CN113318777A - Catalytic cracking catalyst containing rare earth Y-type molecular sieve - Google Patents

Catalytic cracking catalyst containing rare earth Y-type molecular sieve Download PDF

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Publication number
CN113318777A
CN113318777A CN202010126355.0A CN202010126355A CN113318777A CN 113318777 A CN113318777 A CN 113318777A CN 202010126355 A CN202010126355 A CN 202010126355A CN 113318777 A CN113318777 A CN 113318777A
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rare earth
molecular sieve
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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Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN202010126355.0A priority Critical patent/CN113318777A/en
Priority to US17/626,059 priority patent/US20220250924A1/en
Priority to PCT/CN2020/101048 priority patent/WO2021004502A1/en
Priority to KR1020227004473A priority patent/KR20220025200A/en
Priority to EP20836459.6A priority patent/EP3998117A4/en
Priority to PCT/CN2020/101051 priority patent/WO2021004503A1/en
Priority to TW109123252A priority patent/TW202102439A/en
Priority to JP2022501268A priority patent/JP2022540629A/en
Priority to TW109123253A priority patent/TW202104082A/en
Priority to KR1020227004443A priority patent/KR20220034193A/en
Priority to JP2022501264A priority patent/JP2022540221A/en
Priority to EP20837442.1A priority patent/EP3998118A4/en
Priority to US17/626,087 priority patent/US20220259055A1/en
Publication of CN113318777A publication Critical patent/CN113318777A/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
    • B01J35/60—
    • B01J35/643—
    • B01J35/647—
    • B01J35/66—
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Abstract

The invention provides a catalytic cracking catalyst containing a rare earth Y-type molecular sieve, which contains the rare earth Y-type molecular sieve, an inorganic oxide binder and natural mineral substances and is characterized in that the rare earth Y-type molecular sieve at least has mesoporous pore size distribution at 2-3nm, 3-4nm and 10-30nm, 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 10-30nm pore size distribution to the total pore peak area is more than 0.2.

Description

Catalytic cracking catalyst containing rare earth Y-type molecular sieve
Technical Field
The invention relates to a catalytic cracking catalyst, and further relates to a catalytic cracking catalyst containing a rare earth Y-type molecular sieve.
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 roasted at high temperature (550-5)Solid ion exchange is carried out at 80 ℃, and then 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 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.
In the prior art, due to the limitation of a roasting process, during the process that rare earth ions in the rare earth Y molecular sieve are moved to a small cage position at a limited roasting temperature, a part of rare earth ions still exist in an ultra cage and cannot be moved to the small cage in time, so that the hydrothermal stability of the rare earth Y molecular sieve is limited, and the heavy oil cracking conversion capability of the rare earth Y molecular sieve in a catalytic cracking catalyst is further influenced.
Disclosure of Invention
The invention aims to provide a catalytic cracking catalyst containing a rare earth Y-type molecular sieve, which has high exchange degree and unique pore size distribution characteristic, aiming at the problem that the process of the rare earth Y-type molecular sieve in the catalytic cracking catalyst in the prior art is complex when the solid ion exchange degree is improved.
Therefore, the catalytic cracking catalyst containing the rare earth Y-type molecular sieve provided by the invention contains the rare earth Y-type molecular sieve, an inorganic oxide binder and natural mineral substances, and is characterized in that the rare earth Y-type molecular sieve at least has mesoporous pore size distribution at 2-3nm, 3-4nm and 10-30nm, 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 10-30nm pore size distribution to the total pore peak area is greater than 0.2.
The catalyst of the invention comprises 20-60 wt% of rare earth-containing Y-type molecular sieve, 10-30 wt% of inorganic oxide binder and 30-50 wt% of natural mineral substance based on dry weight. Wherein, the ratio of the peak area of the 2-3nm pore size distribution to the total pore peak area of the rare earth Y-type molecular sieve is more than 0.12, preferably more than 0.15, more preferably 0.18-0.26, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area of the rare earth Y-type molecular sieve is more than 0.22, preferably more than 0.25, more preferably 0.27-0.32. The rare earth Y-type molecular sieve has the rare earth content of 1-20 wt%, preferably 8-15 wt%, a unit cell constant of 2.440-2.470 nm and the crystallinity of 30-60% calculated by rare earth oxide.
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 intensity I of the 2 theta-11.8 +/-0.1 DEG peak in an X-ray diffraction pattern of the rare earth Y-type molecular sieve1Intensity 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. The rare earth Y-type molecular sieve adopted by the invention has better migration degree of rare earth ions from the super cage to the small cage.
