CN111747424B

CN111747424B - Preparation method of rare earth and phosphorus-containing porous material

Info

Publication number: CN111747424B
Application number: CN201910236244.2A
Authority: CN
Inventors: 郑金玉; 王成强; 罗一斌; 满征
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-03-27
Filing date: 2019-03-27
Publication date: 2023-05-05
Anticipated expiration: 2039-03-27
Also published as: CN111747424A

Abstract

The preparation method of a porous material containing rare earth and phosphorus, is that a porous material is modified by rare earth and phosphorus, and is obtained by two-to-one baking or two-to-two baking, wherein the porous material has a composite structure of micropores with FAU crystalline phase structure and mesopores with pseudo-boehmite amorphous phase structure, the disordered structure of the pseudo-boehmite part grows along the edge of ordered diffraction fringe of the FAU crystal part, and a/b=1.5-10 in Raman spectrum; BJH curves show gradient pore distribution characteristics, and several pore distributions appear at 3-4 nm, 8-20 nm and 18-40 nm, respectively. The porous material containing rare earth and phosphorus is characterized by more suitable cracking reaction in the pore canal structure and acid distribution due to the organic combination of the micro pore canal structure and the mesoporous pore canal structure and the common modification of the rare earth and the phosphorus, and the improvement of cracking performance is promoted.

Description

Preparation method of rare earth and phosphorus-containing porous material

Technical Field

The invention relates to a preparation method of a porous material, in particular to a preparation method of a porous material containing phosphorus and rare earth and having a micropore structure and a mesoporous structure.

Background

Catalytic cracking is a very important process in petroleum refining, is widely applied to the petroleum processing industry, and plays a role in petroleum refineries. In the catalytic cracking process, heavy fractions such as vacuum distillates or heavier residuum are reacted in the presence of a catalyst to convert them into gasoline, distillate and other liquid cracked products and lighter, four carbon and less gaseous cracked products. Catalytic cracking reactions follow the mechanism of carbonium ion reactions and therefore require the use of acidic catalytic materials, particularly catalytic materials with strong B acid centers. The amorphous silica alumina material is an acidic catalytic material which has both B acid center and L acid center, is the main active component in early catalytic cracking catalysts, but is gradually replaced by crystalline molecular sieves due to lower cracking activity and higher required reaction temperature. The crystalline molecular sieve is a porous material with a pore diameter smaller than 2nm and a special crystal phase structure, and the material with the pore diameter smaller than 2nm is named as a microporous material according to the definition of IUPAC, so that the crystalline molecular sieve or zeolite generally belongs to the microporous material, and the microporous molecular sieve material has stronger acidity and higher structural stability due to a relatively complete crystal structure and a special framework structure, and shows higher catalytic activity in catalytic reaction, and is widely applied to petroleum processing and other catalytic industries.

The Y-type molecular sieve is used as a typical microporous molecular sieve material, and has regular pore canal structure, good stability and strong acidity, thus being applied to the fields of catalytic cracking, hydrocracking and the like on a large scale. When the catalyst is used in a catalytic cracking catalyst, a certain modification treatment is usually required to be carried out on the Y-type molecular sieve, for example, the dealumination of a framework is inhibited through rare earth modification, the structural stability of the molecular sieve is improved, the retention degree of acid centers is increased, and the cracking activity is further improved; or the silicon-aluminum ratio of the framework is improved through ultra-stabilization treatment, so that the stability of the molecular sieve is improved. CN1436727a discloses a modified faujasite and hydrocarbon cracking catalyst containing the zeolite, which adopts a one-to-one baking process, i.e. NaY is firstly subjected to a one-time exchange reaction with phosphorus compound and ammonium compound, then rare earth solution is added for continuous reaction, and then the catalyst is obtained through filtration, washing and hydrothermal baking.

CN1382631A discloses a high-silicon rare earth Y-type zeolite, which is prepared by gas phase reaction of rare earth Y-type zeolite and silicon tetrachloride to obtain rare earth Y-type zeolite with the content of rare earth in a crystal of 4-15 wt%, the unit cell constant of 2.450-2.458 nm, the collapse temperature of 1000-1056 ℃, the silicon-aluminum ratio of 8.3-8.8 and the sodium oxide content of less than 1.0 wt%, and has good heavy oil cracking activity and selectivity, can improve the yield of light oil, improve the quality of gasoline and have good coke selectivity.

CN101823726a discloses a modified Y molecular sieve, which is prepared by a one-to-one baking process, that is, naY is firstly subjected to an exchange reaction with rare earth solution, then phosphorus compound is added to continue the reaction, and then the reaction is filtered, washed and hydrothermally baked, wherein the rare earth content is about 11-23 wt%, most of rare earth is located in sodalite cages, the stability of the molecular sieve is improved, meanwhile, the acidity of the molecular sieve can be adjusted, and the catalyst containing the molecular sieve has the characteristics of strong heavy oil conversion capability and good coke selectivity.

CN100344374C discloses a rare earth Y molecular sieve and a preparation method thereof, wherein the rare earth content is 12-22 wt% of rare earth oxide, and rare earth ions are all positioned in a small cage of the molecular sieve ²⁷ In the Al MAS NMR spectrum, no peak was observed at a chemical shift of 0 ppm. The preparation method comprises the steps of adopting a one-crossing one-baking process, regulating the pH value of the solution to 8-11 by using an alkaline solution after one-crossing, filtering, washing, drying and baking, or separating a molecular sieve filter cake after one-crossing, collecting filtrate, adding the alkaline solution into the filtrate to regulate the pH value of the solution to 8-11, pulping the obtained rare earth hydroxide filter cake and the molecular sieve filter cake by adding water, filtering, washing, drying and baking. The process ensures that redundant rare earth ions in the solution are precipitated to avoid rare earth loss and ensure that the rare earth ions are all positioned in a small cage of the molecular sieve.

CN1317547A discloses an olefin-reducing catalyst and a preparation method thereof, wherein the catalyst mainly comprises REY molecular sieves with the rare earth content of 12-20 percent by weight and the crystallinity of more than 50 percent, and PREY molecular sieves with the rare earth content of 2-12 percent by weight, the phosphorus content of 0.2-3 percent by weight and the unit cell constant of 2.445-2.465 nm, and the catalyst has obvious olefin-reducing effect and can ensure the product distribution and the gasoline octane number compared with the conventional catalyst.

CN1506161A discloses a rare earth ultrastable Y molecular sieve, which also adopts a two-step two-baking process, namely after obtaining one-step one-baking rare earth sodium Y, the rare earth and phosphorus-containing substances react step by step, and the second baking is carried out, so that the composite modified Y molecular sieve with the rare earth content of 8-25% by weight, the phosphorus content of 0.1-3.0% by weight, the crystallinity of 30-55% and the unit cell constant of 2.455-2.477 nm is obtained, and the molecular sieve has the obvious effect of reducing gasoline olefin, moderate coke yield, high diesel yield and high utilization rate of modified elements.

The molecular sieve prepared by the two-stage baking process has other characteristics, such as the molecular sieve capable of improving coking performance disclosed in CN101537366A and the preparation method thereof, and the two-stage baking process is still adopted, wherein the phosphorus content of the molecular sieve is 0.05-5.0%, the rare earth content is less, the rare earth content is only 0.05-4.0%, the unit cell constant is 2.430-2.440 nm, and the crystallinity is 35-55%.

