CN114715911B - Multistage hole ZSM-5 molecular sieve containing phosphorus and metal and preparation method thereof - Google Patents

Multistage hole ZSM-5 molecular sieve containing phosphorus and metal and preparation method thereof Download PDF

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CN114715911B
CN114715911B CN202110008846.XA CN202110008846A CN114715911B CN 114715911 B CN114715911 B CN 114715911B CN 202110008846 A CN202110008846 A CN 202110008846A CN 114715911 B CN114715911 B CN 114715911B
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molecular sieve
phosphorus
zsm
peak area
metal
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CN114715911A (en
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罗一斌
欧阳颖
王成强
邢恩会
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
    • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
    • C07C4/06—Catalytic processes
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    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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Abstract

The invention discloses a multistage hole ZSM-5 molecular sieve containing phosphorus and metal, which is characterized in that in surface XPS element analysis, n1/n2 is less than or equal to 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum; NH after hydrothermal aging at 800 ℃ under 100% steam conditions for 17 hours 3 In the TPD spectrum, the desorption temperature is more than 200 ℃ and the specific gravity of the strong acid center peak area to the total acid center peak area is more than or equal to 45 percent, so that the strong acid center retention degree is higher. The molecular sieve can increase the yield of low-carbon olefin in the process of producing more liquefied gas and produce more high-added-value products.

Description

Multistage hole ZSM-5 molecular sieve containing phosphorus and metal and preparation method thereof
Technical Field
The invention relates to a ZSM-5 molecular sieve and a preparation method thereof, in particular to a multistage pore ZSM-5 molecular sieve containing phosphorus and metal and a preparation method thereof.
Background
ZSM-5 molecular sieve was a widely used catalytic material developed in 1972 by the company Mobil, USA. The ZSM-5 molecular sieve has a three-dimensional crossed pore structure, the pore in the axial direction a is a straight pore, the cross-sectional dimension of the pore in the axial direction a is 0.54 multiplied by 0.56nm, the pore in the axial direction b is a Z-shaped pore, the cross-sectional dimension of the pore in the axial direction b is 0.51 multiplied by 0.56nm, and the pore is elliptical. The openings of the ZSM-5 molecular sieve are formed of ten membered rings, which are sized between small pore zeolite and large pore zeolite, thus having unique shape selective catalytic action. The ZSM-5 molecular sieve has the characteristics of unique pore structure, good shape selective catalysis and isomerization performance, high heat and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon formation, is widely used as a catalyst and a catalyst carrier, and is successfully used in the production processes of alkylation, isomerization, disproportionation, catalytic cracking, methanol to gasoline, methanol to olefin and the like. ZSM-5 molecular sieve is introduced into catalytic cracking and carbon four hydrocarbon catalytic cracking, shows excellent catalytic performance, and can greatly improve the yield of low-carbon olefin.
Since 1983, ZSM-5 molecular sieves have been applied to catalytic cracking processes as an aid to the octane number of catalytic cracking, with the aim of increasing the octane number of catalytically cracked gasoline and the selectivity to lower olefins. US3758403 originally reported the use of ZSM-5 molecular sieves as an active component for propylene production, which together with REY is an active component of FCC catalysts, US5997728 discloses the use of ZSM-5 molecular sieves without any modification as an adjunct for propylene production, but none of their disclosures provides high propylene yields. Although the HZSM-5 molecular sieve has good shape selectivity and isomerization performance, the HZSM-5 molecular sieve has the defects of poor hydrothermal stability, easy deactivation under severe high-temperature hydrothermal conditions and reduced catalytic performance.
In the 80 s of the 20 th century, the Mobil company found that phosphorus improved the hydrothermal stability of ZSM-5 molecular sieves, and the phosphorus improved the yield of low-carbon olefins after modifying ZSM-5 molecular sieves. Typically, it is conventional to include a phosphorus-activated ZSM-5 additive which selectively converts primary cracked products (e.g., gasoline olefins) to C3 and C4 olefins. After the ZSM-5 molecular sieve is synthesized, a proper amount of inorganic phosphorus compound is introduced for modification, so that framework aluminum can be stabilized under severe hydrothermal conditions.
CN 106994364A discloses a method for modifying ZSM-5 molecular sieve by mixing one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, monoammonium phosphate and ammonium phosphate with ZSM-5 molecular sieve with high alkali metal ion content to obtain a catalyst with phosphorus and P 2 O 5 At least 0.1wt% of a carrier amount of the mixtureThrough drying, calcining, ammonium-exchanging step and water washing step, the content of alkali metal ions is reduced to less than 0.10wt%, and then drying and hydrothermal ageing at 400-1000 deg.C and 100% water vapour. The phosphorus-containing ZSM-5 molecular sieve obtained by the method has high total acid content, excellent cracking conversion rate and propylene selectivity, and higher liquefied gas yield.
CN1506161a discloses a method for modifying ZSM-5 molecular sieve, which comprises the following conventional steps: synthesizing, filtering, ammonium exchanging, drying and roasting to obtain a ZSM-5 molecular sieve, modifying the ZSM-5 molecular sieve by phosphoric acid, and then drying and roasting to obtain a phosphorus modified HZSM-5 molecular sieve, wherein P 2 O 5 The loading is generally in the range of 1 to 7 wt%.
CN1147420a discloses a molecular sieve containing phosphorus and rare earth and having MFI structure, its anhydrous chemical composition is aRE 2 O 3 bNa 2 OAl 2 O 3 cP 2 O 5 dSiO 2 Wherein a=0.01 to 0.25, b=0.005 to 0.02, c=0.2 to 1.0, d=35 to 120. The molecular sieve has excellent hydrothermal activity stability and good low-carbon olefin selectivity when being used for hydrocarbon high-temperature conversion.
The method of modifying molecular sieves with metals and their use are reported in, for example, USP5,236,880, which discloses catalysts comprising MFI or MEL structure molecular sieves, the addition of modified molecular sieves to increase the octane number, aromatic content and/or the yield of C5 to C12 gasoline when used for alkane conversion, and the inclusion of such modified molecular sieves to increase the octane number and the yield of C3 to C4 olefins. The molecular sieve used is modified with a group VIII metal, preferably Ni. After Ni is introduced into the molecular sieve, the molecular sieve undergoes heat or hydrothermal treatment under severe control temperature, so that the VIII metal and aluminum are enriched on the surface.
The multi-level hole ZSM-5 molecular sieve is a ZSM-5 molecular sieve containing micropores and mesopores at the same time, and various multi-level hole ZSM-5 molecular sieves with mesopore pore channels are prepared by a common hard template method, a soft template method, an acid-base post-treatment method and the like.
Although a proper amount of inorganic phosphide is adopted to modify the multi-level hole ZSM-5 molecular sieve, the framework dealumination can be slowed down, the hydrothermal stability is improved, and phosphorus atoms can be combined with distorted four-coordination framework aluminum to generate weak B acid centers, so that the higher conversion rate of long-chain alkane pyrolysis and the higher light olefin selectivity are achieved, excessive inorganic phosphide is used for modifying the multi-level hole ZSM-5 molecular sieve, pore channels of the molecular sieve can be blocked, the pore volume and the specific surface area are reduced, and a large amount of strong B acid centers are occupied. In addition, phosphoric acid or ammonium phosphate salt in the roasting process can self-polymerize to generate phosphorus species with different aggregation states, the coordination of phosphorus and framework aluminum is insufficient, the utilization efficiency of phosphorus is low, and the modification of phosphorus does not always obtain satisfactory hydrothermal stability improvement results. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of phosphorus and metal modified hierarchical pore ZSM-5 molecular sieve, and further improve the cracking activity.
Disclosure of Invention
The inventor finds that the multistage hole ZSM-5 molecular sieve containing phosphorus and metal obtained by phosphorus modification treatment under certain conditions and pressurized hydrothermal roasting has physical and chemical characteristics different from those of the conventional multistage hole ZSM-5 molecular sieve containing phosphorus and metal, the utilization efficiency of phosphorus in the molecular sieve is improved, and the hydrothermal stability of the molecular sieve is improved. Based on this, the present invention is formed.
Accordingly, one of the objects of the present invention is to provide a multi-pore ZSM-5 molecular sieve containing phosphorus and metal which is different from the physicochemical characteristics of the prior art, in view of the problems of the prior art such as non-ideal hydrothermal stability; and the second purpose is to provide a preparation method of the multistage hole ZSM-5 molecular sieve containing phosphorus and metal.
In order to achieve one of the purposes of the invention, the multistage pore ZSM-5 molecular sieve containing phosphorus and metal is characterized in that in surface XPS element analysis, n1/n2 is less than or equal to 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum.
In the surface XPS elemental analysis, n1/n2, i.e., n (P)/n (Si+Al), is preferably not more than 0.07, more preferably not more than 0.06. The characterization parameters show that the content of the surface phosphorus species in the molecular sieve is reduced, and the more migration of the surface phosphorus species to the molecular sieve phase is also shown, namely, the numerical value of n1/n2 shows the dispersing effect of the phosphorus species on the surface of the molecular sieve and the migration degree from the surface of the ZSM-5 molecular sieve to the inside of the crystal, and the smaller the numerical value shows the reduction of the content of the surface phosphorus species, the better the dispersion degree and the high migration degree of the phosphorus species to the inside, so that the hydrothermal stability of the molecular sieve is better.