The catalyst of the invention, wherein the rare earth Y-type molecular sieve is obtained by a method 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 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 method for preparing the rare earth Y-type molecular sieve is relatively simple and easy to operate. Wherein, 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 step (2), the rare earth salt solution is selected from a chloride aqueous solution of rare earth ions containing one or more of lanthanum, cerium, praseodymium and neodymium ions.
And (2) carrying out contact treatment on the NaY molecular sieve and a rare earth salt solution or a mixed solution of a rare earth salt solution and an ammonium salt, wherein the contact treatment is carried out on the NaY molecular sieve and the rare earth salt solution or the mixed solution of the ammonium salt and the rare earth salt solution, the contact treatment is carried out on the NaY molecular sieve and the mixed solution of the rare earth salt solution or the mixed solution of the ammonium salt and the rare earth salt solution, the pH value of slurry is 3.0-5.0, the weight ratio of a water sieve is 5-30, and exchange is carried out for at least 0.3 hour at 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.
The hydrothermal roasting treatment in the step (3) is carried out in an atmosphere environment in which external pressure is applied and water is added to the outside. 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. And (3) carrying out hydrothermal roasting at 300-800 ℃, preferably 400-600 ℃.
Step (4) of ammonium exchange may also be included after 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 rare earth Y-type molecular sieve serving as the active component of the catalyst is obtained by performing partial ammonium exchange on the NaY molecular sieve and ammonium salt and performing hydrothermal roasting in an atmosphere environment after rare earth exchange, wherein the treatment mode promotes rare earth ions to migrate from the supercage to the sodalite cages and generates unique pore size distribution characteristics, and the hydrothermal stability and the activity stability of the rare earth Y molecular sieve are improved.
In the catalytic cracking catalyst of the invention, the natural mineral matter is preferably at least one of kaolin, halloysite, montmorillonite, diatomite, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; the inorganic oxide binder is preferably at least one selected from silica sol, aluminum sol, peptized pseudo-boehmite, silica-alumina sol and phosphorus-containing aluminum sol.
The preparation method of the catalytic cracking catalyst comprises the following steps: the rare earth Y-type molecular sieve, natural mineral substances, inorganic oxide binder and the like are mixed with water to prepare the raw materials of the catalytic cracking catalyst, and then the mixture is pulped and spray-dried. Based on the dry weight, the rare earth Y-type molecular sieve contains 20-60 wt% of rare earth Y-type molecular sieve, 10-30 wt% of inorganic oxide binder and 30-50 wt% of natural mineral.
The catalytic cracking catalyst provided by the invention has excellent heavy oil conversion capability, higher gasoline yield and lower coke selectivity when being used for heavy oil catalytic cracking, and has wide application prospect in the field of heavy oil catalysis.
Drawings
FIG. 1 is a pore size distribution curve calculated by a BJH model for a sample PDY-1.
FIG. 2 is an XRD spectrum of PDY-1 sample.
FIG. 3 is a BJH pore size distribution curve for a comparative sample DDY-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 example and comparative example, the unit cell constant and crystallinity of the rare earth Y-type molecular sieve product are determined by X-ray diffraction (XRD), and the BJH pore size distribution curve of the product is measured by low-temperature nitrogen adsorption and desorption.
Example 1
Example 1 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the present invention.
Mixing 100g NaY molecular sieve (Changling division, China petrochemical catalyst, Inc., causticization 74.1 wt%, crystallinity 89.3%, the same below) and 1800g deionized water, pulping, adding 10g ammonium chloride solid, stirring, heating to 70 deg.C, stirring at constant temperature for 2h, 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 carrying out pressurized hydrothermal roasting treatment for 2h at 500 ℃, under the apparent pressure of 0.3Mpa and in the atmosphere of 100% steam to obtain a rare earth NaY molecular sieve sample, which is marked as 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 spectrogram tests intensity I of peak with 2 theta equal to 11.8 +/-0.1 DEG1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.8. The unit cell and crystallinity data are shown in table 1.
Comparative example 1
Comparative example 1 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium cross-linking and calcination at atmospheric pressure.
The procedure of example 1 was followed except that the calcination conditions were atmospheric pressure (apparent pressure 0 MPa). And obtaining a rare earth NaY molecular sieve comparison sample, and marking as D DY-1.
DDY-1, the rare earth oxide is 10.1 wt%.
