can also comprise a step (4) of ammonium exchange after the step (3). And (4) exchanging the ammonium in the step (4) at room temperature to 100 ℃ for at least 0.3 hour, wherein the weight ratio of the rare earth sodium Y molecular sieve to ammonium salt and water is 1: (0.05-0.5): (5-30).
The Y-type molecular sieve containing rare earth has unique pore size distribution characteristics, and at least has mesoporous pore size distribution at positions of 2-3nm, 3-4nm and 10-30nm, wherein the ratio of the peak area of the pore size distribution at 2-3nm to the total peak area of pores is more than 0.1, and the ratio of the peak area of the pore size distribution at 10-30nm to the total peak area of pores is more than 0.2. The preparation method provided by the invention comprises the steps of firstly carrying out partial ammonium exchange and rare earth exchange on the NaY molecular sieve and ammonium salt, then promoting the migration of rare earth ions from the supercage to the sodalite cages and generating unique pore size distribution characteristics in a treatment mode of hydrothermal roasting in an atmosphere environment as described by the invention, wherein the intensity I of a peak with the 2 theta of 11.8 +/-0.1 degrees in an X-ray diffraction pattern of the molecular sieve1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is more than 4.0, and the hydrothermal stability and the activity stability of the rare earth-containing Y molecular sieve are improved.
Drawings
FIG. 1 is a pore size distribution curve calculated by a BJH model for PDY-1 of a sample of the present invention.
FIG. 2 is an XRD spectrum of PDY-1 of the inventive sample.
FIG. 3 is a BJH pore size distribution curve for a comparative sample DBY-1 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 of examples and comparative examples, the unit cell constant and crystallinity of the sample were determined by X-ray diffraction (XRD), and the BJH pore size distribution curve of the sample was measured by low-temperature nitrogen desorption.
Example 1
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding 10g ammonium chloride solid, stirring, heating to 70 deg.C, stirring at constant temperature for 2 hr, filtering, washing with water, drying, adding 20ml of 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, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2h at 500 ℃, with apparent pressure of 0.3Mpa and 100% steam atmosphere to obtain the rare earth NaY molecular sieve PDY-1.
The chemical composition of PDY-1 contains rare earth oxide 10.1 wt%.
PDY-1, wherein the ratio of the peak area of the pore size distribution of 2-3nm to the peak area of the total pores is 0.25, and the ratio of the peak area of the pore size distribution of 10-30nm to the peak area of the total pores is 0.3.
FIG. 1 is a pore size distribution curve calculated by PDY-1 according to a BJH model, wherein at least 3 kinds of mesoporous pore size distributions exist, and 3 kinds of obvious mesoporous distributions exist at positions of 2-3nm, 3-4nm and 10-30nm respectively.
FIG. 2 is an XRD spectrum of PDY-1, which shows that the molecular sieve of the obtained sample has a pure-phase FAU crystal structure and no mixed crystal is formed. XRD tests intensity I of peak with 2 theta being 11.8 +/-0.1 DEG1And 2 theta is 12.3 ±)Intensity of 0.1 ° peak I2The ratio of (A) to (B) is 5.8.
Comparative example 1
This comparative example illustrates the process and results of obtaining a rare earth Y-type molecular sieve with partial ammonium exchange and calcination at atmospheric pressure.
The same as example 1, except that the firing conditions were atmospheric pressure.
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding 10g ammonium chloride solid, stirring, heating to 70 deg.C, stirring at constant temperature for 2 hr, filtering, washing with water, drying, adding 20ml of 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.
After filtering, water washing and drying, the product is obtained by pressurized hydrothermal roasting treatment for 2 hours at 500 ℃ and under the apparent pressure of 0Mpa and the atmosphere of 100 percent water vapor, and is marked as a comparative sample DBY-1.
The chemical composition of the comparative sample DBY-1 was 10.1 wt% rare earth oxide.