Further, the multistage pore ZSM-5 molecular sieve containing phosphorus and metal of the invention, 27 in the Al MAS-NMR spectrum, the ratio of the resonance signal peak area of 39+ -3 ppm of the framework aluminum species coordinated with phosphorus to the resonance signal peak area of 54 ppm+ -3 ppm of the tetra-coordinated framework aluminum species, the preferred area ratio is not less than 1, and the more preferred area ratio is not less than 8. 27 In Al MAS-NMR, a chemical shift of 39.+ -.3 ppm resonance signal indicates a skeletal aluminum species coordinated with phosphorus (phosphorus stabilized skeletal aluminum, i.e., distorted tetra-coordinated skeletal aluminum); the resonance signal with a chemical shift of 54 ppm.+ -.3 ppm indicates a tetra-coordinated framework aluminum species.
Further, the multistage pore ZSM-5 molecular sieve containing phosphorus and metal of the invention has NH after being subjected to hydrothermal aging for 17 hours under the conditions of 800 ℃ and 100 percent water vapor 3 In the TPD spectrum, the specific gravity of the strong acid center peak area with the desorption temperature of more than 200 ℃ to the total acid center peak area is more than or equal to 45 percent, the preferred range is more than or equal to 50 percent, the more preferred range is more than or equal to 60 percent, and the most preferred range is 60 to 80 percent. The multistage hole ZSM molecular sieve containing phosphorus and metal has higher strong acid center retention degree after being subjected to hydrothermal aging for 17 hours under the conditions of 800 ℃ and 100 percent of water vapor, so that the multistage hole ZSM molecular sieve has higher cracking activity.
The content of phosphorus in the molecular sieve of the invention, when phosphorus and aluminum are counted by mole, the ratio of the phosphorus to the aluminum is 0.01-2; preferably, the ratio of the two is 0.1-1.5; more preferably, the ratio of the two is 0.2 to 1.5. The metal is selected from one or more of VIII, IIB, VIIB, IIIA, IVA and lanthanide metals; further, the metal is selected from one or more of Fe, co, ni, zn, mn, ga, sn, la, ce, and the metal is 0.1 to 10 wt%, preferably 0.2 to 5 wt% in terms of oxide.
In order to achieve the second object of the present invention, the present invention also provides a method for preparing the above-mentioned multi-pore ZSM-5 molecular sieve containing phosphorus and metal, one of the methods comprising: contacting phosphorus-containing compound solution and metal compound solution with hydrogen type hierarchical pore ZSM-5 molecular sieve, drying, and performing hydrothermal roasting treatment under external applied pressure and external water-added atmosphere environment to recover the product; wherein, in the hydrogen type multistage pore ZSM-5 molecular sieve, the proportion of the mesoporous volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm; the contact is to mix and contact the aqueous solution of the phosphorus-containing compound with the temperature of 0-150 ℃ with the hydrogen type multistage pore ZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour by adopting an impregnation method; or, the contact is to mix and slurry the phosphorous compound, the hydrogen-type hierarchical pore ZSM-5 molecular sieve and water, and then keep the mixture at 0 to 150 ℃ for at least 0.1 hour;
Alternatively, a second method may be employed, the second method including: contacting a solution containing a phosphorus compound with a hydrogen type hierarchical pore ZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under external applied pressure and external water-added atmosphere, recovering a product to obtain a phosphorus type hierarchical pore ZSM-5 molecular sieve, and then impregnating and roasting with a solution of a metal compound; the contact is to mix and contact the aqueous solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the hydrogen-type ZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour by adopting an impregnation method, or the contact is to mix and pulp the phosphorus-containing compound, the hydrogen-type ZSM-5 molecular sieve and water and then keep the mixture at the temperature of 0-150 ℃ for at least 0.1 hour;
the apparent pressure of the atmosphere environment is 0.01-1.0Mpa and contains 1-100% of water vapor.
The hierarchical pore means that the porous membrane contains micropores and mesopores at the same time. In the preparation method of the invention, the hydrogen type hierarchical pore ZSM-5 molecular sieve, na 2 O<0.1wt%, and the volume of mesopores (2 nm-50 nm) accounts for more than 10% of the total pore volume, usually 10% -90%, and the average pore diameter is 2-20 nm. The silicon-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide) is more than or equal to 10, and is usually 10-200.
In the preparation method of the invention, the phosphorus-containing compound is selected from organic phosphide and/or inorganic phosphide. The organic phosphide is selected from trimethyl phosphate, triphenyl phosphate, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenyl ethyl phosphine bromide, triphenyl butyl phosphine bromide, triphenyl benzyl phosphine bromide, hexamethylphosphoric triamide, dibenzyldiethyl phosphorus and 1, 3-dimethylbenzene bis-triethyl phosphorus, and the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
In the preparation method of the invention, the metal is selected from one or more of Fe, co, ni, zn, mn, ga, sn, la, ce. The metal compound is a water-soluble salt. The water-soluble salt is selected from sulfate, nitrate or chloride salt, such as one or more of ferric nitrate, nickel nitrate, zinc sulfate, manganese nitrate, gallium nitrate, tin nitrate, lanthanum nitrate and cerium chloride.
In one of the preparation methods of the present invention, the contacting is performed by immersing the aqueous solution of the phosphorus-containing compound and the metal compound at a temperature of 0 to 150 ℃ in a hydrogen-type hierarchical pore ZSM-5 molecular sieve at a temperature of 0 to 150 ℃ for at least 0.1 hour. For example, the contacting may be performed at a normal temperature range of 0 to 30 ℃, preferably at a higher temperature range of 40 ℃ or higher, for example, 50 to 150 ℃, more preferably 70 to 130 ℃, to obtain a better effect, i.e., better dispersion of phosphorus species, easier migration of phosphorus into the molecular sieve crystal to bond with framework aluminum, further improving the coordination degree of phosphorus and framework aluminum, and finally improving the hydrothermal stability of the molecular sieve. The substantially same temperature refers to the temperature difference between the aqueous solution of the phosphorus-containing compound and the metal compound and the temperature of each hydrogen type hierarchical pore ZSM-5 molecular sieve being within +/-5 ℃; for example, the aqueous solution of the phosphorus-containing compound and the metal compound is at a temperature of 80℃and the hydrogen-type hierarchical pore ZSM-5 molecular sieve is heated to 75 to 85 ℃.
In one of the preparation methods of the present invention, the contacting may be performed by mixing a phosphorus-containing compound, a metal compound, a hydrogen-form hierarchical pore ZSM-5 molecular sieve, and water and then maintaining the mixture at 0 to 150℃for at least 0.1 hour. For example, the mixing is carried out at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, and preferably, in order to obtain a better effect, that is, in order to achieve better dispersion of phosphorus species, phosphorus migrates into the molecular sieve crystal to bond with framework aluminum more easily, so as to further increase the coordination degree of phosphorus and framework aluminum, and finally, the hydrothermal stability of the molecular sieve is improved, and the mixing is carried out at a higher temperature range of 40 ℃ or higher for 0.1 hour, for example, a temperature range of 50 to 150 ℃ and more preferably a temperature range of 70 to 130 ℃.
In one of the preparation methods of the present invention, the solution of the phosphorus compound and the metal compound are contacted with the hydrogen-type ZSM-5 molecular sieve, which may be a manner of simultaneously impregnating the hydrogen-type ZSM-5 molecular sieve with the solution of the metal compound and the solution of the phosphorus compound, or a manner of impregnating the hydrogen-type ZSM-5 molecular sieve with the solution of the metal compound and the solution of the phosphorus compound, respectively. The recovery of the product described in one of the preparation methods is well known to those skilled in the art and generally comprises the steps of washing, drying and atmospheric calcination.
The second preparation method of the invention is that firstly, the solution of the phosphorus-containing compound is contacted with the hydrogen ZSM-5 molecular sieve, after drying treatment, the hydrothermal roasting treatment is carried out under the atmosphere environment of externally applied pressure and externally added water, the product is recovered to obtain the phosphorus-containing multistage hole ZSM-5 molecular sieve, and then the metal loading is carried out on the phosphorus-containing multistage hole ZSM-5 molecular sieve by adopting the means of impregnating the molecular sieve with the solution of the metal compound and roasting commonly used in the field.
In the preparation method, when the phosphorus-containing compound is counted by phosphorus and the hydrogen type hierarchical pore ZSM-5 molecular sieve is counted by aluminum, the molar ratio of the phosphorus-containing compound to the hydrogen type hierarchical pore ZSM-5 molecular sieve is 0.01-2; preferably, the molar ratio of the two is 0.1-1.5; more preferably, the molar ratio of the two is 0.3-1.3. The weight ratio of the water sieve in the contact is 0.5-1, and the preferable contact time is 0.5-40 hours.