FIG. 3 is a pore size distribution curve calculated by DDY-1 according to BJH model, wherein there are mainly 1 kind of mesoporous pore size distribution, that is, there is one kind of mesoporous pore size distribution at 3-4nm, but there is no mesoporous pore size distribution at 2-3nm and 10-30 nm.
DDY-1, the ratio of the peak area of the 2-3nm pore size distribution to the peak area of the total pores was 0, and the ratio of the peak area of the 10-30nm pore size distribution to the peak area of the total pores was 0.
DDY-1, characterized by the same pattern as figure 2, and tested the intensity of the peak at 11.8 + -0.1 deg. 2 theta1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 3.5. The unit cell and crystallinity data are shown in table 1.
Example 2
Example 2 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the present invention.
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 rare earth chloride solution and 8g ammonium chloride solid, stirring, heating to 60 deg.C, and adding dilute hydrochloric acidThe pH value of the slurry is adjusted to 4.0, and the slurry is stirred for 1.5h at constant temperature.
And filtering, washing with water, drying, applying external pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 0.5h at the temperature of 430 ℃ and under the apparent pressure of 0.8Mpa in a 50% steam atmosphere to obtain a rare earth NaY molecular sieve sample, which is marked as 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 PDY-2, 2-3nm pore size distribution to the total pore peak area was 0.12, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area was 0.25.
XRD spectrogram test shows that the intensity I of the peak with the 2 theta being 11.8 +/-0.1 DEG is1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.4. The unit cell and crystallinity data are shown in table 1.
Comparative example 2
Comparative example 2 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium cross-linking and calcination at atmospheric pressure.
The procedure of example 2 was repeated, except that the calcination conditions were atmospheric pressure and pressure (apparent pressure 0 MPa). A rare earth NaY molecular sieve comparison sample was obtained and is noted as DDY-2. The rare earth NaY molecular sieve comparative sample obtained is recorded as DDY-2.
DDY-2, the rare earth oxide is 8.2 wt%.
DDY-2, the XRD spectrum and BJH pore size distribution curve have the characteristics of figure 2 and figure 3 respectively.
DDY-2, the ratio of the peak area of the 2-3nm pore size distribution to the peak area of the total pores was 0, and the ratio of the peak area of the 10-30nm pore size distribution to the peak area of the total pores was 0.
DDY-2, and has an intensity I of 11.8 + -0.1 deg. peak with 2 theta1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 3.2. The unit cell and crystallinity data are shown in table 1.
Example 3
Example 3 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the invention.
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, applying external 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 a rare earth NaY molecular sieve sample, which is marked as PDY-3.
The chemical composition of PDY-3 contains rare earth oxide 11.4 wt%.
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 2-3nm pore size distribution to the total pore peak area of PDY-3 was 0.23, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area was 0.25.
XRD spectrogram test shows that the intensity I of the peak with the 2 theta being 11.8 +/-0.1 DEG is1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.4. The unit cell and crystallinity data are shown in table 1.
Comparative example 3
Comparative example 2 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium cross-linking and calcination at atmospheric pressure.
The procedure of example 2 was repeated, except that the calcination conditions were atmospheric pressure and pressure (apparent pressure 0 MPa). A rare earth NaY molecular sieve comparison sample was obtained and is noted as DDY-2. The rare earth NaY molecular sieve comparative sample obtained is recorded as DDY-3.
DDY-3, the rare earth oxide is 11.4 wt%.
DDY-3, the XRD spectrum and BJH pore size distribution curve have the characteristics of figure 2 and figure 3 respectively.
DDY-3, the ratio of the peak area of the molecular sieve with 2-3nm pore size distribution to the total pore peak area is 0, and the ratio of the peak area of the molecular sieve with 10-30nm pore size distribution to the total pore peak area is 0.
DDY-3, 2 theta 11.8 ±. + -.)Intensity of 0.1 ° peak I1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.1. The unit cell and crystallinity data are shown in table 1.
Example 4
Example 4 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the invention.
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 at 580 deg.C under an apparent pressure of 0.5Mpa in an atmosphere of 100% steam for 2h to obtain a rare earth NaY molecular sieve sample, which is marked as PDY-4.
The chemical composition of PDY-4 contains rare earth oxide 12.6 wt%.
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 2-3nm pore size distribution to the total pore peak area of PDY-4 was 0.23, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area was 0.21.
XRD spectrogram test shows that the intensity I of the peak with the 2 theta being 11.8 +/-0.1 DEG is1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.2. The unit cell and crystallinity data are shown in table 1.