FIG. 3 is a pore size distribution curve calculated by DBY-1 according to a BJH model, wherein 1 kind of mesoporous pore size distribution mainly exists, namely, one kind of mesoporous pore size distribution exists at 3-4nm, but the mesoporous pore size distribution does not exist at 2-3nm and 10-30 nm.
The ratio of the peak area of the comparative sample DBY-13nm pore size distribution to the total pore peak area was 0, and the ratio of the peak area of the comparative sample 10-30nm pore size distribution to the total pore peak area was 0.
The XRD spectrum of DBY-1 is characterized by that of figure 2. The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 3.5.
Example 2
Mixing 100g NaY molecular sieve (Changling Branch of China petrochemical catalyst, caustic soda 74.1 wt%, crystallinity 89.3%, the same below) and 1000g deionized water, pulping, adding 5g ammonium sulfate solid, stirring, heating to 80 deg.C, stirring at constant temperature for 2 hr, filtering, washing with water, drying, adding 16ml of 357gRE2O3L of chlorinated rare earth salt solution and 8g of chlorineDissolving ammonium solid, stirring, heating to 60 deg.C, adjusting pH to 4.0 with dilute hydrochloric acid, and stirring at constant temperature for 1.5 hr.
Filtering, washing with water, drying, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 430 ℃ and an apparent pressure of 0.8Mpa for 0.5h in a 50% steam atmosphere to obtain the single-exchange single-roasting rare earth sodium Y molecular sieve PDY-2.
The chemical composition of PDY-2 is 8.2 wt% of rare earth oxide.
The BJH pore size distribution curve and the XRD spectrogram of PDY-2 have the characteristics of figure 1 and figure 2 respectively.
The ratio of the peak area of the molecular sieve with the pore diameter distribution of 2-3nm to the peak area of the total pores is 0.12, and the ratio of the peak area of the molecular sieve with the pore diameter distribution of 10-30nm to the peak area of the total pores is 0.25.
The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.4.
Example 3
Mixing 100g NaY molecular sieve and 2200g deionized water, pulping, adding 20g ammonium sulfate solid, stirring, heating to 80 deg.C, stirring at constant temperature for 1.5h, filtering, washing with water, drying, adding 24ml 357gRE2O3The temperature is raised to 70 ℃ after the mixture is evenly stirred, the PH value of the serous fluid is adjusted to 3.5 by dilute hydrochloric acid, and the mixture is stirred for 1 hour at constant temperature.
Filtering, washing with water, drying, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 520 ℃ and an apparent pressure of 0.4Mpa for 1.5h in a 100% steam atmosphere to obtain the rare earth NaY molecular sieve PDY-3.
The chemical composition of the PDY-3 molecular sieve is 11.4 weight percent of rare earth oxide.
The BJH pore size distribution curve and XRD spectrogram of PDY-3 have the characteristics of figure 1 and figure 2 respectively.
The ratio of the peak area of the molecular sieve with the pore diameter distribution of 2-3nm to the peak area of the total pores is 0.23, and the ratio of the peak area of the molecular sieve with the pore diameter distribution of 10-30nm to the peak area of the total pores is 0.25.
The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.4.
Example 4
Mixing 100g NaY molecular sieve and 2800g deionized water, pulping, adding 50g ammonium chloride solid, stirring, heating to 60 deg.C, stirring at constant temperature for 2 hr, filtering, washing with water, drying, adding 28ml 357gRE2O3And (3) uniformly stirring the chlorinated rare earth salt solution, heating to 80 ℃, adjusting the pH value of the slurry to 3.8 by using dilute hydrochloric acid, and stirring for 1 hour at constant temperature.
Filtering, washing with water, drying, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2h at 580 ℃ under the apparent pressure of 0.5Mpa in the atmosphere of 100% steam to obtain the one-way-one-baking rare earth sodium Y molecular sieve PDY-4.