With the increasing depletion of petroleum resources, the trend of heavy and inferior crude oil is obvious, the blending proportion is continuously improved, and meanwhile, the demand of the market for light oil products is not reduced, so that the deep processing of heavy oil and residual oil is increasingly emphasized in the petroleum processing industry in recent years, many refineries already begin to blend vacuum residual oil, even directly taking the atmospheric residual oil as a cracking raw material, and the catalytic cracking of heavy oil gradually becomes a key technology for improving economic benefits of oil refining enterprises, wherein the macromolecule cracking capability of a catalyst is the focus of attention. The Y-type molecular sieve is the most main cracking active component in the conventional cracking catalyst, but has a relatively obvious pore canal limiting effect in macromolecular reactions due to the smaller pore canal structure, and also has a certain inhibiting effect on the cracking reactions of macromolecules such as heavy oil or residual oil. Therefore, for catalytic cracking of heavy oils, it is desirable to use materials that have larger pore sizes, no diffusion limitations on reactant molecules, and higher cracking activity.

According to IUPAC definition, the material with pore diameter between 2-50 nm is mesoporous material, and the size range of macromolecules such as heavy oil or residual oil is in the pore diameter range, so the research of mesoporous material, especially mesoporous silicon-aluminum material, is of great interest to researchers in the catalysis field. Mesoporous materials were first developed in 1992 by the company Mobil in the united states (Beck J S, varuli J Z, roth WJ et al, j.am.chem.comm.soc.,1992, 114, 10834-10843), named M41S series mesoporous molecular sieves, including MCM-41 (Mobil Corporation Material-41) and MCM-48, etc., with pore diameters of 1.6-10 nm, uniform and adjustable pore size distribution, large specific surface area and pore volume, and strong adsorption capacity; however, the pore wall structure of the molecular sieve is an amorphous structure, so that the molecular sieve has poor hydrothermal stability and weak acidity, cannot meet the operation conditions of catalytic cracking, and is greatly limited in industrial application.

In order to solve the problem of poor hydrothermal stability of the mesoporous molecular sieve, part of research work is focused on improving the wall thickness of the molecular sieve hole, for example, a molecular sieve with thicker hole wall can be obtained by adopting a neutral template agent, but the defect of weaker acidity still exists. In CN 1349929a, a novel mesoporous molecular sieve is disclosed, in which the primary and secondary structural units of zeolite are introduced into the wall of molecular sieve hole, so that it has the basic structure of traditional zeolite molecular sieve, and said mesoporous molecular sieve has strong acidity and superhigh hydrothermal stability. However, the molecular sieve has the defects that a template agent with high price is needed, the pore diameter is only about 2.7nm, the steric hindrance effect on the macromolecular cracking reaction is still large, the structure is easy to collapse under the high-temperature hydrothermal condition, and the cracking activity is poor.

In the field of catalytic cracking, silicon-aluminum materials are widely used because of their strong acidic centers and good cracking properties. The proposal of the mesoporous concept provides possibility for the preparation of novel catalysts, and the current research results are mainly focused on using expensive organic templates and organic silicon sources, and most of the research results are subjected to a high-temperature hydrothermal post-treatment process. In order to reduce the preparation cost and obtain the porous material in the mesoporous range, more research work is focused on the development of disordered mesoporous materials. US5,051,385 discloses a monodisperse mesoporous silica-alumina composite material prepared by mixing acidic inorganic aluminum salt and silica sol, adding alkali, and reacting, wherein the aluminum content is 5-40 wt%, the pore diameter is 20-50 nm, and the specific surface area is 50-100 m ² And/g. The method disclosed in US4,708,945 comprises loading silica particles or hydrated silica on porous boehmite, and hydrothermally treating the obtained composite at above 600deg.C for a certain time to obtain a catalyst with silica supported on the surface of boehmite, wherein the silica is combined with hydroxyl groups of transition boehmite, and the surface area is 100-200 m ² And/g, average pore diameter of 7-7.5 nm. A series of acid cracking catalysts are disclosed in US4,440,872, wherein the support of some of the catalysts is obtained by reacting gamma-Al ₂ O ₃ Impregnating silane, and roasting at 500 ℃ or treating by water vapor. In CN1353008A, inorganic aluminum salt and water glass are used as raw materials, stable and clear silica-alumina sol is formed through the processes of precipitation, washing, de-gelling and the like, white gel is obtained through drying, and the silica-alumina catalytic material is obtained through roasting for 1 to 20 hours at the temperature of 350 to 650 ℃. In CN1565733A a is disclosedThe mesoporous silica-alumina material has pseudo-boehmite structure, concentrated pore size distribution and specific surface area of about 200-400 m ² The mesoporous silica-alumina material has the advantages of high cracking activity and hydrothermal stability, and good macromolecule cracking performance in catalytic cracking reaction, and the preparation of the mesoporous silica-alumina material does not need an organic template agent, and has the advantages of 0.5-2.0 ml/g of pore volume, 8-20 nm of average pore diameter and 5-15 nm of most probable pore diameter.

Disclosure of Invention

The invention aims to provide a preparation method of a porous material containing rare earth and phosphorus, micropores and mesopores, which is different from the prior art.

In order to achieve the purpose of the invention, the preparation method of the rare earth and phosphorus-containing porous material provided by the invention comprises the following steps: (1) Carrying out first contact treatment on a porous material and a rare earth solution and/or an ammonium salt solution, filtering, washing with water and drying; (2) Performing primary roasting treatment on the water vapor obtained in the step (1) under the condition of 0-100%; (3) And (3) adding water into the porous material obtained in the step (2), pulping, carrying out secondary contact treatment with an ammonium salt solution and a phosphorus source, filtering, washing and drying, or carrying out secondary roasting treatment under the condition of 0-100% water vapor to obtain the rare earth and phosphorus-containing porous material, wherein the porous material in the step (1) contains a FAU crystalline phase structure and a pseudo-boehmite amorphous phase structure in an XRD spectrogram, an ordered diffraction stripe of a FAU crystal part and a disordered structure of a pseudo-boehmite part are simultaneously visible in a transmission electron microscope TEM, the disordered structure grows along the edge of the ordered diffraction stripe, and the two structures are effectively combined together to form a micropore and mesoporous composite structure. The porous material of step (1) has an anhydrous chemical expression of: (4-12) Na ₂ O·(25～65)SiO ₂ ·(25～70)Al ₂ O ₃ The specific surface area is 350-750 m ² Per gram, the specific surface area of the mesoporous is 50-450 m ² Per gram, the total pore volume is 0.5-1.5 ml/g, and the mesoporous volume is 0.2-1.2 ml/g. Raman spectroscopy (Ramam) can be used for structural analysis, which is based on changes in polarization degree upon vibration, by generating energy exchange with incident photons, causing scattered photonsThe energy of the incident photon is differentiated from the energy of the incident photon, i.e., raman shift (Raman shift), to determine the corresponding structure. The porous material of step (1) having a Raman (Raman) spectrum with a/b=1.5 to 10.0, wherein a represents a Raman shift of 500cm ^-1 The spectral peak intensity of b represents a Raman shift of 350cm ^-1 Peak intensities of the spectra of (2).

In the porous material in the step (1), ordered diffraction fringes of the FAU crystal part and disordered structures of the pseudo-boehmite part are simultaneously visible in a transmission electron microscope TEM, disordered structures of the pseudo-boehmite part grow along the edge derivatives of the ordered diffraction fringes of the FAU crystal phase, edge lines of the crystal structure disappear, and the two structures are effectively combined together to form a microporous and mesoporous composite structure. Wherein, the FAU crystal phase structure shows ordered and orderly arranged diffraction fringes in a transmission electron microscope. The pseudo-boehmite structure is in a disordered structure in a transmission electron microscope, and has no fixed crystal face trend. SEM characterization shows that both the pleated structure and a portion of the grains of the Y-type molecular sieve are visible, with the majority of the molecular sieve grains being encapsulated by the surface-grown pleated mesoporous structure.