In the preparation method of the invention, the hydrothermal roasting treatment is carried out under the atmosphere of externally applied pressure and externally added water. The atmosphere is obtained by externally applying pressure and externally adding water, and preferably has an apparent pressure of 0.1 to 0.8MPa, more preferably has an apparent pressure of 0.3 to 0.6MPa, preferably contains 30 to 100% of water vapor, and still more preferably contains 60 to 100% of water vapor. The external pressure is applied to the prepared material during the hydrothermal roasting treatment, for example, inert gas is introduced from the outside to maintain a certain back pressure. The external water is added in an amount which satisfies the condition that the atmosphere contains 1 to 100 percent of water vapor. The step of the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.
The multistage pore ZSM-5 molecular sieve containing phosphorus and metal contains phosphorus and metal components. The migration of surface phosphorus species to the multistage pore ZSM-5 molecular sieve phase ensures that the phosphorus species are better dispersed, the phosphorus is fully coordinated with framework aluminum in the molecular sieve, the framework aluminum is fully protected, the structural stability of the multistage pore molecular sieve can be improved, the pore canal of the molecular sieve is narrowed by adding metal, and the generation of coking precursors is inhibited, so that the effects of reducing the coking amount and improving the stability are achieved. For example, the molecular sieve of the present invention has a higher crystalline retention after 17h hydrothermal aging at 800 ℃ under 100% steam conditions.
The multistage hole ZSM-5 molecular sieve containing phosphorus and metal has the acid center closely combined with the dehydrogenation center of the metal. The addition of the metal modulates the surface acid nature of the catalyst and the presence of phosphorus partially poisons the dehydrogenation capacity of the metal. The introduction of the multistage holes improves the accessibility of acid centers, under the synergistic effect of different active centers, the multistage hole ZSM-5 molecular sieve containing phosphorus and metal has excellent n-tetradecane catalytic cracking activity, and the main technical indexes such as conversion rate, liquefied gas yield, triene (ethylene, propylene and butylene) yield and the like are all improved, for example, the ethylene yield is increased by 0.5 unit, the propylene is increased by 1.8 unit, the low-carbon olefin yield is increased, and meanwhile, the multistage hole ZSM-5 molecular sieve containing phosphorus and metal has higher liquefied gas yield and high added value products are produced in a more way.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of molecular sieves and examine the migration status of phosphorus compounds, using an ESCALAB 250 type X-ray photoelectron spectrometer from Thermo Fisher-VG company. Instrument parameters: the excitation source was an AlK alpha X-ray with monochromized power of 150W, the charge potential shift was corrected with the C1s peak (284.8 eV) from contaminated carbon, and the parameters of each peak were obtained by integration after subtraction of the back of Shirley line type using XPS Peak Avantage 4.15.15 software.
The X-ray diffraction (XRD) pattern was measured on a Japanese national TTR-3 powder X-ray diffractometer. Instrument parameters: copper target (tube voltage 40kV, tube current 250 mA), scintillation counter, step width 0.02 DEG, scan rate 0.4 (°)/min. The ZSM-5 molecular sieve synthesized by the method of example 1 in CN1056818C was used as a standard, and the crystallinity thereof was set to 100%. The relative crystallinity is expressed as a percentage of the ratio of the sum of the peak areas of five characteristic diffraction peaks having 2 theta between 22.5 and 25.0 DEG in the X-ray diffraction (XRD) spectrum of the obtained product and the hierarchical pore ZSM-5 molecular sieve standard sample.
The nitrogen adsorption and desorption curves were measured on an ASAP 2420 adsorber from Micromeritics. The samples are subjected to vacuum degassing at 100 ℃ and 300 ℃ for 0.5h and 6h respectively, N2 adsorption and desorption tests are carried out at 77.4K, and the adsorption amount and the desorption amount of the purified samples on nitrogen under different specific pressure conditions are tested to obtain an N2 adsorption-desorption isothermal curve. BET specific surface area is calculated by using a BET formula, micropore area is calculated by using t-plot, and aperture distribution is calculated by using BJH.
27 Al MAS-NMR was performed on a Bruker AVANCE III WB spectrometer. Instrument parameters: the diameter of the rotor is 4mm, the resonance frequency spectrum is 156.4MHz, the pulse width is 0.4 mu s (corresponding to 15 DEG spanner chamfer angle), the rotation speed of the magic angle is 12kHz, and the delay time is 1s. 27 Al MAS-NMR spectrum was characterized in that characteristic peak 1 at 54.+ -.3 pp m was attributed to tetradentate aluminum, and characteristic peak 2 at 39.+ -.3 ppm was attributed to phosphorus-stabilized aluminum skeleton (distorted tetradentate aluminum). And each peak area is calculated by an integration method after peak-dividing fitting is carried out on characteristic peaks.
Temperature programmed desorption analysis (NH) 3 TPD) characterization an AutoChen II temperature programmed adsorber from Micromeritics was used. Weighing 0.1-0.2 g of sample, placing into quartz adsorption tube, introducing carrier gas (high purity)He. Flow rate 50 mL/min), heating to 600 ℃ at a speed of 20 ℃/min, and keeping the temperature for 2 hours to remove water and air adsorbed on the sample; reducing the temperature to 100 ℃ at a speed of 20 ℃/min, and keeping the temperature constant for 30min; switching carrier gas to NH 3 He mixed gas is kept at a constant temperature for 30min, so that ammonia adsorption of the sample is saturated; NH is added to 3 The He mixed gas is switched into high-purity He carrier gas, and purged for 1h so as to desorb and absorb ammonia by material resources; then heating to 600 ℃ at the speed of 10 ℃/min to obtain a programmed heating desorption curve. The desorbed ammonia is detected by a thermal conductivity cell. Converting the programmed temperature desorption curve into NH 3 After the desorption rate-temperature curve, the acid center density data are obtained through the spectrum decomposition of the peak type.
Example 1A
Example 1A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
18.5g of diammonium phosphate and 1.8g of Fe (NO) 3 ) 3 Dissolving in 60g deionized water, stirring for 0.5 hr to obtain phosphorus-containing aqueous solution, adding 108g hydrogen-containing hierarchical porous ZSM-5 molecular sieve (supplied by Qilu division of China petrochemical catalyst Co., relative crystallinity of 88.6%, silica/alumina molar ratio of 20.8, na) 2 O content of 0.017 wt% and specific surface area of 373m 2 Per g, total pore volume of 0.256ml/g, mesoporous volume of 0.119ml/g, average pore diameter of 5.8nm, the same applies an impregnation method, after impregnation at 20 ℃ for 2 hours, drying in an oven at 110 ℃, externally applying pressure and adding water, and treating for 0.5 hours under a water vapor atmosphere of 0.4Mpa and 60% at 450 ℃, the obtained multistage pore ZSM-5 molecular sieve sample containing phosphorus and iron is denoted as PAMZ-1.
Example 1B
Example 1B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The same materials, proportions, drying and calcination as in example 1A were distinguished by the fact that diammonium phosphate, fe (NO 3 ) 3 The hydrogen type hierarchical pore ZSM-5 molecular sieve is mixed with water and made into slurry, and then the slurry is heated to 100 ℃ and kept for 2 hours. The resulting phosphorus and iron containing hierarchical pore ZSM-5 molecular sieve sample was designated PBMZ-1.
Comparative examples 1 to 1
Comparative example 1-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 1A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 3 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D1-1.
Comparative examples 1 to 2
Comparative examples 1-2 illustrate comparative samples of phosphorus and metal containing, multi-pore ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination. The procedure is as in example 1A, except that the calcination condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D1-2.
XPS elemental analysis data for surfaces of PAMZ-1, PBMZ-1, D1-2 are shown in Table 1-1; XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in tables 1-2; 27 the peak area ratio data of the Al MAS-NMR spectrum are shown in tables 1-3; NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The data of the ratio of the area of the center peak of the strong acid to the area of the center peak of the total acid at the desorption temperature of more than 200 ℃ in the TPD spectrogram are shown in tables 1-4.
PAZ-1, PBZ-1, D1-1 and D1-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation. Micro-inverse evaluation conditions: the molecular sieve is 2g in loading, the raw oil is n-tetradecane, the oil inlet amount is 1.56g, the reaction temperature is 550 ℃, and the regeneration temperature is 600 ℃ (the same applies below). The evaluation data are shown in tables 1 to 5.
TABLE 1-1
TABLE 1-2
Tables 1 to 3
Tables 1 to 4
Sample name The area of the strong acid center peak occupies the area specific gravity of the total acid center peak
PAMZ-1 42％
PBMZ-1 50％
D1-1 14％
D1-2 21％
Tables 1 to 5
PAMZ-1 PBMZ-1 D1-1 D1-2
Material balance/m%
Dry gas 4.4 4.2 5.3 4.0
Liquefied gas 46.4 44.9 33.5 32.9
Gasoline 18.0 19.6 31.3 34.3
Diesel oil 26.3 24.3 28.2 23.1
The main product m% of the cracked gas
Ethylene 3.9 4.0 3.5 3.4
Propylene 19.8 18.7 12.8 14.8
Total butenes 13.2 14.5 5.9 6.9
Conversion/m% 72.8 74.3 64.7 67.4
Example 2A
Example 2A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
18.5g of diammonium phosphate and 2.1g of Fe (NO) 3 ) 3 Dissolving in 120g deionized water, stirring for 0.5h to obtain phosphorus-containing aqueous solution, adding 108g hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking at 20deg.C for 2 hr, and baking at 110deg.CAfter drying in a box, pressure was applied externally and water was added thereto, and the mixture was treated at 600℃under a steam atmosphere of 0.4MPa and 50% for 2 hours to obtain a sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron, designated as PAMZ-2.