Comparative example 4
Comparative example 4 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium exchange and calcination at atmospheric pressure.
The procedure of example 4 was repeated, except that the calcination conditions were atmospheric pressure and pressure (apparent pressure 0 MPa). A rare earth NaY molecular sieve comparison sample was obtained and is noted as DDY-2. The rare earth NaY molecular sieve comparative sample obtained is recorded as DDY-4.
DDY-4, the rare earth oxide is 12.6 wt%.
DDY-4, the XRD spectrum and BJH pore size distribution curve have the characteristics of figure 2 and figure 3 respectively.
DDY-4, the ratio of the peak area of the 2-3nm pore size distribution to the peak area of the total pores is 0, and the ratio of the peak area of the 10-30nm pore size distribution to the peak area of the total pores is 0.
DDY-4, and has an intensity I of 11.8 + -0.1 deg. peak with 2 theta1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.2. The unit cell and crystallinity data are shown in table 1.
Example 5
Example 5 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the invention.
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 carrying out pressurized hydrothermal roasting treatment for 1.5h at 550 ℃, under the apparent pressure of 0.4Mpa and in the atmosphere of 100% steam to obtain a rare earth NaY molecular sieve sample, which is marked as 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 2-3nm pore size distribution to the total pore peak area of PDY-5 was 0.24, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area was 0.29.
The strength I of the peak of PDY-5 with 2 theta 11.8 +/-0.1 DEG is tested by XRD1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 5.5. The unit cell and crystallinity data are shown in table 1.
Comparative example 5
Comparative example 5 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium cross-linking and calcination at atmospheric pressure.
The procedure of example 5 was repeated, except that the calcination conditions were atmospheric pressure and pressure (apparent pressure 0 MPa). A rare earth NaY molecular sieve comparison sample was obtained and is noted as DDY-2. The rare earth NaY molecular sieve comparative sample is recorded as DDY-5.
DDY-5, the rare earth oxide is 13.4 wt%.
DDY-5, the XRD spectrum and BJH pore size distribution curve have the characteristics of figure 2 and figure 3 respectively.
DDY-5, the ratio of the peak area of the 2-3nm pore size distribution to the peak area of the total pores is 0, and the ratio of the peak area of the 10-30nm pore size distribution to the peak area of the total pores is 0.
DDY-5, by XRD test, has an intensity I of 11.8 + -0.1 deg. peak 2 theta1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.4. The unit cell and crystallinity data are shown in table 1.
Example 6
Example 6 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the invention.
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.
And filtering, washing with water, drying, applying external pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 430 ℃ and under the apparent pressure of 0.6Mpa and the atmosphere of 100% steam to obtain a rare earth NaY molecular sieve sample, which is marked as 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 2-3nm pore size distribution to the total pore peak area of PDY-6 was 0.18, and the ratio of the peak area of the 10-30nm pore size distribution to the total pore peak area was 0.22.
The strength I of the peak of PDY-6 with 2 theta 11.8 +/-0.1 DEG is tested by XRD1Peak 12.3 ± 0.1 ° with 2 θStrength I of2The ratio of (A) to (B) is 4.9. The unit cell and crystallinity data are shown in table 1.
Comparative example 6
Comparative example 6 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium cross-linking and calcination at atmospheric pressure.
The procedure of example 6 was repeated, except that the calcination conditions were atmospheric pressure and pressure (apparent pressure 0 MPa). A rare earth NaY molecular sieve comparison sample was obtained and is noted as DDY-2. The rare earth NaY molecular sieve comparative sample is recorded as DDY-6.
DDY-6, the rare earth oxide is 10.0 wt%.
DDY-6 has the characteristics of figure 2 and figure 3 in XRD spectrum and BJH pore size distribution curve.
DDY-6, the ratio of the peak area of the 2-3nm pore size distribution to the peak area of the total pores is 0, and the ratio of the peak area of the 10-30nm pore size distribution to the peak area of the total pores is 0.
DDY-6 by XRD test, its 2 theta is 11.8 + -0.1 deg. peak intensity I1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 2.8. The unit cell and crystallinity data are shown in table 1.
Example 7
Example 7 illustrates the preparation of a rare earth NaY molecular sieve in a catalytic cracking catalyst of the invention.
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.