The porous material in the step (1) has gradient pore distribution characteristics formed by a micropore structure and a mesoporous structure, and obvious pore distribution can be respectively formed at 3-4 nm, 8-20 nm and 18-40 nm.

Further, the porous material in the step (1) may be prepared by the following process: adding water into molecular sieve dry powder with FAU crystal structure, pulping, stirring uniformly, adding aluminum source and alkali solution at room temperature to 85deg.C, mixing thoroughly, controlling pH value of slurry system to 7-11, performing contact reaction, and taking aluminum oxide in the aluminum source as reference, and SiO ₂ :Al ₂ O ₃ And (1) adding a silicon source calculated by silicon oxide into the reaction slurry according to the weight ratio of (1-9), continuously reacting for 1-10 hours at the temperature of room temperature to 90 ℃, or stirring for 1-4 hours at the constant temperature of room temperature to 90 ℃, crystallizing for 3-30 hours at the temperature of 95-105 ℃ in a closed reaction kettle, and recycling the product.

In the preparation of the porous material in the above step (1), theThe molecular sieve of the FAU crystal structure is a NaY molecular sieve. NaY molecular sieves of different silica to alumina ratios, different crystallinity, different grain sizes, preferably more than 70%, more preferably more than 80%. For example, naY molecular sieve dry powder can be obtained by mixing and stirring water glass, sodium metaaluminate, aluminum sulfate, a directing agent and deionized water according to a certain proportion and a specific feeding sequence, crystallizing for a plurality of times at a temperature of 95-105 ℃, filtering, washing and drying. The addition ratio of the sodium silicate, the sodium metaaluminate, the aluminum sulfate, the guiding agent and the deionized water can be the addition ratio of a conventional NaY molecular sieve, and can also be the addition ratio of a NaY molecular sieve for preparing special performance, such as the addition ratio of a large-grain or small-grain NaY molecular sieve, and the like, and the addition ratio and the concentration of each raw material are not particularly limited, so long as the NaY molecular sieve with FAU crystal phase structure can be obtained. The order of addition may be in various ways, and is not particularly limited. The guiding agent is prepared by various methods, for example, the guiding agent can be prepared according to the methods disclosed in the prior art (US 3639099 and US 3671191), and the typical guiding agent is prepared by using a silicon source, an aluminum source, alkali liquor and deionized water according to (15-18) Na ₂ O:Al ₂ O ₃ :(15～17)SiO ₂ :(280～380)H ₂ Mixing the O in a molar ratio, uniformly stirring, and standing and aging for 0.5-48 h at the temperature of between room temperature and 70 ℃ to obtain the catalyst. The silicon source used for preparing the guiding agent is sodium silicate, the aluminum source is sodium metaaluminate, and the alkali liquor is sodium hydroxide solution.

In the preparation of the porous material in the step (1), as described above, the aluminum source is selected from one or more of aluminum nitrate, aluminum sulfate or aluminum chloride; the alkali solution is selected from one or more of ammonia water, potassium hydroxide, sodium hydroxide or sodium metaaluminate, and when sodium metaaluminate is taken as the alkali solution, the alumina content accounts for the total alumina content. The contact reaction temperature is from room temperature to 85℃and preferably from 30 to 70 ℃.

In the preparation of the porous material in the step (1), the silicon source is selected from one or more of sodium silicate, tetraethoxysilane, tetramethoxysilane and silicon oxide. The temperature at which the reaction is continued after the addition of the silicon source is from room temperature to 90 ℃, preferably from 40 to 80 ℃, and the reaction time is from 1 to 10 hours, preferably from 2 to 8 hours. The process for recovering the product generally comprises the steps of filtering, washing and drying the crystallized product, which are well known to those skilled in the art and will not be described in detail herein.

In the first contact treatment process of the porous material and the rare earth solution and/or the ammonium salt solution in the step (1), the weight ratio of the rare earth solution to the porous material is 0.02-0.14, preferably 0.03-0.13, and the weight ratio of the ammonium salt to the porous material is 0.05-0.2, wherein the contact temperature is 40-90 ℃, preferably 50-80 ℃, and the contact time is 0.5-3.0 hours, preferably 1-2 hours.

The first or second calcination treatment in the steps (2) and (3) is a calcination treatment at 500 to 700 ℃, preferably 530 to 680 ℃, under 0 to 100% steam, preferably 20 to 100% steam, for 0.5 to 4.0 hours, preferably 1 to 3 hours.

The second contact treatment in the step (3) can adopt a mixed contact treatment mode of an ammonium salt solution and a phosphorus source, namely, the second contact treatment mode is that the solution obtained in the step (2) is simultaneously contacted with the ammonium salt solution and the phosphorus source, and the solution is filtered, washed and dried; or adopting a step-by-step treatment mode, namely, adding water into the mixture obtained in the step (2), pulping, then carrying out contact treatment on the mixture and an ammonium salt solution, filtering, washing, then contacting the mixture with a phosphorus source, filtering or filtering-free drying; the weight ratio of the ammonium salt to the phosphorus source obtained in the step (2) is 0.1-0.4, the weight ratio of the phosphorus source to the phosphorus source obtained in the step (2) is 0.01-0.06, the contact temperature is room temperature-90 ℃, preferably 50-80 ℃, and the contact time is 0.5-3.0 hours, preferably 1-2 hours.

The preparation method of the invention, the rare earth solution is well known to the person skilled in the art, can be rare earth chloride or rare earth nitrate composed of single rare earth element, wherein common rare earth solutions comprise lanthanum chloride, lanthanum nitrate, cerium chloride or cerium nitrate, and the like, can also be mixed rare earth with different rare earth element proportions, such as cerium-rich or lanthanum-rich mixed rare earth, and can be of any concentration; the mixed solution of the rare earth solution and the ammonium salt can be prepared by mixing the ammonium salt and the rare earth solution in proportion, or adding the ammonium salt and the rare earth solution one by one in proportion, wherein the ammonium salt can be one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate. The phosphorus source can be one or more of ammonium phosphate, diammonium phosphate, monoammonium phosphate and phosphoric acid. The filtering, washing and drying processes are well known to those skilled in the art, and are not described herein.

In the method provided by the invention, in the process of treating the porous material by using rare earth and phosphorus, the treatment sequence of rare earth modification and phosphorus modification is adopted. The introduction of rare earth can play a role in stabilizing the microporous part, namely stabilizing the framework structure of the molecular sieve, and the subsequent introduction of phosphorus is mainly used for modifying the mesoporous part and further optimizing the respective structural characteristics of the micropores and the mesopores.

The porous material containing rare earth and phosphorus, which is prepared by the method, is characterized in that the rare earth content is 2-14 wt% based on rare earth oxide, and the phosphorus content is 1-6 wt% based on phosphorus pentoxide; microporous structure containing FAU crystal phase and gamma-Al ₂ O ₃ Mesoporous structure, said gamma-Al ₂ O ₃ The mesoporous structure grows in a derivative way on the edge of the FAU crystal phase structure, and the two structures are organically connected; the unit cell constant is 2.455-2.470 nm, the relative crystallinity is 25-65%, and the total specific surface area is 350-600 m ² Per gram, total pore volume of 0.5-1.0 cm ³ /g。

The porous material containing rare earth and phosphorus of the invention has XRD spectra with characteristic diffraction peaks of FAU crystal phase structure at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 31.4 degrees and the like, and wide peaks between 20 degrees and 30 degrees and characteristic diffraction peaks around 66 degrees show gamma-Al ₂ O ₃ Structure is as follows.

Drawings

FIG. 1 is an X-ray diffraction pattern of the porous material YCMN-1 of example 1.