Example 2B
Example 2B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieve and method of the present invention.
The same materials, proportions, drying and calcination as in example 2A were distinguished by the fact that diammonium phosphate, fe (NO 3 ) 3 Mixing the hydrogen-type hierarchical pore ZSM-5 molecular sieve and water, pulping, and heating to 70 ℃ for 2 hours. The resulting phosphorus-containing, multi-pore ZSM-5 molecular sieve sample was designated PBMZ-2.
Comparative example 2-1
Comparative example 2-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 2A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D2-1.
Comparative examples 2 to 2
Comparative example 2-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference between the method and the method in example 2A is that the baking condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D2-2.
The XPS elemental analysis data for the surfaces of PAMZ-2, PBMZ-2, D2-1, D2-2 are shown in Table 2-1. XRD crystallinity and BET pore parameters of PAZ-2, PBZ-2, D2-1 and D2-2 before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 2-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 2 to 3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 2-4.
PAMZ-2, PBMZ-2, D2-1 and D2-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in tables 2 to 5.
TABLE 2-1
TABLE 2-2
Tables 2 to 3
Tables 2 to 4
Tables 2 to 5
PAMZ-2 PBMZ-2 D2-1 D2-2
Material balance/m%
Dry gas 4.4 5.0 5.2 3.9
Liquefied gas 36.9 42.6 32.4 33.4
Gasoline 26.5 23.4 32.2 22.6
Diesel oil 26.0 22.5 25.1 33.2
The main product m% of the cracked gas
Ethylene 3.8 4.7 3.5 3.2
Propylene 17.2 18.0 12.4 14.8
Total butenes 8.3 9.6 6.2 7.96
Conversion/m% 73.7 76.4 65.7 66.9
Example 3A
Example 3A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
11.8g of phosphoric acid and 2.4g of Fe (NO) were taken 3 ) 3 Dissolving in 60g deionized water at normal temperature, stirring for 2h to obtain a phosphorus-containing aqueous solution, adding into 108g hydrogen-containing hierarchical pore ZSM-5 molecular sieve, soaking at 20deg.C for 4 hr, drying in a 110 deg.C oven, and treating at 430 deg.C under 0.4Mpa and 100% steam atmosphere for 2h to obtain the final product, namely PAMZ-3.
Example 3B
Example 3B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The same materials, proportions, drying and calcination as in example 3A were followed except that the 80℃aqueous phosphorus-containing solution was mixed with the hydrogen-type multistage pore ZSM-5 molecular sieve heated to 80℃for 4 hours. The resulting multi-pore ZSM-5 molecular sieve containing phosphorus and iron was designated PBMZ-3.
Comparative example 3-1
Comparative example 3-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 3A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D3-1.
Comparative example 3-2
Comparative example 3-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The procedure is as in example 3A, except that the calcination condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D3-2.
The XPS elemental analysis data for the surfaces of PAMZ-3, PBMZ-3, D3-1, D3-2 are shown in Table 3-1. XRD crystallinity and BET pore parameters of PAMZ-3, PBMZ-3, D3-1 and D3-2 before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 3-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 3-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 3-4.
PAMZ-3, PBMZ-3, D3-1, D3-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in tables 3 to 5.
TABLE 3-1
TABLE 3-2
TABLE 3-3
Tables 3 to 4
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Tables 3 to 5
PAMZ-3 PBMZ-3 D3-1 D3-2
Material balance/m%
Dry gas 4.9 5.3 3.8 5.0
Liquefied gas 40.6 51.9 30.9 32.1
Gasoline 29.0 25.1 35.2 33.0
Diesel oil 19.0 11.5 26.9 27.9
The main product m% of the cracked gas
Ethylene 4.3 5.2 3.2 3.8
Propylene 16.9 19.4 13.9 13.4
Total butenes 9.7 13.8 6.7 6.8
Conversion/m% 79.8 88.1 66.3 66.9
Example 4A
Example 4A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
9.3g of diammonium phosphate and 1.8g of Fe (NO) 3 ) 3 Dissolving in 120g deionized water at normal temperature, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding into 108g hydrogen type hierarchical pore ZSM-5 molecular sieve, soaking for 2h at 20 ℃, drying in a baking oven at 110 ℃, and treating for 2h at 350 ℃ under 0.2Mpa and 100% steam atmosphere to obtain the hierarchical pore ZSM-5 molecular sieve containing phosphorus and iron, which is denoted as PAMZ-4.
Example 4B
Example 4B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The same materials and proportions as in example 4A are distinguished by the fact that diammonium phosphate, fe (NO 3 ) 3 Mixing hydrogen-type hierarchical pore ZSM-5 molecular sieve and water, pulping, heating to 70 ℃ and keeping for 2 hours. The obtained phosphor and iron containingA sample of the hierarchical pore ZSM-5 molecular sieve was designated PBMZ-4.
Comparative example 4-1
Comparative example 4-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 1A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D4-1.
Comparative example 4-2
Comparative example 4-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The procedure is as in example 1A, except that the calcination condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D4-2.
The XPS elemental analysis data for the surfaces of PAMZ-4, PBMZ-4, D4-1, D4-2 are shown in Table 4-1. XRD crystallinity and BET pore parameters of PAZ-4, PBZ-4, D4-1 and D4-2 before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 4-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 4 to 3. NH of PAZ-4 and PBZ-4 subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 4-4.
PAZ-4, PBZ-4, D4-1 and D4-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in Table 4-5.
TABLE 4-1
TABLE 4-2
TABLE 4-3
Tables 4 to 4
Tables 4 to 5
PAMZ-4 PBMZ-4 D4-1 D4-2
Material balance/m%
Dry gas 4.9 5.9 5.1 5.0
Liquefied gas 51.9 52.3 32.6 35.4
Gasoline 23.8 32.8 40.3 33.2
Diesel oil 14.7 5.0 16.7 25.0
The main product m% of the cracked gas
Ethylene 4.5 5.4 4.4 3.9
Propylene 19.3 20.1 14.8 15.0
Total butenes 15.8 13.4 5.9 6.9
Conversion/m% 84.3 93.9 73.6 75.4
Example 5A
Example 5A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
9.7g of trimethyl phosphate and 1.5g of Fe (NO) were taken 3 ) 3 Dissolving in 80g deionized water at 90 ℃ and stirring for 1h to obtain a phosphorus-containing aqueous solution, adding into 108g hydrogen-containing hierarchical pore ZSM-5 molecular sieve, modifying by an impregnation method, impregnating at 20 ℃ for 8 hours, drying in a baking oven at 110 ℃, and performing pressurized hydrothermal roasting treatment for 4h at 500 ℃ under 0.6Mpa in a 40% steam atmosphere to obtain a phosphorus-and iron-containing hierarchical pore ZSM-5 molecular sieve sample, which is denoted as PAMZ-5.
Example 5B
Example 5B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The same materials, proportions, drying and calcination as in example 5A are distinguished by trimethyl phosphate, fe (NO 3 ) 3 The hydrogen type hierarchical pore ZSM-5 molecular sieve is mixed with water and beaten into slurry, and then the slurry is heated to 120 ℃ and kept for 8 hours. The resulting phosphorus and iron containing hierarchical pore ZSM-5 molecular sieve sample was designated PBMZ-5.
Comparative example 5-1
Comparative example 5-1 illustrates the current industry conventional process and the resulting multi-pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 5A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D5-1.
Comparative example 5-2
Comparative example 5-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference between the method and the method in example 5A is that the baking condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D5-2.
The XPS elemental analysis data for the surfaces of PAMZ-5, PBMZ-5, D5-1, D5-2 are shown in Table 5-1. XRD crystallinity and BET pore parameters of PAZ-5, PBZ-5, D5-1 and D5-2 before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 5-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 5 to 3.PAMZ-5, PBMZ-5, D5-1, D5-2 NH treated with 800 ℃, 100% steam, 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 5-4.
PAZ-5, PBZ-5, D5-1 and D5-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in Table 5-5.
TABLE 5-1
TABLE 5-2
TABLE 5-3
Tables 5 to 4
Sample name The area of the strong acid center peak occupies the area specific gravity of the total acid center peak
PAMZ-5 51％
PBMZ-5 56％
D5-1 34％
D5-2 36％
Tables 5 to 5
Example 6A
Example 6A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
13.2g of boron phosphate and 1.5g of Fe (NO) 3 ) 3 Dissolving in 100g deionized water at 100deg.C, stirring for 3 hr to obtain phosphorus-containing water solution, adding into 108g hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking at 20deg.C for 2 hr, drying in oven at 110deg.C, and collecting the final productThe sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron, which is obtained by pressurized hydrothermal roasting at 350 ℃ under 0.4Mpa in a 60% steam atmosphere, is denoted as PAMZ-6.