And filtering, washing with water, drying, applying external pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 400 ℃ and under the apparent pressure of 0.8Mpa and the atmosphere of 100% steam to obtain a rare earth NaY molecular sieve sample, which is marked as 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 PDY-7 at 2-3nm to the total pore content is 0.13, and the ratio of the pore size distribution content of PDY-7 at 10-30nm to the total pore content is 0.21.
The strength I of the peak of PDY-7 with 2 theta 11.8 +/-0.1 DEG is tested by XRD1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 4.4. The unit cell and crystallinity data are shown in table 1.
Comparative example 7
Comparative example 7 illustrates a comparative sample of rare earth NaY molecular sieve obtained with partial ammonium cross-linking and calcination at atmospheric pressure.
The procedure of example 7 was repeated, except that the calcination conditions were atmospheric pressure and pressure (apparent pressure 0 MPa). A rare earth NaY molecular sieve comparison sample was obtained and is noted as DDY-2. The rare earth NaY molecular sieve comparative sample obtained is recorded as DDY-7.
DDY-7, the rare earth oxide is 9.8 wt%.
DDY-7, the XRD spectrum and BJH pore size distribution curve have the characteristics of figure 2 and figure 3 respectively.
DDY-7, the ratio of the peak area of the 2-3nm pore size distribution to the peak area of the total pores was 0, and the ratio of the peak area of the 10-30nm pore size distribution to the peak area of the total pores was 0.
DDY-7, by XRD test, has an intensity I of 11.8 + -0.1 deg. peak 2 theta1Intensity of peak 12.3 + -0.1 DEG with 2 theta2The ratio of (A) to (B) is 3.2. The unit cell and crystallinity data are shown in table 1.
Test example 1
Test example 1 the crystal cells and crystallinity of the rare earth Y-type molecular sieve samples PDY-1 to PDY-7 after aging treatment were tested. Hydrothermal aging treatment conditions: 800 ℃, 100 percent of water vapor and 17 hours.
The data are shown in Table 1.
Comparative test example 1
Comparative test example 1 the unit cell and crystallinity of rare earth Y-type molecular sieve comparative samples DDY-1 to DDY-7 after aging treatment (hydrothermal aged samples) were tested. Hydrothermal aging treatment conditions: 800 ℃, 100 percent of water vapor and 17 hours.
The data are shown in Table 1.
TABLE 1
Figure BDA0002394476660000121
Figure BDA0002394476660000131
As can be seen from Table 1, the rare earth Y-type molecular sieve samples PDY-1-PDY-7 still have higher crystallinity after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, and the crystallinity of the samples PDY-1-PDY-7 is obviously higher than that of a comparison sample, which shows that compared with the normal pressure hydrothermal roasting, the rare earth Y-type molecular sieve obtained by hydrothermal treatment under the atmosphere environment condition of the invention has higher hydrothermal stability and obviously improved hydrothermal stability.
Examples 8 to 14
Examples 8-14 illustrate catalysts provided by the present invention, wherein the properties of the raw materials used are as follows: kaolin (Kaolin, Suzhou, China, 75 wt% solids), alumina sol (Qilu catalyst division, 21.5 wt% alumina), and pseudoboehmite (10 wt% solids).
Mixing and pulping pseudo-boehmite and deionized water, adding hydrochloric acid with the concentration of 36 wt% into the obtained slurry for peptization, wherein the acid-aluminum ratio (the weight ratio of the 36 wt% hydrochloric acid to the pseudo-boehmite calculated on a dry basis) is 0.20, heating to 65 ℃, acidifying for 1 hour, respectively adding kaolin slurry and alumina sol calculated on a dry basis, stirring for 20 minutes, then respectively adding rare earth Y-type molecular sieve samples PDY-1-PDY-7 calculated on a dry basis, stirring for 30 minutes to obtain slurry with the solid content of 30 wt%, and spray drying to obtain the microsphere catalyst. Then roasting the microspherical catalyst at 500 ℃ for 1 hour, washing the microspherical catalyst with an ammonium chloride aqueous solution at 60 ℃ (wherein the ammonium chloride is the microspherical catalyst and the water is 0.2:1:10) until the content of sodium oxide is less than 0.30 wt%, then washing the microspherical catalyst with deionized water for multiple times, filtering the microspherical catalyst, and drying the microspherical catalyst in a constant-temperature oven at 120 ℃ for 12 hours to obtain the catalyst marked as CD-1-CD-7.
The catalyst proportions on a dry basis are shown in Table 2.