FIG. 2 is a TEM transmission electron micrograph of the porous material YCMN-1 of example 1.

FIG. 3 is a BJH pore size distribution curve of the porous material YCMN-1 of example 1.

FIG. 4 is an SEM image of the porous material YCMN-1 of example 1.

FIG. 5 is an X-ray diffraction pattern of the porous material RPA-1 containing rare earth and phosphorus prepared in example 1.

FIG. 6 is a BJH pore size distribution curve of the porous material YCM-1 of example 4.

FIG. 7 is an X-ray diffraction pattern of the porous material YCM-1 of example 4.

FIG. 8 is a TEM transmission electron micrograph of the porous material YCM-1 of example 4.

FIG. 9 is an SEM photograph of the porous material YCM-1 of example 4.

Detailed Description

The following examples further illustrate the invention but are not intended to limit it.

The preparation process of the guiding agent adopted in the examples is as follows: 5700g of water glass (supplied by Kagaku catalyst Co., ltd., siO) ₂ 261g/L, modulus 3.31, density 1259 g/L) was placed in a beaker, and 4451g of sodium highly basic metaaluminate (supplied by Kaolin catalyst Co., ltd., al) was added under vigorous stirring ₂ O ₃ 39.9g/L，Na ₂ 279.4g/L of O, 1326g/L of density) and standing and aging for 18 hours at 30 ℃ to obtain the catalyst with the molar ratio of 16.1Na ₂ O:Al ₂ O ₃ :15SiO ₂ :318.5H ₂ And a directing agent for O.

In various embodiments, RE of the material ₂ O ₃ 、P ₂ O ₅ 、Na ₂ O、Al ₂ O ₃ 、SiO ₂ The content was measured by X-ray fluorescence (see "petrochemical analysis method (RIPP Experimental method)", yang Cuiding et al, scientific Press, 1990).

The phase, unit cell constant, crystallinity, and the like were measured by an X-ray diffraction method. Wherein, the crystallinity is measured according to the industrial standards SH/T0340-92 and SH/T0339-92 of China petrochemical industry Co., ltd: naY molecular sieves (GS BG 75004-1988).

Transmission electron microscope TEM test was performed using a FEI Tecnai F20G2S-TWIN transmission electron microscope, operating at 200kV.

Scanning electron microscope SEM test using a field emission scanning electron microscope, hitachi S4800 model, japan, accelerating voltage 5kV, spectra were collected and processed using Horiba 350 software.

The pore parameters were determined using a low temperature nitrogen adsorption-desorption capacity method.

The laser Raman spectrum adopts LabRAM HR UV-NIR laser confocal Raman spectrometer of HORIBA company in Japan, the wavelength of excitation light source is 325nm, the ultraviolet is 15 times of objective lens, confocal pinhole is 100 μm, and spectrum scanning time is 100s.

Examples 1-8 illustrate the preparation of the rare earth and phosphorus containing porous materials provided by the present invention.

Example 1

According to 8.5SiO ₂ ：Al ₂ O ₃ ：2.65Na ₂ O：210H ₂ Mixing water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water according to a certain proportion, stirring for 1 hour, crystallizing the gel at 100 ℃ for 30 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours to obtain the NaY molecular sieve.

Adding water again to the obtained NaY molecular sieve dry powder, pulping, stirring uniformly, heating to 50 ℃, and stirring vigorously while simultaneously stirring AlCl ₃ Solution (concentration 60 gAl) ₂ O ₃ L) and NaAlO ₂ Solution (concentration 102 gAl) ₂ O ₃ and/L) is added in parallel to carry out contact reaction, the pH value of the slurry system is controlled to be 8.5, and after a certain period of reaction, the reaction is carried out according to the total Al in the aluminum chloride solution and the sodium metaaluminate solution ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ Tetraethoxysilane was added to the reaction slurry at a weight ratio of 1:8, and the reaction was continued at 80 ℃ for 6 hours, followed by filtration, washing and oven drying at 120 ℃ to give porous material YCMN-1.

YCMN-1 fluorescence analysis chemical composition is 9.41Na ₂ O·53.6SiO ₂ ·37.2Al ₂ O ₃ The X-ray diffraction diagram is shown in fig. 1, and shows that the crystal contains both FAU crystal phase structure and pseudo-boehmite structure. Y is YA TEM photograph of CMN-1 transmission electron microscope is shown in fig. 2, showing that two structures exist simultaneously and are bonded together, and that the amorphous phase of pseudo-boehmite, the amorphous structure, grows along the edges of the FAU crystalline phase structure to form a composite structure. The BJH pore size distribution curve is shown in fig. 3, showing the characteristic of a gradient pore distribution, with distinct collisional pore distributions at 3.8nm, 11.5nm, and 19.2nm, respectively. SEM is shown in fig. 4, and it can be seen that the pleated structure and a part of the grains of the Y-type molecular sieve are mostly covered by the pleated mesoporous structure grown on the surface. Its BET specific surface area is 623m ² /g, mesoporous specific surface area of 89m ² Per gram, the total pore volume is 0.70ml/g, and the mesoporous volume is 0.44ml/g; a/b=7.3 for YCMN-1, where a represents a Raman shift of 500cm in the Raman (Raman) spectrum ^-1 The spectral peak intensity of b represents a Raman shift of 350cm ^-1 Peak intensities of the spectra of (2).

The porous material YCMN-1 and the rare earth chloride solution are contacted with the ammonium salt solution for 2 hours at 60 ℃ according to the weight ratio of rare earth oxide to porous material of 0.1 and the weight ratio of 0.05, filtered, washed and dried; roasting at 600 deg.c and 100% water vapor for 2 hr; and (3) adding water into the roasted sample, pulping, carrying out contact treatment for 0.5 hour at 60 ℃ according to the weight ratio of ammonium chloride to the roasted sample of 0.4, filtering, washing with water, mixing with phosphoric acid, carrying out contact treatment for 0.5 hour at 60 ℃ continuously, wherein the weight ratio of phosphoric acid to the roasted sample is 0.04 (calculated by phosphorus pentoxide), filtering, and drying to obtain the porous material containing rare earth and phosphorus, namely RPA-1.

The XRD diffraction pattern of RPA-1 is shown in FIG. 5, which shows the FAU crystalline phase structure and gamma-Al containing both Y-type molecular sieves ₂ O ₃ Structurally, FAU structural characteristic peaks (peaks corresponding to the signs in the figure) appear at 6.2 degrees, 10.1 degrees, 11.9 degrees, 15.7 degrees, 18.7 degrees, 20.4 degrees, 23.7 degrees, 27.1 degrees, 31.4 degrees and the like, and gamma-Al appears between 20 degrees and 30 degrees and around 66 degrees respectively ₂ O ₃ Structural characteristic peaks (peaks corresponding to brackets in the figure).

RE is contained in RPA-1 ₂ O ₃ 9.8 wt%, P ₂ O ₅ 3.9% by weight, unit cell is alwaysNumber 2.462nm, relative crystallinity 60%, total specific surface area 580m ² Per gram, total pore volume 0.63cm ³ /g。

Example 2

According to the molar ratio of the gel charge of the NaY molecular sieve described in example 1, water glass, a directing agent, aluminum sulfate, sodium metaaluminate and required deionized water are sequentially mixed and stirred for 1 hour, wherein the mass ratio of the directing agent is 6%, the gel is crystallized at 100 ℃ for 25 hours, and then the crystallized slurry is filtered and washed, and is oven-dried at 120 ℃ for 10 hours to obtain the NaY molecular sieve.