The chemical composition of the PDY-4 molecular sieve is 12.6 wt% of rare earth oxide.
The BJH pore size distribution curve and XRD spectrogram of PDY-4 have the characteristics of figure 1 and figure 2 respectively.
The ratio of the peak area of the molecular sieve with the pore diameter distribution of 2-3nm to the peak area of the total pores is 0.23, and the ratio of the peak area of the molecular sieve with the pore diameter distribution of 10-30nm to the peak area of the total pores is 0.21.
The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.2.
Example 5
Mixing 100g NaY molecular sieve and 2000g deionized water, pulping, adding 200g ammonium chloride solid, stirring, heating to 60 deg.C, stirring at constant temperature for 1h, filtering, washing with water, drying, 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, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment at 550 ℃ and an apparent pressure of 0.4Mpa for 1.5h in a 100% steam atmosphere to obtain the rare earth NaY molecular sieve PDY-5.
The chemical composition of the PDY-5 molecular sieve is 13.4 weight percent of rare earth oxide.
The BJH pore size distribution curve and XRD spectrogram of PDY-5 have the characteristics of figure 1 and figure 2 respectively.
The ratio of the peak area of the molecular sieve with the pore diameter distribution of 2-3nm to the peak area of the total pores is 0.24, and the ratio of the peak area of the molecular sieve with the pore diameter distribution of 10-30nm to the peak area of the total pores is 0.29.
The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.5.
Example 6
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding 50g ammonium sulfate solid, stirring, heating to 70 deg.C, stirring at constant temperature for 2 hr, filtering, washing with water, drying, 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, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2h at 430 ℃ and an apparent pressure of 0.6Mpa in a 100% steam atmosphere to obtain the rare earth NaY molecular sieve PDY-6.
The chemical composition of the PDY-6 molecular sieve is 10.0 wt% of rare earth oxide.
The BJH pore size distribution curve and XRD spectrogram of PDY-6 have the characteristics of figure 1 and figure 2 respectively.
The ratio of the peak area of the molecular sieve with the pore diameter distribution of 2-3nm to the peak area of the total pores is 0.18, and the ratio of the peak area of the molecular sieve with the pore diameter distribution of 10-30nm to the peak area of the total pores is 0.22.
The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.9.
Comparative example 2
This comparative example illustrates the process and results of partial ammonium cross-linking of a rare earth-containing Y-type molecular sieve obtained under atmospheric pressure calcination.
The same as example 6, except that the firing conditions were atmospheric pressure.
Mixing 100g of NaY molecular sieve and 1800g of deionized water, pulping, adding 50g of ammonium sulfate solid, stirring uniformly, heating to 70 ℃, stirring at constant temperature for 2 hours, filteringWashing with water, drying, 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.
And filtering, washing with water, drying, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 430 ℃ under the apparent pressure of 0Mpa in the 100% steam atmosphere to obtain a rare earth NaY molecular sieve comparison sample, which is marked as DBY-2.
The chemical composition of the DBY-2 molecular sieve is 10.0 weight percent of rare earth oxide.
The ratio of the peak area of the molecular sieve with the pore size distribution of 2-3nm to the peak area of the total pores is 0, and the ratio of the peak area of the molecular sieve with the pore size distribution of 10-30nm to the peak area of the total pores is 0.
The XRD results are shown in Table 1, and the intensity I of the peak with 2 theta being 11.8 +/-0.1 DEG is shown1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 2.8.
The XRD spectrum and BJH pore size distribution curve of DBY-2 have the characteristics of figure 2 and figure 3 respectively.
Example 7
Mixing 100g NaY molecular sieve and 1800g deionized water, pulping, adding 20g ammonium sulfate solid, stirring, heating to 80 deg.C, stirring at constant temperature for 2 hr, filtering, washing with water, drying, 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, externally applying pressure and adding water, and performing pressurized hydrothermal roasting treatment for 2h at 400 ℃ and under the apparent pressure of 0.8Mpa and the atmosphere of 100% steam to obtain the rare earth NaY molecular sieve PDY-7.