Comparative examples 8 to 14
A catalytic cracking catalyst was prepared by following the procedure of example 8 except that the rare earth Y-type molecular sieve PDY-1 in example 8 was replaced with comparative examples DDY-1 to DDY-7 of the rare earth Y-type molecular sieve prepared in comparative examples 1 to 7, respectively, and the prepared catalysts were designated as DCD-1 to DCD-7, respectively.
The catalyst proportions on a dry basis are shown in Table 2.
TABLE 2
Figure BDA0002394476660000141
Test example 2
This test example illustrates the reaction effects of the catalytic cracking catalysts of examples 8 to 14 and comparative examples 3 and 4.
And (3) respectively carrying out heavy oil micro-reverse evaluation on the catalyst samples CD-1-CD-7 and the comparative catalyst samples DCD-1 and DCD-2 after carrying out hydrothermal aging treatment at 800 ℃ for 100% of water vapor for 17 hours.
Heavy oil micro-reverse evaluation conditions: the loading of the catalyst is 5g, the raw oil is mixed three heavy oil (physicochemical properties are shown in Table 3), the oil inlet amount is 1.384g, the reaction temperature is 500 ℃, and the regeneration temperature is 600 ℃.
The evaluation results are shown in Table 4.
TABLE 3
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 4
Figure BDA0002394476660000161
As can be seen from table 4, the catalyst prepared by the present invention has excellent heavy oil conversion ability and higher gasoline yield. For example, compared with a DCD-1 comparison sample, the CD-1 sample of 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 5.85 percentage points, the gasoline yield is improved by 2.52 percentage points, and the coke/conversion rate is reduced by 0.01.

Claims (10)

1. A catalytic cracking catalyst containing a rare earth Y-type molecular sieve contains the rare earth Y-type molecular sieve, an inorganic oxide binder and natural mineral substances, and is characterized in that the rare earth Y-type molecular sieve at least has mesoporous pore size distribution at 2-3nm, 3-4nm and 10-30nm, 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 10-30nm pore size distribution to the total pore peak area is greater than 0.2.
2. The catalyst according to claim 1, wherein the rare earth Y-type molecular sieve comprises 20-60 wt% of the rare earth Y-type molecular sieve, 10-30 wt% of the inorganic oxide binder and 30-50 wt% of the natural mineral substance, based on the dry weight.
3. The catalyst according to claim 1, wherein the rare earth Y-type molecular sieve has a ratio of a peak area of a pore size distribution of 2-3nm to a peak area of total pores of more than 0.12, preferably more than 0.15, more preferably 0.18 to 0.26, and a ratio of a peak area of a pore size distribution of 10-30nm to a peak area of total pores of more than 0.22, preferably more than 0.25, more preferably 0.27 to 0.32.
4. The catalyst according to claim 1, wherein the rare earth Y-type molecular sieve has a rare earth content of 1 to 20 wt%, preferably 8 to 15 wt%, a unit cell constant of 2.440 to 2.470nm and a crystallinity of 30 to 60%, based on the rare earth oxide.
5. The catalyst according to claim 1 wherein said rare earth Y-type molecular sieve is characterized by an intensity I of the peak at 11.8 ± 0.1 ° 2 Θ in the X-ray diffraction pattern1Intensity 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.
6. The catalyst of claim 1, wherein said rare earth Y-type molecular sieve is obtained by a process comprising the steps of:
(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.
7. The catalyst according to claim 6, wherein the ammonium salt in the steps (1) and (2) is selected from a mixture of any one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate; in the step (2), the rare earth salt solution is selected from a chloride aqueous solution of rare earth ions containing one or more of lanthanum, cerium, praseodymium and neodymium ions.
8. The catalyst according to claim 6, wherein the contact treatment in step (2) is carried out 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 catalyst according to claim 6, wherein the atmosphere in step (3) has an apparent pressure of preferably 0.1 to 0.8MPa, more preferably 0.3 to 0.6MPa, and contains 30 to 100% of water vapor, preferably 60 to 100% of water vapor; and (3) carrying out hydrothermal roasting at 300-800 ℃, preferably 400-600 ℃.
10. The catalyst according to claim 1, wherein the natural mineral is at least one selected from the group consisting of kaolin, halloysite, montmorillonite, diatomaceous earth, attapulgite, sepiolite, halloysite, hydrotalcite, bentonite and rectorite; the inorganic oxide binder is at least one selected from silica sol, aluminum sol, peptized pseudo-boehmite, silicon-aluminum sol and phosphorus-containing aluminum sol.
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