Adding water again to the obtained NaY molecular sieve dry powder, pulping, stirring uniformly, heating to 40 ℃, and stirring vigorously while simultaneously adding Al ₂ (SO ₄ ) ₃ Solution (concentration 50 gAl) ₂ O ₃ L) and NaAlO ₂ Solution (concentration 102 gAl) ₂ O ₃ and/L) is added in parallel to carry out contact reaction, the pH value of the slurry system is controlled to be 9.0, and after a certain period of reaction, the reaction is carried out according to the total Al in the aluminum sulfate solution and the sodium metaaluminate solution ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ =1:5 by weight, a water glass solution (concentration 120gSiO ₂ and/L) is added to the reaction slurry and the reaction is continued at 55 ℃ for 6 hours, and then the porous material YCMN-3 is obtained by filtration, washing and oven drying at 120 ℃.

YCMN-3 has a fluorescence analysis chemical composition of 5.70Na ₂ O·34.0SiO ₂ ·59.4Al ₂ O ₃ The X-ray diffraction pattern of the fluorescent powder has the characteristics shown in figure 1 and simultaneously contains a FAU crystalline phase structure and a pseudo-boehmite structure. The transmission electron microscope TEM image has the characteristics shown in figure 2, two structures exist at the same time, the two structures are combined together, and the amorphous phase and the amorphous structure of the pseudo-boehmite grow along the edge of the FAU crystalline phase structure to form a composite structure. The SEM photograph has the characteristics shown in fig. 4, and at the same time, the fold-shaped structure and part of crystal grains of the Y-shaped molecular sieve can be seen, and most of the crystal grains of the molecular sieve are covered by the fold-shaped mesoporous structure grown on the surface. Its BET specific surface area is 427m ² Per gram, mesoporous specific surface area of 241m ² Per g, total pore volume ofThe mesoporous volume was 0.74ml/g at 0.83ml/g, and the BJH pore size distribution curve was characterized by the gradient pore distribution shown in FIG. 3. In the Raman spectrum, a/b=2.1 of YCMN-3.

The porous material YCMN-3 and the rare earth chloride solution are contacted and treated for 3 hours at 50 ℃ according to the weight ratio of rare earth oxide to porous material of 0.12, filtered, washed and dried; roasting at 550 ℃ under 100% steam condition for 2 hours; and (3) adding water into the roasted sample, pulping, carrying out secondary contact treatment for 1 hour at 70 ℃ according to the weight ratio of ammonium salt to the roasted sample of 0.2 and the weight ratio of monoammonium phosphate to the roasted sample of 0.02 (calculated by phosphorus pentoxide), filtering, washing with water and drying to obtain the porous material containing rare earth and phosphorus, and marking as RPA-2.

The XRD diffraction pattern of RPA-2 has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure is as follows.

RE is contained in RPA-2 ₂ O ₃ 11.7 wt%, P ₂ O ₅ 2.0% by weight, unit cell constant 2.466nm, relative crystallinity 28%, total specific surface area 375m ² Per gram, total pore volume 0.79cm ³ /g。

Example 3

According to 7.5SiO ₂ ：Al ₂ O ₃ ：2.15Na ₂ O：190H ₂ Mixing water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and deionized water according to a certain proportion, stirring for 1 hour, crystallizing the gel at 100 ℃ for 50 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours to obtain the NaY molecular sieve.

Adding water again to the obtained NaY molecular sieve dry powder, pulping, stirring uniformly, heating to 45deg.C, stirring vigorously, and simultaneously adding Al (NO) ₃ ) ₃ Solution (concentration 50 gAl) ₂ O ₃ And ammonia water (25% by mass) are added in parallel to carry out contact reaction, the pH value of the slurry system is controlled to be 9.5, and after a certain period of reaction, the reaction is carried out according to the Al in the aluminum nitrate solution ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ =1:1 by weight, water glass solution (concentration 120gSiO ₂ and/L) is added to the reaction slurry and the reaction is continued at 50 ℃ for 10 hours, and then the porous material YCMN-5 is obtained by filtration, washing and oven drying at 120 ℃.

YCMN-5 has a fluorescence analysis chemical composition of 11.2Na ₂ O·56.0SiO ₂ ·32.5Al ₂ O ₃ The X-ray diffraction pattern of the fluorescent powder has the characteristics shown in figure 1 and simultaneously contains a FAU crystalline phase structure and a pseudo-boehmite structure. The transmission electron microscope TEM image has the characteristics shown in figure 2, two structures exist at the same time, the two structures are combined together, and the amorphous phase and the amorphous structure of the pseudo-boehmite grow along the edge of the FAU crystalline phase structure to form a composite structure. The SEM photograph has the characteristics shown in fig. 4, and at the same time, the fold-shaped structure and part of crystal grains of the Y-shaped molecular sieve can be seen, and most of the crystal grains of the molecular sieve are covered by the fold-shaped mesoporous structure grown on the surface. Its BET specific surface area is 719m ² /g, mesoporous specific surface area of 68m ² And/g, the total pore volume is 0.52ml/g, the mesoporous pore volume is 0.21ml/g, and the BJH pore size distribution curve has the characteristic of gradient pore distribution shown in figure 3. In the Raman spectrum, a/b=9.6 of YCMN-5.

The porous material YCMN-5 and the rare earth chloride solution are contacted and treated for 1 hour at 65 ℃ according to the weight ratio of rare earth oxide to porous material of 0.13, filtered, washed and dried; roasting at 580 deg.c and 100% water vapor for 4 hr; adding water into the roasted sample for pulping, carrying out secondary contact treatment for 1 hour at 65 ℃ according to the weight ratio of ammonium salt to the roasted sample of 0.3, filtering, washing with water, mechanically mixing phosphoric acid and filter cake according to the weight ratio of phosphoric acid to the roasted sample of 0.025 (calculated by phosphorus pentoxide), grinding uniformly, drying, and carrying out secondary roasting treatment for 2 hours at 580 ℃ under the condition of 100% water vapor to obtain the porous material containing rare earth and phosphorus, namely RPA-3.

The XRD diffraction pattern of RPA-3 has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure of the。

RE is contained in RPA-3 ₂ O ₃ 12.8 wt%, P ₂ O ₅ 2.3% by weight, unit cell constant 2.465nm, relative crystallinity 58%, total specific surface area 576m ² Per gram, total pore volume 0.50cm ³ /g。

Example 4

According to the mole ratio of gel feeding of NaY molecular sieve of 8.5SiO ₂ ：Al ₂ O ₃ ：2.65Na ₂ O：210H ₂ Sequentially mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 20 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water into the obtained NaY molecular sieve dry powder again, pulping, homogenizing, stirring vigorously at room temperature, and simultaneously adding Al ₂ (SO ₄ ) ₃ Solution (concentration 50 gAl) ₂ O ₃ And ammonia water (mass fraction: 25%) were added thereto in parallel, the pH of the mixed slurry was adjusted to 9.5, the reaction slurry was collected and the reaction slurry was purified according to Al in the aluminum sulfate solution used ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ Ratio=1:4, water glass solution (concentration 120gSiO ₂ and/L) adding the porous material into the slurry, stirring the slurry at a constant temperature of 50 ℃ for 4 hours, placing the slurry into a stainless steel reaction kettle, crystallizing the slurry for 10 hours under a closed condition of 100 ℃, filtering the slurry after crystallization, washing the slurry, and drying the slurry in an oven at 120 ℃ to obtain the porous material YCM-1.