Example 6B
Example 6B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The same materials and proportions as in example 6A are distinguished by the fact that boron phosphate, fe (NO 3 ) 3 The hydrogen type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 150 ℃ and kept for 2 hours. The resulting multi-pore ZSM-5 molecular sieve containing phosphorus and iron was designated PBMZ-6.
Comparative example 6-1
Comparative example 6-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The procedure is as in example 6A, except that the calcination conditions are normal pressure (apparent pressure 0 MPa) and air calcination is carried out in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D6-1.
Comparative example 6-2
Comparative example 6-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The procedure is as in example 6A, except that the calcination condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D6-2.
The XPS elemental analysis data for the surfaces of PAMZ-6, PBMZ-6, D6-1, D6-2 are shown in Table 6-1. XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 6-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 6-3. NH of PAMZ-6, PBMZ-6, D6-1, D6-2 subjected to hydrothermal aging at 800 ℃ with 100% steam for 17 hours 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 6-4.
PAZ-6, PBZ-6, D6-1 and D6-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in Table 6-5.
TABLE 6-1
TABLE 6-2
TABLE 6-3
Tables 6 to 4
Tables 6 to 5
PAMZ-6 PBMZ-6 D6-1 D6-2
Material balance/m%
Dry gas 5.3 5.4 4.9 4.4
Liquefied gas 51.6 53.1 36.4 36.9
Gasoline 19.8 28.9 27.1 27.3
Diesel oil 19.7 7.1 27.0 28.4
The main product m% of the cracked gas
Ethylene 4.5 5.0 3.9 3.9
Propylene 18.1 18.5 15.9 16.2
Total butenes 12.9 13.9 7.2 11.8
Conversion/m% 79.8 85.1 73.8 74.8
Example 7A
Example 7A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
16.3g of triphenylphosphine and 1.8g of Fe (NO) 3 ) 3 Dissolving in 80g deionized water, stirring for 2h to obtain a phosphorus-containing aqueous solution, adding into 108g hydrogen type multistage hole ZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating at 20 ℃ for 4 hours, drying in a 110 ℃ oven, and carrying out pressurized hydrothermal roasting treatment for 2h at 600 ℃ under 1.0Mpa and 50% steam atmosphere to obtain a phosphorus-and iron-containing multistage hole ZSM-5 molecular sieve sample which is denoted as PAMZ-7.
Example 7B
Example 7B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
Materials and formulations as in example 7AThe difference is that the composition contains phosphorus and Fe (NO) 3 ) 3 Is mixed and contacted with hydrogen-type multistage hole ZSM-5 molecular sieve heated to 80 ℃ for 4 hours. The resulting phosphorus and iron containing hierarchical pore ZSM-5 molecular sieve sample was designated PBMZ-7.
Comparative example 7-1
Comparative example 7-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The procedure is as in example 7A, except that the calcination conditions are normal pressure (apparent pressure 0 MPa) and air-calcination is carried out in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is marked as D7-1.
Comparative example 7-2
Comparative example 7-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The procedure is as in example 7A, except that the calcination condition is normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D7-2.
XPS element analysis data of surfaces of PAMZ-7, PBMZ-7, D7-1 and D7-2 are shown in Table 7-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 7-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 7-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 7-4.
PAZ-7, PBZ-7, D7-1 and D7-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 7-5.
TABLE 7-1
TABLE 7-2
TABLE 7-3
TABLE 7-4
Sample name The area of the strong acid center peak occupies the area specific gravity of the total acid center peak
PAMZ-7 49％
PBMZ-7 58％
D7-1 32％
D7-2 38％
TABLE 7-5
PAMZ-7 PBMZ-7 D7-1 D7-2
Material balance/m%
Dry gas 4.9 5.0 4.6 6.6
Liquefied gas 43.8 50.1 39.4 40.8
Gasoline 31.3 29.3 29.3 31.4
Diesel oil 5.0 9.8 21.6 20.1
In cracked gasThe main product is m%
Ethylene 4.4 4.7 3.5 4.7
Propylene 18.1 18.7 14.1 14.8
Total butenes 10.4 13.5 9.4 9.1
Conversion/m% 82.6 86.3 71.1 72.0
Example 8A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 2.2 g of cobalt nitrate, and the resulting phosphorus and cobalt containing multi-pore ZSM-5 molecular sieve sample No. PAMZ-8 is obtained.
Example 8B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 2.2 g of cobalt nitrate, and the obtained phosphorus and cobalt containing multi-stage pore ZSM-5 molecular sieve sample No. PBMZ-8.
Comparative example 8-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 2.2 g of cobalt nitrate, and the obtained phosphorus and cobalt-containing multi-pore ZSM-5 molecular sieve was compared with sample number D8-1.
Comparative example 8-2
The same as comparative example 4-2, except that 1.8 g of iron nitrate was changed to 2.2 g of cobalt nitrate, and the obtained phosphorus and cobalt-containing multi-pore ZSM-5 molecular sieve was compared with sample number D8-2.
XPS element analysis data of surfaces of PAMZ-8, PBMZ-8, D8-1 and D8-2 are shown in Table 8-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 8-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 8-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 8-4.
PAZ-8, PBZ-8, D8-1 and D8-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 8-5.
TABLE 8-1
TABLE 8-2
TABLE 8-3
Tables 8 to 4
Tables 8 to 5
PAMZ-8 PBMZ-8 D8-1 D8-2
Material balance/m%
Dry gas 5.1 6.1 5.3 5.2
Liquefied gas 50.8 51.1 31.9 34.6
Gasoline 23.2 32.0 39.3 32.4
Diesel oil 14.4 4.9 16.4 24.5
The main product m% of the cracked gas
Ethylene 4.2 5.1 4.1 3.6
Propylene 18.6 19.4 14.1 14.3
Total butenes 15.4 13.0 5.5 6.5
Conversion/m% 83.0 92.5 72.5 74.3
Example 9A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 2.1 g of nickel nitrate, and the resulting phosphorus and nickel containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-9.
Example 9B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 2.1 g of nickel nitrate, and the obtained phosphorus and nickel containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-9.
Comparative example 9-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 2.1 g of nickel nitrate, and the obtained phosphorus and nickel-containing multi-pore ZSM-5 molecular sieve was compared with sample No. D9-1.
Comparative example 9-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 2.1 g of nickel nitrate, and the obtained multi-pore ZSM-5 molecular sieve containing phosphorus and nickel was compared with sample No. D9-2.
The XPS elemental analysis data of the surfaces of PAMZ-9, PBMZ-9, D9-1 and D9-2 are shown in Table 9-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 9-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 9-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 9-4.
PAZ-7, PBZ-7, D7-1 and D7-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in Table 9-5.
TABLE 9-1
TABLE 9-2
TABLE 9-3
Tables 9 to 4
Tables 9 to 5
PAMZ-9 PBMZ-9 D9-1 D9-2
Material balance/m%
Dry gas 5.1 6.2 5.4 5.3
Liquefied gas 50.4 50.8 31.7 34.4
Gasoline 23.1 31.8 39.1 32.2
Diesel oil 14.2 4.8 16.2 24.2
The main product m% of the cracked gas
Ethylene 4.1 5.0 4.0 3.5
Propylene 18.5 19.3 14.0 14.2
Total butenes 15.3 12.9 5.4 6.4
Conversion/m% 82.2 91.6 71.8 73.5
Example 10A
The procedure is as in example 4A except that 1.8 g of ferric nitrate is changed to 1.2 g of zinc sulfate, and the obtained phosphorus and zinc containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-10.
Example 10B
The procedure is as in example 4B except that 1.8 g of ferric nitrate is changed to 1.2 g of zinc sulfate, and the obtained phosphorus and zinc containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-10.
Comparative example 10-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.2 g of zinc sulfate, and the obtained phosphorus and zinc-containing multi-pore ZSM-5 molecular sieve was compared with sample No. D10-1.
Comparative example 10-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 1.2 g of zinc sulfate, and the obtained phosphorus and zinc-containing multi-pore ZSM-5 molecular sieve was compared with sample No. D10-2.
XPS element analysis data of surfaces of PAMZ-10, PBMZ-10, D10-1 and D10-2 are shown in Table 10-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 10-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 10-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 10-4.
PAZ-10, PBZ-10, D10-1 and D10-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 10-5.
TABLE 10-1
TABLE 4-2
TABLE 10-3
TABLE 10-4
TABLE 10-5
PAMZ-10 PBMZ-10 D10-1 D10-2
Material balance/m%
Dry gas 5.2 6.3 5.4 5.3
Liquefied gas 50.2 50.6 31.6 34.3
Gasoline 22.8 31.5 38.7 31.9
Diesel oil 14.4 4.9 16.3 24.5
The main product m% of the cracked gas
Ethylene 4.1 5.0 4.0 3.5
Propylene 18.7 19.5 14.2 14.4
Total butenes 15.5 13.1 5.6 6.6
Conversion/m% 81.1 90.3 70.8 72.5
Example 11A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 1.5 g of manganese nitrate, and the obtained phosphorus and manganese containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-11.