The chemical composition of the PDY-7 molecular sieve is 9.8 weight percent of rare earth oxide.
The BJH pore size distribution curve and XRD spectrogram of PDY-7 have the characteristics of figure 1 and figure 2 respectively.
The ratio of the pore size distribution content of the PDY-7 molecular sieve of 2-3nm to the total pore content is 0.13, and the ratio of the pore size distribution content of 10-30nm to the total pore content is 0.21.
The XRD results are shown in Table 1, and the 2 theta is 11.8 +/-0.1 DEG peak strongDegree I1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.4.
Examples 8 to 14
Examples 8-14 illustrate the unit cell and crystallinity of the rare earth Y-type molecular sieve of the present invention after aging.
The rare earth Y-type molecular sieve samples PDY-1 to PDY-7 prepared in examples 1 to 7 were subjected to hydrothermal aging treatment at 800 ℃ for 17 hours with 100% steam, and the data are shown in Table 1.
Comparative examples 3 and 4
Comparative examples 3 and 4 illustrate the unit cell and crystallinity after aging treatment of comparative samples of rare earth Y-type molecular sieves of comparative examples 1 and 2.
Comparative samples DBY-1 and DBY-2 of the rare earth Y-type molecular sieve prepared in comparative examples 3 and 4 are subjected to hydrothermal aging treatment at 800 ℃ for 17 hours by 100 percent of water vapor, and the data are shown in Table 1.
TABLE 1
Figure BDA0002122845040000111
As can be seen from table 1, the rare earth Y-type molecular sieve prepared by the method of the present invention has a higher crystallinity after being subjected to hydrothermal aging treatment at 800 ℃, 100% steam and 17 hours, and the crystallinity in examples 1 to 7 is significantly higher than that in comparative examples 1 to 2, wherein the sample of example 2 is more preferable, and shows a higher crystallinity, which indicates that compared with the normal pressure hydrothermal calcination, the rare earth Y-type molecular sieve obtained by hydrothermal treatment under the atmosphere environment condition of the present invention has a higher hydrothermal stability, and the hydrothermal stability is significantly improved.
Example 15
This example illustrates the cracking performance of heavy oil after the rare earth Y-type molecular sieve provided by the present invention is subjected to hydrothermal aging treatment at 800 deg.c with 100% steam for 17 h.
The rare earth Y-type molecular sieves in the above example 1 and comparative example 1 were mixed with ammonium chloride solution for exchange, and Na was added thereto2Washing to below 0.3 wt% with O%, filtering, drying, and performing hydrothermal aging treatment at 800 deg.C with 100% steam for 17 hr to perform micro-reverse evaluation on heavy oil.
Heavy oil micro-reverse 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
Sample numbering PDY-1 DBY-1 PDY-6 DBY-2
Ratio of agent to oil 1.45 1.45 1.45 1.45
Material balance/m%
Dry gas 1.52 1.20 1.40 1.13
Liquefied gas 9.90 7.44 9.63 7.55
Gasoline (gasoline) 55.17 45.63 46.55 42.82
Diesel oil 16.14 19.63 18.63 18.66
Heavy oil 6.53 17.07 14.90 21.50
Coke 10.74 9.03 8.88 8.34
Conversion/m% 77.34 63.30 66.46 59.84
Yield of light oil/m% 71.21 65.25 65.18 61.48
Light harvesting + liquefied gas/m% 81.23 72.70 74.81 69.03
Coke/conversion ratio 0.14 0.15 0.13 0.14
As can be seen from Table 3, compared with a comparative sample DBY-1 molecular sieve, the sample PDY-1 molecular sieve provided by the invention has excellent heavy oil cracking activity after being subjected to hydrothermal aging treatment at 800 ℃, 100% of water vapor and 17 hours, the conversion rate is improved by 14.04 percentage points, the gasoline yield is improved by nearly 9.54 percentage points, and the coke/conversion rate is reduced by 0.01.