YCM-1 contains sodium oxide 4.7 wt%, silicon oxide 27.9 wt%, aluminum oxide 66.5 wt%, and specific surface area 521m ² Per gram, total pore volume 1.10cm ³ The ratio of the mesoporous volume to the total pore volume was 0.91. The BJH pore size distribution curve is shown in FIG. 6, and has the characteristic of gradient pore distribution, and several pore distribution appears at 3.8nm, 11nm and 32nm respectively. The XRD spectrum is shown in figure 7, and contains FAU crystal phase structure and pseudo-boehmite amorphous phase structure, namely, characteristic diffraction peaks of FAU crystal phase structure appear at 6.2 degree, 10.1 degree, 11.9 degree, 15.7 degree, 18.7 degree, 20.4 degree, 23.7 degree, 27.1 degree and 31.4 degree of 2 theta, and the 2 theta is 14 degreeCharacteristic diffraction peaks of 5 pseudo-boehmite structures appear at 28 °, 38.5 °, 49 ° and 65 °; the transmission electron microscope TEM photograph is shown in figure 8, and the two structures are combined and the amorphous structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM photograph of the scanning electron microscope is shown in fig. 9, and it can be seen that the pseudo-boehmite with the wrinkled mesoporous structure grows on the surface of the crystal grain of the Y-type molecular sieve and completely covers the crystal grain. In the Raman spectrum, YCM-1 a/b=1.6.

The porous material YCM-1 and the rare earth chloride solution are contacted with the ammonium salt solution for 1 hour at 80 ℃ according to the weight ratio of rare earth oxide to porous material of 0.04 and the weight ratio of 0.15, filtered, washed and dried; roasting at 530 deg.c and 100% water vapor for 2 hr; and (3) adding water into the roasted sample, pulping, carrying out secondary contact treatment for 1 hour at 55 ℃ according to the proportion of ammonium salt to the roasted sample of 0.2 and the proportion of phosphoric acid to the roasted sample of 0.06 (calculated by phosphorus pentoxide), filtering, washing with water and drying to obtain the porous material containing rare earth and phosphorus, and marking as RPA-4.

The XRD diffraction pattern of RPA-4 has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure is as follows.

RE is contained in RPA-4 ₂ O ₃ 3.9 wt%, P ₂ O ₅ 5.8% by weight, unit cell constant 2.458nm, relative crystallinity 29%, total specific surface area 512m ² Per gram, total pore volume 0.98cm ³ /g。

Example 5

According to the gel feeding mole ratio of a conventional NaY molecular sieve, such as 8.7SiO ₂ ：Al ₂ O ₃ ：2.75Na ₂ O：200H ₂ Sequentially mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 40 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder, pulping, homogenizing, and heatingTo 40 ℃, under vigorous stirring, alCl is simultaneously added ₃ Solution (concentration 60 gAl) ₂ O ₃ And ammonia water (mass fraction: 25%) were added thereto in parallel, the pH of the mixed slurry was adjusted to 8.5, the reaction slurry was collected and the reaction slurry was purified according to Al in the aluminum chloride solution used ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ The tetraethoxysilane was added to the above slurry at a ratio of =1:6, and stirring was continued at a constant temperature of 60 ℃ for 2 hours, then the slurry was placed in a stainless steel reaction vessel and crystallized at 100 ℃ for 5 hours, and after crystallization, the slurry was filtered, washed and oven-dried at 120 ℃ to obtain a porous material YCM-4.

YCM-4 contains 6.5 wt% of sodium oxide, 41.9 wt% of silicon oxide, 50.8 wt% of aluminum oxide and has a specific surface area of 540m ² Per gram, total pore volume 0.99cm ³ The ratio of the mesoporous volume to the total pore volume was 0.84. The BJH pore size distribution curve has the characteristics shown in fig. 6, exhibiting a gradient pore distribution characteristic. The X-ray diffraction spectrum of the crystal has the characteristics shown in figure 7 and simultaneously contains a FAU crystal phase structure and a pseudo-boehmite amorphous phase structure; the transmission electron microscope TEM photo has the characteristics shown in figure 8, two structures coexist and the amorphous structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM (scanning electron microscope) photograph has the characteristics shown in figure 9, and the pseudo-boehmite with the wrinkled mesoporous structure grows on the surface of the crystal grain of the Y-type molecular sieve and completely covers the crystal grain. In the Raman spectrum, YCM-4 a/b=3.1.

The porous material YCM-4 and the rare earth chloride solution are contacted with the ammonium salt solution for 1 hour at 55 ℃ according to the weight ratio of rare earth oxide to porous material of 0.1 and the weight ratio of ammonium salt solution of 0.05, filtered, washed and dried; roasting at 620 ℃ under 100% steam condition for 3 hours; adding water into the roasted sample for pulping, carrying out secondary contact treatment for 1 hour at 55 ℃ according to the weight ratio of ammonium salt to the roasted sample of 0.3, filtering, washing with water, mechanically mixing diammonium hydrogen phosphate with a filter cake according to the weight ratio of diammonium hydrogen phosphate to the roasted sample of 0.05 (calculated by phosphorus pentoxide), grinding uniformly, drying, and carrying out secondary roasting treatment for 2 hours at 600 ℃ under the condition of 100% water vapor to obtain the porous material containing rare earth and phosphorus, which is denoted as RPA-5.

The XRD diffraction pattern of RPA-5 has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure is as follows.

RE is contained in RPA-5 ₂ O ₃ 9.8 wt%, P ₂ O ₅ 5.0% by weight, unit cell constant 2.460nm, relative crystallinity 44%, total specific surface area 501m ² Per gram, total pore volume 0.86cm ³ /g。

Example 6

According to the mole proportion of gel feeding of a conventional NaY molecular sieve, such as 7.5SiO ₂ ：Al ₂ O ₃ ：2.15Na ₂ O：190H ₂ Sequentially mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 15 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder, pulping, homogenizing, heating to 35deg.C, and stirring vigorously while adding Al (NO) ₃ ) ₃ Solution (concentration 50 gAl) ₂ O ₃ And ammonia water (mass fraction: 25%) were added thereto in parallel, the pH of the mixed slurry was adjusted to 9.5, the reaction slurry was collected and the reaction slurry was purified according to Al in the aluminum nitrate solution used ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ The porous material YCM-6 was obtained by adding tetraethoxysilane to the above slurry at a ratio of 1:5, stirring at a constant temperature of 70 ℃ for 4 hours, placing the slurry in a stainless steel reaction vessel, crystallizing at 100 ℃ for 15 hours, filtering the slurry after crystallization, washing, and oven-drying at 120 ℃.

YCM-6 contains 10.8 wt% of sodium oxide, 55.7 wt% of silicon oxide, 32.1 wt% of aluminum oxide and has a specific surface area of 620m ² Per gram, total pore volume 0.59cm ³ The ratio of the mesoporous volume to the total pore volume was 0.57. The BJH pore size distribution curve has the characteristics shown in fig. 6, exhibiting a gradient pore distribution characteristic. The X-ray diffraction pattern has the characteristics shown in figure 7 and is the same asWhen the crystal contains FAU crystal phase structure and pseudo-boehmite amorphous phase structure; the transmission electron microscope TEM photo has the characteristics shown in figure 8, two structures coexist and the amorphous structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM (scanning electron microscope) photograph has the characteristics shown in figure 9, and the pseudo-boehmite with the wrinkled mesoporous structure grows on the surface of the crystal grain of the Y-type molecular sieve and completely covers the crystal grain. In the Raman spectrum, YCM-6 a/b=7.7.

The porous material YCM-6 and the rare earth chloride solution are contacted with the ammonium salt solution for 2 hours at 50 ℃ according to the weight ratio of rare earth oxide to porous material of 0.06 and the weight ratio of 0.15, filtered, washed and dried; roasting at 500 deg.c and 100% water vapor for 2 hr; and (3) adding water into the roasted sample for pulping, and carrying out contact treatment for 1 hour at 50 ℃ successively according to the proportion of ammonium salt to the roasted sample of 0.4 and the proportion of phosphoric acid to the roasted sample of 0.04 (calculated by phosphorus pentoxide), filtering, washing with water and drying to obtain the porous material containing rare earth and phosphorus, which is denoted as RPA-6.