Example 11B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 1.5 g of manganese nitrate, and the obtained phosphorus and manganese containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-11.
Comparative example 11-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.5 g of manganese nitrate, and the obtained phosphorus and manganese-containing multi-pore ZSM-5 molecular sieve was compared with sample number D11-1.
Comparative example 11-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 1.5 g of manganese nitrate, and the obtained phosphorus and manganese-containing multi-pore ZSM-5 molecular sieve was compared with sample No. D11-2.
XPS element analysis data of surfaces of PAMZ-11, PBMZ-11, D11-1 and D11-2 are shown in Table 11-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 11-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 11-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The data of the ratio of the area of the center peak of the strong acid to the area of the center peak of the total acid at the desorption temperature of more than 200 ℃ in the TPD spectrogram are shown in the table 11-4.
PAMZ-11, PBMZ-11, D11-1 and D11-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 11-5.
TABLE 11-1
TABLE 11-2
TABLE 11-3
TABLE 11-4
TABLE 11-5
PAMZ-11 PBMZ-11 D11-1 D11-2
Material balance/m%
Dry gas 5.0 6.0 5.2 5.1
Liquefied gas 50.6 51.0 31.8 34.5
Gasoline 22.4 30.8 37.9 31.2
Diesel oil 14.2 4.8 16.1 24.1
The main product m% of the cracked gas
Ethylene 4.2 5.1 4.1 3.6
Propylene 19.1 19.9 14.6 14.8
Total butenes 15.7 13.3 5.8 6.8
Conversion/m% 82.8 92.2 72.3 74.0
Example 12A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 2.0 g of gallium nitrate, and the obtained phosphorus and gallium containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-12.
Example 12B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 2.0 g of gallium nitrate, and the obtained phosphorus and gallium containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-12.
Comparative example 12-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 2.0 g of gallium nitrate, and the obtained multi-pore ZSM-5 molecular sieve containing phosphorus and gallium was compared with sample number D12-1.
Comparative example 12-2
The same as comparative example 4-2, except that 1.8 g of iron nitrate was changed to 2.0 g of gallium nitrate, and the obtained multi-pore ZSM-5 molecular sieve containing phosphorus and gallium was compared with sample number D12-2.
XPS element analysis data of surfaces of PAMZ-12, PBMZ-12, D12-1 and D12-2 are shown in Table 12-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 12-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 12-3. Water heating at 800 deg.C with 100% water vapor for 17 hrAging-treated NH 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 12-4.
PAMZ-12, PBMZ-12, D12-1 and D12-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 12-5.
TABLE 12-1
TABLE 12-2
TABLE 12-3
TABLE 12-4
TABLE 12-5
PAMZ-12 PBMZ-12 D12-1 D12-2
Material balance/m%
Dry gas 5.1 6.1 5.3 5.2
Liquefied gas 51.1 51.5 32.1 34.9
Gasoline 22.6 31.2 38.3 31.5
Diesel oil 14.3 4.9 16.2 24.3
The main product m% of the cracked gas
Ethylene 4.4 5.3 4.3 3.8
Propylene 19.2 20.0 14.7 14.9
Total butenes 15.6 13.2 5.7 6.7
Conversion/m% 83.2 92.7 72.6 74.4
Example 13A
The procedure is as in example 4A except that 1.8 g of ferric nitrate is changed to 2.0 g of stannic chloride, and the resulting phosphorus and stannic hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-13.
Example 13B
The procedure is as in example 4B except that 1.8 g of ferric nitrate is changed to 2.0 g of stannic chloride, and the obtained phosphorus and stannic hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-13.
Comparative example 13-1
The same as comparative example 4-1 except that 1.8 g of ferric nitrate was changed to 2.0 g of tin chloride, the obtained phosphorus and tin-containing multi-pore ZSM-5 molecular sieve was compared with sample No. D13-1.
Comparative example 13-2
The same as comparative example 4-2 except that 1.8 g of ferric nitrate was changed to 2.0 g of tin chloride, the obtained phosphorus and tin-containing multi-pore ZSM-5 molecular sieve was compared with sample No. D13-2.
XPS element analysis data of surfaces of PAMZ-13, PBMZ-13, D13-1 and D13-2 are shown in Table 13-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 13-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 13-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 13-4.
PAMZ-13, PBMZ-13, D13-1 and D13-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 13-5.
TABLE 13-1
TABLE 13-2
TABLE 13-3
TABLE 13-4
TABLE 13-5
PAMZ-13 PBMZ-13 D13-1 D13-2
Material balance/m%
Dry gas 5.2 6.3 5.4 5.3
Liquefied gas 50.3 50.7 31.6 34.3
Gasoline 22.5 31.0 38.1 31.4
Diesel oil 14.5 4.9 16.5 24.7
The main product m% of the cracked gas
Ethylene 4.3 5.2 4.2 3.7
Propylene 19.0 19.8 14.5 14.7
Total butenes 15.4 13.0 5.5 6.5
Conversion/m% 81.9 91.2 71.5 73.2
Example 14A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 3.3 g of lanthanum nitrate, and the obtained phosphorus and lanthanum containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-14.
Example 14B
The procedure is as in example 4B except that 1.8 grams of iron nitrate is changed to 3.3 grams of lanthanum nitrate and that a sample of the resulting phosphorus and lanthanum containing hierarchical pore ZSM-5 molecular sieve, sample No. PBMZ-14.
Comparative example 14-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 3.3 g of lanthanum nitrate, and the obtained phosphorus and lanthanum containing multi-pore ZSM-5 molecular sieve was compared with sample No. D14-1.
Comparative example 14-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 3.3 g of lanthanum nitrate, and the obtained phosphorus and lanthanum containing multi-pore ZSM-5 molecular sieve was compared with sample No. D14-2.
The XPS elemental analysis data of the surfaces of PAMZ-14, PBMZ-14, D14-1 and D14-2 are shown in Table 14-1, and XRD crystallinity and BET pore parameters before and after the hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 14-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 14-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 14-4.
PAZ-14, PBZ-14, D14-1 and D14-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 14-5.
TABLE 14-1
TABLE 14-2
TABLE 14-3
TABLE 14-4
TABLE 14-5
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Example 15A
The procedure is as in example 4A except that 1.8 g of ferric nitrate is changed to 1.8 g of cerium chloride, and the obtained phosphorus and cerium containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-15.
Example 15B
The procedure is as in example 4B except that 1.8 g of ferric nitrate is changed to 1.8 g of cerium chloride, and the obtained phosphorus and cerium containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-15.
Comparative example 15-1
The same as comparative example 4-1 except that 1.8 g of ferric nitrate was changed to 1.8 g of cerium chloride, and the obtained multi-pore ZSM-5 molecular sieve containing phosphorus and cerium was compared with sample number D15-1.
Comparative example 15-2
The same as comparative example 4-2 except that 1.8 g of ferric nitrate was changed to 1.8 g of cerium chloride, and the obtained multi-pore ZSM-5 molecular sieve containing phosphorus and cerium was compared with sample No. D15-2.
The XPS elemental analysis data of the surfaces of PAMZ-15, PBMZ-15, D15-1 and D15-2 are shown in Table 15-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 15-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 15-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The data of the ratio of the area of the center peak of the strong acid to the area of the center peak of the total acid at the desorption temperature of more than 200 ℃ in the TPD spectrogram are shown in tables 15-4.
PAMZ-156, PBMZ-15, D15-1, D15-2 were subjected to 800 ℃, 100% steam, 17h hydrothermal aging, and then subjected to n-tetradecane cracking evaluation, and the evaluation data are shown in Table 15-5.
TABLE 15-1
TABLE 15-2
TABLE 15-3
TABLE 15-4
TABLE 15-5
PAMZ-15 PBMZ-15 D15-1 D15-2
Material balance/m%
Dry gas 5.1 6.2 5.4 5.3
Liquefied gas 52.2 52.6 32.8 35.6
Gasoline 24.4 33.6 41.3 34.0
Diesel oil 14.1 4.8 16.0 24.0
The main product m% of the cracked gas
Ethylene 4.6 5.5 4.5 4.0
Propylene 19.4 20.2 14.9 15.1
Total butenes 15.9 13.5 6.0 7.0
Conversion/m% 85.1 94.8 74.3 76.2
Example 16A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 0.8 g of iron nitrate and 0.8 g of nickel nitrate, and the resulting phosphorus, iron and nickel containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-16 is obtained.
Example 16B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 0.8 g of iron nitrate and 0.8 g of nickel nitrate, and the obtained phosphorus, iron and nickel containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-16 is used.
Comparative example 16-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 0.8 g of iron nitrate and 0.8 g of nickel nitrate, the obtained multi-pore ZSM-5 molecular sieve containing phosphorus, iron and nickel was compared with sample No. D16-1.
Comparative example 16-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 0.8 g of iron nitrate and 0.8 g of nickel nitrate, the obtained multi-pore ZSM-5 molecular sieve containing phosphorus, iron and nickel was compared with sample No. D16-2.
The XPS elemental analysis data of the surfaces of PAMZ-16, PBMZ-16, D16-1 and D16-2 are shown in Table 16-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 16-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 16-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 16-4.