Compared with a comparative sample DBY-2 molecular sieve, the sample PDY-6 molecular sieve provided by the invention has excellent heavy oil cracking activity after being subjected to hydrothermal aging treatment at 800 ℃, 100% of water vapor and 17 hours, the conversion rate is improved by 6.62 percentage points, the gasoline yield is improved by nearly 3.73 percentage points, and the coke/conversion rate is reduced by 0.01.
The heavy oil micro-reverse evaluation shows that the activity stability and gasoline selectivity of heavy oil catalytic cracking are improved on the premise that the coke yield is reduced to a certain extent.

Claims (10)

1. The Y-type molecular sieve containing rare earth is characterized in that at least mesoporous pore size distribution at 2-3nm, 3-4nm and 10-30nm exists, in a BJH pore size distribution spectrogram, the ratio of the peak area of the 2-3nm pore size distribution to the total pore peak area is greater than 0.1, and the ratio of the peak area of the 20nm pore size distribution to the total pore peak area is greater than 0.2.
2. The molecular sieve according to claim 1, wherein the ratio of the peak area of the 2-3nm pore size distribution to the total pore peak area is greater than 0.12, preferably greater than 0.15, more preferably 0.18 to 0.26, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area is greater than 0.22, preferably greater than 0.25, more preferably 0.27 to 0.32.
3. A molecular sieve according to claim 1 wherein said rare earth is present in an amount of 2 to 18 wt%, preferably 8 to 15 wt%, calculated as rare earth oxide, and has a unit cell constant of 2.440 to 2.470nm and a crystallinity of 30 to 60%.
4. Molecular sieve according to claim 1, characterized in that the intensity I of the peak at 11.8 ± 0.1 ° 2 θ in the X-ray diffraction diagram1Intensity of peak 12.3 + -0.1 DEG with 2 theta2Is greater than 4.0, preferably greater than 4.3, more preferably 4.8 to 6.0.
5. The preparation method of the Y-type molecular sieve containing the rare earth comprises the following steps:
(1) partial ammonium exchange is carried out on the NaY molecular sieve and ammonium salt to remove 10-80% of sodium ions, and NH is obtained after filtration, washing and drying4A NaY molecular sieve;
(2) NH obtained in the step (1)4The method comprises the following steps of (1) carrying out contact treatment on a NaY molecular sieve and a rare earth salt solution or a mixed solution of the rare earth salt solution and ammonium salt, filtering, washing and drying to obtain a rare earth NaY molecular sieve;
(3) and (3) carrying out hydrothermal roasting treatment on the rare earth NaY molecular sieve obtained in the step (2) 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.
6. The method according to claim 5, wherein the ammonium salt in the steps (1) and (2) is selected from any one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.
7. The method of claim 5, wherein the rare earth salt solution in step (2) is an aqueous chloride solution containing one or more of lanthanum, cerium, praseodymium, and neodymium ions.
8. The method according to claim 5, wherein the step (2) is carried out by exchanging the NaY molecular sieve with a rare earth salt solution or a mixed solution of the rare earth salt solution and an ammonium salt at a slurry pH of 3.0 to 5.0, a water sieve weight ratio of 5 to 30, and an exchange temperature of room temperature to 100 ℃ for at least 0.3 hour.
9. The method according to claim 5, wherein the atmosphere in the step (3) has an apparent pressure of 0.1 to 0.8MPa, preferably 0.3 to 0.6MPa, and contains 30 to 100% of water vapor, preferably 60 to 100% of water vapor.
10. The method according to claim 5, wherein the hydrothermal calcination in the step (3) is performed at 300 to 800 ℃, preferably 400 to 600 ℃.
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