The XRD diffraction pattern of RPA-6 has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure is as follows.

RE is contained in RPA-6 ₂ O ₃ 5.9 wt%, P ₂ O ₅ 3.8% by weight, unit cell constant 2.459nm, relative crystallinity 28%, total specific surface area 432m ² Per gram, total pore volume 0.91cm ³ /g。

Example 7

According to the mole proportion of gel feeding of a conventional NaY molecular sieve, such as 7.5SiO ₂ ：Al ₂ O ₃ ：2.15Na ₂ O：190H ₂ Sequentially mixing and uniformly stirring water glass, aluminum sulfate, sodium metaaluminate, a guiding agent and required deionized water, wherein the mass ratio of the guiding agent is 5%, crystallizing the gel at 100 ℃ for 30 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the NaY molecular sieve dry powder, pulping, homogenizing, stirring at room temperature under intense condition, and simultaneouslyAl is added with ₂ (SO ₄ ) ₃ Solution (concentration 90 gAl) ₂ O ₃ And ammonia water (mass fraction: 25%) were added thereto in parallel, the pH of the mixed slurry was adjusted to 8.5, the reaction slurry was collected and the reaction slurry was purified according to Al in the aluminum sulfate solution used ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ =1:7 ratio, water glass solution (concentration 120gSiO ₂ and/L) adding the porous material into the slurry, stirring the mixture at the constant temperature of 80 ℃ for 1 hour, placing the slurry into a stainless steel reaction kettle, crystallizing the slurry at the temperature of 100 ℃ for 28 hours, filtering the slurry after crystallization, washing the slurry, and drying the slurry in an oven at the temperature of 120 ℃ to obtain the porous material YCM-10.

YCM-10 contains 5.2% by weight of sodium oxide, 31.5% by weight of silicon oxide, 62.6% by weight of aluminum oxide, and has a specific surface area of 442m ² Per gram, total pore volume 1.0cm ³ The ratio of the mesoporous volume to the total pore volume was 0.94. The BJH pore size distribution curve has the characteristics shown in fig. 6, exhibiting a gradient pore distribution characteristic. The X-ray diffraction spectrum of the crystal has the characteristics shown in figure 7 and simultaneously contains a FAU crystal phase structure and a pseudo-boehmite amorphous phase structure; the transmission electron microscope TEM photo has the characteristics shown in figure 8, two structures coexist and the amorphous structure of the pseudo-boehmite extends and grows along the edge of the FAU crystalline phase structure, and the two structures are organically combined together; the SEM (scanning electron microscope) photograph has the characteristics shown in figure 9, and the pseudo-boehmite with the wrinkled mesoporous structure grows on the surface of the crystal grain of the Y-type molecular sieve and completely covers the crystal grain. In the Raman spectrum, YCM-10 a/b=1.7.

The porous material YCM-10 and the rare earth chloride solution are contacted with the ammonium salt solution for 2 hours at 70 ℃ according to the weight ratio of rare earth oxide to porous material of 0.08 and the weight ratio of 0.10, filtered, washed and dried; roasting at 650 deg.c and 100% water vapor for 2 hr; and (3) adding water into the roasted sample, pulping, carrying out secondary contact treatment for 1 hour at 65 ℃ according to the proportion of ammonium salt to the roasted sample of 0.3 and the proportion of phosphoric acid to the roasted sample of 0.03 (calculated by phosphorus pentoxide), filtering, washing with water and drying to obtain the porous material containing rare earth and phosphorus, and marking as RPA-7.

RPA-The XRD diffraction pattern of 7 has the characteristics shown in figure 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure is as follows.

RE is contained in RPA-7 ₂ O ₃ 8.0 wt%, P ₂ O ₅ 2.9% by weight, unit cell constant 2.457nm, relative crystallinity 59%, total specific surface area 593m ² Per gram, total pore volume 0.52cm ³ /g。

Example 8

According to the molar ratio of the gel of the NaY molecular sieve in the embodiment 6, sequentially mixing and uniformly stirring water glass, a guiding agent, aluminum sulfate, sodium metaaluminate and required deionized water, wherein the mass ratio of the guiding agent is 6%, crystallizing the gel at 100 ℃ for 45 hours, filtering and washing the crystallized slurry, and drying in an oven at 120 ℃ for 10 hours; adding water again to the obtained NaY molecular sieve dry powder, pulping, homogenizing, heating to 45deg.C, stirring vigorously, and simultaneously adding Al (NO) ₃ ) ₃ Solution (concentration 50 gAl) ₂ O ₃ And ammonia water (mass fraction: 25%) were added thereto in parallel, the pH of the mixed slurry was adjusted to 10.0, the reaction slurry was collected and the reaction slurry was purified according to Al in the aluminum nitrate solution used ₂ O ₃ By weight of SiO ₂ :Al ₂ O ₃ Ratio=1:9, water glass solution (concentration 120gSiO ₂ and/L) adding the porous material into the slurry, continuously stirring at the constant temperature of 60 ℃ for 2 hours, then placing the slurry into a stainless steel reaction kettle and crystallizing at the temperature of 100 ℃ for 25 hours, filtering, washing and drying in an oven at the temperature of 120 ℃ to obtain the porous material YCM-5.

YCM-5 contains 8.12% by weight of sodium oxide, 47.2% by weight of silicon oxide, 44.5% by weight of aluminum oxide, and has a specific surface area of 595m ² Per gram, total pore volume 0.85cm ³ The ratio of the mesoporous volume to the total pore volume was 0.74. The BJH pore size distribution curve has the characteristics shown in fig. 6, exhibiting a gradient pore distribution characteristic. The X-ray diffraction spectrum of the crystal has the characteristics shown in figure 7 and simultaneously contains a FAU crystal phase structure and a pseudo-boehmite amorphous phase structure; the transmission electron microscope TEM photograph has the characteristics shown in figure 8, two structures coexist and the amorphous phase structure of pseudo-boehmite is along the FAU crystalline phase structureEdge extension growth, and the two structures are organically combined together; the SEM (scanning electron microscope) photograph has the characteristics shown in figure 9, and the pseudo-boehmite with the wrinkled mesoporous structure grows on the surface of the crystal grain of the Y-type molecular sieve and completely covers the crystal grain. In the Raman spectrum, YCM-5 a/b=5.5.

The porous material YCM-5 and rare earth chloride solution are contacted and treated for 1 hour at 75 ℃ according to the weight ratio of rare earth oxide to porous material of 0.12, filtered, washed and dried; roasting at 580 deg.c and 100% water vapor for 3 hr; and (3) adding water into the roasted sample, pulping, carrying out secondary contact treatment for 1 hour at 70 ℃ according to the weight ratio of ammonium salt to the roasted sample of 0.3 and the weight ratio of diammonium phosphate to the roasted sample of 0.015 (calculated as phosphorus pentoxide), filtering, washing with water, drying, and roasting at 550 ℃ for 1 hour under the condition of 100% water vapor to obtain the porous material containing rare earth and phosphorus, which is denoted as RPA-8.

The XRD diffraction pattern of RPA-8 has the characteristics shown in FIG. 5, and shows that the FAU crystal phase structure and gamma-Al of the Y-type molecular sieve are simultaneously contained ₂ O ₃ Structure is as follows.