PAZ-16, PBZ-16, D16-1 and D16-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 16-5.
TABLE 16-1
TABLE 16-2
TABLE 16-3
TABLE 16-4
TABLE 16-5
PAMZ-16 PBMZ-16 D16-1 D16-2
Material balance/m%
Dry gas 5.6 6.8 5.9 5.8
Liquefied gas 52.5 52.9 33.0 35.8
Gasoline 24.5 33.8 41.5 34.2
Diesel oil 14.0 4.8 15.9 23.8
The main product m% of the cracked gas
Ethylene 4.7 5.6 4.6 4.1
Propylene 19.6 20.4 15.1 15.3
Total butenes 16.0 13.6 6.1 7.1
Conversion/m% 86.0 95.8 75.1 76.9
Example 17A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 1.2 g of iron nitrate and 0.8 g of manganese nitrate, and the obtained phosphorus, iron and manganese containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-17 is used.
Example 17B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 1.2 g of iron nitrate and 0.8 g of manganese nitrate, and the obtained phosphorus, iron and manganese containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-17 is used.
Comparative example 17-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.2 g of iron nitrate and 0.8 g of manganese nitrate, the obtained phosphorus, iron and manganese-containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D17-1.
Comparative example 17-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 1.2 g of iron nitrate and 0.8 g of manganese nitrate, the obtained phosphorus, iron and manganese-containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D17-2.
XPS element analysis data of surfaces of PAMZ-17, PBMZ-17, D17-1 and D17-2 are shown in Table 17-1, and XRD crystallinity and BET pore parameters before and after hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours are shown in Table 17-2. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 17-3. Through a temperature of 800℃,NH treated by 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 17-4.
PAMZ-17, PBMZ-17, D17-1 and D17-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 17-5.
TABLE 17-1
TABLE 17-2
TABLE 17-3
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TABLE 17-4
TABLE 17-5
PAMZ-17 PBMZ-17 D17-1 D17-2
Material balance/m%
Dry gas 5.9 7.1 6.1 6.0
Liquefied gas 52.1 52.5 32.7 35.5
Gasoline 23.5 32.4 39.8 32.8
Diesel oil 14.4 4.9 16.4 24.5
The main product m% of the cracked gas
Ethylene 4.6 5.5 4.5 4.0
Propylene 19.5 20.3 15.0 15.2
Total butenes 15.9 13.5 6.0 7.0
Conversion/m% 83.4 92.9 72.8 74.6
Example 18A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 1.0 g of cobalt nitrate and 0.8 g of manganese nitrate, and the obtained phosphorus, cobalt and manganese containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-18 is used.
Example 18B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 1.0 g of cobalt nitrate and 0.8 g of manganese nitrate, and the obtained phosphorus, cobalt and manganese containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-18 is used.
Comparative example 18-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.0 g of cobalt nitrate and 0.8 g of manganese nitrate, and the obtained multi-pore ZSM-5 molecular sieve containing phosphorus, cobalt and manganese was compared with sample number D18-1.
Comparative example 18-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 1.0 g of cobalt nitrate and 0.8 g of manganese nitrate, the obtained phosphorus, cobalt and manganese-containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D18-2.
The XPS elemental analysis data of the surfaces of PAMZ-18, PBMZ-18, D18-1 and D18-2 are shown in Table 18-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 18-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 18-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 18-4.
PAZ-7, PBZ-7, D7-1 and D7-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 18-5.
TABLE 18-1
TABLE 18-2
TABLE 18-3
TABLE 18-4
TABLE 18-5
PAMZ-18 PBMZ-18 D18-1 D18-2
Material balance/m%
Dry gas 5.4 6.5 5.6 5.5
Liquefied gas 52.2 52.6 32.8 35.6
Gasoline 23.2 32.0 39.3 32.4
Diesel oil 14.6 5.0 16.5 24.8
The main product m% of the cracked gas
Ethylene 4.6 5.5 4.5 4.0
Propylene 19.5 20.3 15.0 15.2
Total butenes 15.7 13.3 5.8 6.8
Conversion/m% 81.9 91.2 71.5 73.2
Example 19A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 1.0 g of iron nitrate and 1.2 g of tin chloride, and the resulting phosphorus, iron and tin containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-19.
Example 19B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 1.0 g of iron nitrate and 1.2 g of tin chloride, and the resulting phosphorus, iron and tin containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-19.
Comparative example 19-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.0 g of iron nitrate and 1.2 g of tin chloride, the obtained phosphorus, iron and tin-containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D19-1.
Comparative example 19-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 1.0 g of iron nitrate and 1.2 g of tin chloride, the obtained phosphorus, iron and tin-containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D19-2.
The XPS elemental analysis data of the surfaces of PAMZ-19, PBMZ-19, D19-1 and D19-2 are shown in Table 19-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 19-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 19-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at desorption temperature above 200 ℃ in the TPD spectrum are shown in Table 19-4.
PAMZ-19, PBMZ-19, D19-1, D19-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data of which are shown in Table 19-5.
TABLE 19-1
TABLE 19-2
TABLE 19-3
TABLE 19-4
TABLE 19-5
PAMZ-19 PBMZ-19 D19-1 D19-2
Material balance/m%
Dry gas 5.6 6.8 5.9 5.8
Liquefied gas 51.2 51.6 32.1 34.9
Gasoline 22.8 31.5 38.7 31.9
Diesel oil 15.0 5.1 17.0 25.5
The main product m% of the cracked gas
Ethylene 4.6 5.5 4.5 4.0
Propylene 19.1 19.9 14.6 14.8
Total butenes 15.6 13.2 5.7 6.7
Conversion/m% 80.9 90.1 70.7 72.4
Example 20A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 1.0 g of iron nitrate and 1.2 g of lanthanum nitrate, and the obtained phosphorus, iron and lanthanum containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-20.
Example 20B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 1.0 g of iron nitrate and 1.2 g of lanthanum nitrate, and the obtained phosphorus, iron and lanthanum containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-20 is used.
Comparative example 20-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.0 g of iron nitrate and 1.2 g of lanthanum nitrate, and the obtained phosphorus, iron and lanthanum containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D20-1.
Comparative example 20-2
The same as comparative example 4-2 except that 1.8 g of iron nitrate was changed to 1.0 g of iron nitrate and 1.2 g of lanthanum nitrate, and the obtained phosphorus, iron and lanthanum containing hierarchical pore ZSM-5 molecular sieve was compared with sample number D20-2.
The XPS elemental analysis data of the surfaces of PAMZ-20, PBMZ-20, D20-1 and D20-2 are shown in Table 20-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 20-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 20-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 20-4.
PAMZ-20, PBMZ-20, D20-1 and D20-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 20-5.
TABLE 20-1
TABLE 20-2
TABLE 20-3
TABLE 20-4
TABLE 20-5
PAMZ-20 PBMZ-20 D20-1 D20-2
Material balance/m%
Dry gas 5.5 6.6 5.7 5.6
Liquefied gas 54.0 54.4 33.9 36.8
Gasoline 22.6 31.2 38.3 31.5
Diesel oil 14.4 4.9 16.4 24.5
The main product m% of the cracked gas
Ethylene 4.7 5.6 4.6 4.1
Propylene 19.6 20.4 15.1 15.3
Total butenes 16.0 13.6 6.1 7.1
Conversion/m% 86.8 96.7 75.8 77.7
Example 21A
The procedure is as in example 4A except that 1.8 g of iron nitrate is changed to 1.0 g of iron nitrate and 1.0 g of cerium chloride, and the resulting phosphorus, iron and cerium containing hierarchical pore ZSM-5 molecular sieve sample No. PAMZ-21.
Example 21B
The procedure is as in example 4B except that 1.8 g of iron nitrate is changed to 1.0 g of iron nitrate and 1.0 g of cerium chloride, and the obtained phosphorus, iron and cerium containing hierarchical pore ZSM-5 molecular sieve sample No. PBMZ-21.
Comparative example 21-1
The same as comparative example 4-1 except that 1.8 g of iron nitrate was changed to 1.0 g of iron nitrate and 1.0 g of cerium chloride, the obtained multi-pore ZSM-5 molecular sieve containing phosphorus, iron and cerium was compared with sample No. D21-1.
Comparative example 21-2
The same as comparative example 4-2 except that 1.8g of iron nitrate was changed to 1.0 g of iron nitrate and 1.0 g of cerium chloride, the obtained multi-pore ZSM-5 molecular sieve containing phosphorus, iron and cerium was compared with sample No. D21-2.
The XPS elemental analysis data of the surfaces of PAMZ-21, PBMZ-21, D21-1 and D21-2 are shown in Table 21-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 21-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 21-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in tables 21-4.
PAMZ-21, PBMZ-21, D21-1 and D21-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 21-5.