RE is contained in RPA-8 ₂ O ₃ 11.9 wt%, P ₂ O ₅ 1.4% by weight, unit cell constant 2.464nm, relative crystallinity 43% and total specific surface area 556m ² Per gram, total pore volume 0.78cm ³ /g。

Examples 9 to 16

Examples 9-16 illustrate the cracking performance of the rare earth and phosphorus containing porous materials prepared according to the present invention.

The porous materials RPA-1 to RPA-8 containing rare earth and phosphorus prepared in examples 1 to 8 were mixed and exchanged with an ammonium chloride solution, the sodium oxide content was washed to 0.3% by weight or less, and after filtration and drying, the mixture was tabletted and sieved into 20 to 40 mesh particles, and the particles were subjected to aging treatment at 800℃for 17 hours under 100% steam conditions, and then the cracking performance was evaluated on a light oil microreaction evaluation device.

Light oil micro-reverse evaluation condition: the raw oil is large harbor straight-run light diesel oil, the sample loading is 2g, the mass ratio of the catalyst to the oil is 1.3, and the reaction temperature is 460 ℃.

The evaluation results are shown in Table 1.

TABLE 1

Sample of	RPA-1	RPA-2	RPA-3	RPA-4	RPA-5	RPA-6	RPA-7	RPA-8
									MA	61	55	65	52	57	54	60	58

As can be seen from the reaction data in Table 2, the rare earth and phosphorus-containing porous materials RPA-1 to RPA-8 prepared in examples 1 to 8 can maintain high cracking performance after being subjected to 100% steam aging treatment for 17 hours at 800 ℃, and the micro-reactivity index reaches 52 to 65.

The porous material containing rare earth and phosphorus prepared by the invention has the characteristics of more suitable cracking reaction in pore canal structure and acid distribution due to the organic combination of micro-pore canal structure and mesoporous pore canal structure and common modification of rare earth and phosphorus, and promotes the improvement of cracking performance.

Claims

1. The preparation method of the porous material containing rare earth and phosphorus is characterized by comprising the following steps: (1) Carrying out first contact treatment on a porous material and a rare earth solution and/or an ammonium salt solution, filtering, washing with water and drying; (2) Performing primary roasting treatment on the water vapor obtained in the step (1) under the condition of 0-100%; (3) Pulping the water obtained in the step (2), carrying out secondary contact treatment on the pulp and an ammonium salt solution and a phosphorus source, filtering, washing and drying, or carrying out secondary roasting treatment under the condition of 0-100% water vapor to obtain a porous material containing rare earth and phosphorus;

the rare earth content of the rare earth and phosphorus-containing porous material is 2-14wt% based on rare earth oxide, and the phosphorus content is 1-6wt% based on phosphorus pentoxide; the porous material containing rare earth and phosphorus contains a microporous structure of FAU crystalline phase and gamma-Al ₂ O ₃ Mesoporous structure of said gamma-Al ₂ O ₃ The mesoporous structure grows in a derivative way on the edge of the FAU crystal phase structure, and the two structures are organically connected; the unit cell constant is 2.455-2.470 nm, the relative crystallinity is 25-65%, and the total specific surface area is 350-600 m ² Per gram, total pore volume of 0.5-1.0 cm ³ /g；

The porous material in the step (1) contains a FAU crystalline phase structure and a pseudo-boehmite amorphous phase structure in an XRD spectrogram, ordered diffraction fringes of the FAU crystalline part and disordered structures of the pseudo-boehmite part are simultaneously visible in a transmission electron microscope TEM, the disordered structures grow along the edges of the ordered diffraction fringes, and the two structures are effectively combined together to form a microporous and mesoporous composite structure; in Raman (Raman) spectra, a/b=1.5 to 10, where a represents a displacement of 500cm ^-1 The spectral peak intensity of b represents the shift350cm ^-1 Peak intensity of spectrum of (2); the anhydrous chemical expression of the porous material is (4-12) Na ₂ O·(25～65)SiO ₂ ·(25～70)Al ₂ O ₃ A specific surface area of 350 to 750m ² Per gram, the specific surface area of the mesoporous is 50-450 m ² Per g, the total pore volume is 0.5-1.5 ml/g, the mesoporous volume is 0.2-1.2 ml/g, and BJH curves show gradient pore distribution characteristics, and can be distributed in pores of 3-4 nm, 8-20 nm and 18-40 nm respectively;

the porous material in the step (1) is prepared by adding water into molecular sieve dry powder with FAU crystal structure, pulping, stirring uniformly, adding aluminum source and alkali solution at room temperature to 85deg.C, mixing thoroughly, controlling pH value of slurry system to 7-11, performing contact reaction, and taking aluminum oxide in the aluminum source as reference, and SiO ₂ :Al ₂ O ₃ And (1) adding a silicon source calculated by silicon oxide into the slurry according to the weight ratio of (1-9), continuously reacting for 1-10 hours at the temperature of room temperature to 90 ℃ to recover a product, or stirring for 1-4 hours at the constant temperature of room temperature to 90 ℃ after adding the silicon source, crystallizing for 3-30 hours at the temperature of 95-105 ℃ in a closed reaction kettle, and recovering the product.

2. The process according to claim 1, wherein the aluminum source is one or more selected from the group consisting of aluminum nitrate, aluminum sulfate and aluminum chloride.

3. The process according to claim 1, wherein the base is selected from one or more of ammonia water, potassium hydroxide and sodium hydroxide, or the base is replaced with sodium metaaluminate, and when the base is replaced with sodium metaaluminate, the alumina content thereof is calculated to be the total alumina content.

4. The method according to claim 1, wherein the silicon source is one or more selected from the group consisting of water glass, tetraethoxysilicon, tetramethoxysilicon and silicon oxide.

5. The preparation method according to claim 1, wherein the first contact treatment in step (1) has a weight ratio of rare earth solution to the porous material of 0.02 to 0.14 in terms of rare earth oxide, a weight ratio of ammonium salt to the porous material of 0.05 to 0.2, a contact temperature of 40 to 90 ℃ and a contact time of 0.5 to 3.0 hours.

6. The preparation method according to claim 5, wherein the first contact treatment in step (1) has a weight ratio of the rare earth solution to the porous material of 0.03 to 0.13 in terms of rare earth oxide, a contact temperature of 50 to 80 ℃ and a contact time of 1 to 2 hours.

7. The process according to claim 1, wherein the first calcination treatment and the second calcination treatment in steps (2) and (3) are each carried out at 500 to 700℃and 0 to 100% water vapor for 0.5 to 4.0 hours.

8. The process according to claim 7, wherein the first calcination treatment and the second calcination treatment in steps (2) and (3) are carried out at 530 to 680℃and 20 to 100% steam for 1 to 3 hours.

9. The process according to claim 1, wherein the second contact treatment in the step (3) is a contact treatment with an ammonium salt solution and a phosphorus source simultaneously obtained in the step (2), filtration, washing with water and drying; or, the step (2) is carried out the contact treatment with ammonium salt solution after the water is added and pulped, and the mixture is filtered, washed and then contacted with phosphorus source, filtered or not filtered and dried; the weight ratio of the ammonium salt to the phosphorus source obtained in the step (2) is 0.1-0.5, the weight ratio of the phosphorus source to the phosphorus source obtained in the step (2) is 0.01-0.06, the contact temperature is room temperature-90 ℃, and the contact time is 0.5-3.0 hours.

10. The preparation method according to claim 1, wherein the ammonium salt in the step (1) and the step (3) is one or more of ammonium chloride, ammonium nitrate, ammonium carbonate and ammonium bicarbonate.

11. The process according to claim 1, wherein the phosphorus source in the step (3) is one or more of ammonium phosphate, diammonium phosphate, monoammonium phosphate, and phosphoric acid.