TABLE 21-1
TABLE 21-2
TABLE 21-3
TABLE 21-4
TABLE 21-5
PAMZ-21 PBMZ-21 D21-1 D21-2
Material balance/m%
Dry gas 5.4 6.5 5.7 5.6
Liquefied gas 53.5 53.9 33.6 36.5
Gasoline 24.3 33.5 41.1 33.9
Diesel oil 14.1 4.8 16.0 24.0
The main product m% of the cracked gas
Ethylene 4.8 5.7 4.7 4.2
Propylene 19.5 20.3 15.0 15.2
Total butenes 15.9 13.5 6.0 7.0
Conversion/m% 85.6 95.3 74.7 76.5
Example 22A
Example 22A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
9.3g of diammonium hydrogen phosphate is taken and dissolved in 120g of deionized water at normal temperature, stirred for 0.5h to obtain a phosphorus-containing aqueous solution, the phosphorus-containing aqueous solution is added into 108g of hydrogen-containing multi-level pore ZSM-5 molecular sieve, the solution is immersed for 2h at 20 ℃ and then dried in a baking oven at 110 ℃, the solution is treated for 2h in a steam atmosphere of 350 ℃ and 0.2Mpa and 100%, and 1.8g of Fe (NO 3 ) 3 Dissolving in 60g deionized water, mixing, soaking and drying the obtained sample with the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, roasting the obtained sample at 550 ℃ for 2 hours, and marking the obtained phosphorus-and iron-containing hierarchical pore ZSM-5 molecular sieve as PAMZ-22.
Example 22B
Example 22B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The materials and proportions of example 22A were varied in that diammonium hydrogen phosphate, hydrogen-type hierarchical pore ZSM-5 molecular sieve and water were mixed and slurried, and then heated to 70℃and maintained for 2 hours. The resulting phosphorus and iron containing hierarchical pore ZSM-5 molecular sieve sample was designated PBMZ-22.
Comparative example 22-1
Comparative example 22-1 illustrates the current industry conventional process and the resulting multi-pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 22A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and iron is denoted as D22-1.
Comparative example 22-2
Comparative example 22-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The procedure of example 22A was repeated except that the firing condition was normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and iron was obtained and designated D22-2.
The XPS elemental analysis data of the surfaces of PAMZ-22, PBMZ-22, D22-1 and D22-2 are shown in Table 22-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 22-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 22-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 22-4.
PAMZ-22, PBMZ-22, D22-1 and D22-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 22-5.
TABLE 22-1
TABLE 22-2
TABLE 22-3
TABLE 22-4
/>
TABLE 22-5
PAMZ-22 PBMZ-22 D22-1 D22-2
Material balance/m%
Dry gas 5.1 6.2 5.4 5.3
Liquefied gas 54.5 54.9 34.2 37.2
Gasoline 24.8 34.1 41.9 34.5
Diesel oil 14.4 4.9 16.4 24.5
The main product m% of the cracked gas
Ethylene 4.7 5.6 4.6 4.1
Propylene 19.7 20.5 15.2 15.4
Total butenes 16.0 13.6 6.1 7.1
Conversion/m% 86.0 95.8 75.1 76.9
Example 23A
Example 23A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The procedure of example 22A was repeated except that after the obtained phosphorus-containing ZSM-5 molecular sieve sample was dissolved in 60g of deionized water, 2.0 g of g zinc sulfate was again dissolved, the obtained mixture was subjected to impregnation modification and mixed with the obtained phosphorus-containing ZSM-5 molecular sieve sample, the obtained sample was subjected to impregnation drying, and the obtained sample was subjected to calcination treatment at 550℃for 2 hours, and the obtained phosphorus-and zinc-containing hierarchical pore ZSM-5 molecular sieve sample was designated as PAMZ-23.
Example 23B
Example 23A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The materials, proportions, drying and calcination of example 23A were identical except that diammonium hydrogen phosphate, hydrogen-type hierarchical pore ZSM-5 molecular sieve and water were mixed and slurried, and then heated to 100deg.C and maintained for 2 hours. A sample of the multi-stage pore ZSM-5 molecular sieve containing phosphorus and zinc was obtained and designated PBMZ-23.
Comparative example 23-1
Comparative example 23-1 illustrates the conventional process of the prior art and the resulting multi-stage pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 23A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus and zinc is marked as D23-1.
Comparative example 23-2
Comparative example 23-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The procedure of example 23A was repeated except that the firing condition was normal pressure (apparent pressure 0 MPa). A comparative sample of ZSM-5 molecular sieve containing phosphorus and zinc was obtained and designated D23-2.
The XPS elemental analysis data of the surfaces of PAMZ-23, PBMZ-23, D23-1 and D23-2 are shown in Table 23-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 23-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 23-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 23-4.
PAMZ-23, PBMZ-23, D23-1, D23-2 were subjected to 800℃100% steam, 17h hydrothermal aging, and then subjected to n-tetradecane cleavage evaluation, the evaluation data are shown in Table 23-5.
TABLE 23-1
TABLE 23-2
TABLE 23-3
TABLE 23-4
TABLE 23-5
PAMZ-23 PBMZ-23 D23-1 D23-2
Material balance/m%
Dry gas 5.5 6.6 5.7 5.6
Liquefied gas 52.7 53.1 33.2 36.0
Gasoline 23.7 32.8 40.2 33.2
Diesel oil 14.1 4.8 16.0 24.0
The main product m% of the cracked gas
Ethylene 4.3 5.2 4.2 3.7
Propylene 19.1 19.9 14.6 14.8
Total butenes 15.7 13.3 5.8 6.8
Conversion/m% 82.7 92.1 72.2 74.0
Example 24A
Example 24A illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The procedure of example 22A was repeated except that after the obtained sample of the phosphorus-containing ZSM-5 molecular sieve, 1.2 g of iron nitrate and 2.0g of zinc sulfate were dissolved in 60g of deionized water, and the obtained sample was modified by an impregnation method, mixed with the obtained sample of the phosphorus-containing iron and zinc-containing multi-stage pore ZSM-5 molecular sieve, impregnated and dried, and the obtained sample was calcined at 550℃for 2 hours, and the obtained sample of the phosphorus-containing, iron-and zinc-containing multi-stage pore ZSM-5 molecular sieve was designated as PAMZ-24.
Example 24B
Example 24B illustrates the phosphorus and metal containing, multi-stage pore ZSM-5 molecular sieves and methods of the present invention.
The materials, proportions, drying and calcination of example 24A were identical except that diammonium hydrogen phosphate, hydrogen-type hierarchical pore ZSM-5 molecular sieve and water were mixed and slurried, and then heated to 100deg.C and maintained for 2 hours. The resulting multi-pore ZSM-5 molecular sieve sample containing phosphorus, iron and zinc was designated PBMZ-24.
Comparative example 24-1
Comparative example 24-1 illustrates the current industry conventional process and the resulting multi-pore ZSM-5 comparative sample containing phosphorus and metal.
The same as in example 23A was conducted except that the firing conditions were normal pressure (apparent pressure 0 MPa) and air was blown in a muffle furnace at 550℃for 2 hours. The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus, iron and zinc is marked as D24-1.
Comparative example 24-2
Comparative example 24-2 illustrates a comparative sample of a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The same as in example 24A was conducted except that the firing condition was normal pressure (apparent pressure 0 MPa). The obtained comparative sample of the multistage pore ZSM-5 molecular sieve containing phosphorus, iron and zinc is marked as D24-2.
The XPS elemental analysis data of the surfaces of PAMZ-24, PBMZ-24, D24-1 and D24-2 are shown in Table 24-1, and XRD crystallinity and BET pore parameters of the surfaces are shown in Table 24-2 before and after the surfaces are subjected to hydrothermal aging treatment at 800 ℃ and 100% steam for 17 hours. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 24-3. NH treated by 800 ℃ and 100% steam and 17h hydrothermal aging 3 The specific gravity data of the strong acid center peak area to total acid center peak area at the desorption temperature above 200 ℃ in the TPD spectrogram are shown in Table 24-4.
PAMZ-24, PBMZ-24, D24-1 and D24-2 were subjected to hydrothermal aging at 800℃with 100% steam for 17 hours, and then subjected to n-tetradecane cleavage evaluation, the evaluation data being shown in Table 24-5.
TABLE 24-1
TABLE 24-2
TABLE 24-3
TABLE 24-4
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TABLE 13-5
PAMZ-24 PBMZ-24 D24-1 D24-2
Material balance/m%
Dry gas 5.4 6.6 5.6 5.5
Liquefied gas 53.0 53.4 33.3 36.2
Gasoline 23.8 32.9 40.4 33.3
Diesel oil 14.0 4.8 15.8 23.8
The main product m% of the cracked gas
Ethylene 4.4 5.3 4.3 3.8
Propylene 19.0 19.8 14.5 14.7
Total butenes 15.7 13.3 5.8 6.8
Conversion/m% 83.1 92.6 72.6 74.3
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (32)

1. A multistage pore ZSM-5 molecular sieve containing phosphorus and metal is characterized in that in surface XPS elemental analysis, n1/n2 is less than or equal to 0.08, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum; 27 in AlMAS-NMR, the ratio of the resonance signal peak area with the chemical shift of 39+/-3 ppm to the resonance signal peak area with the chemical shift of 54 ppm+/-3 ppm is more than or equal to 1; when phosphorus and aluminum are counted in mol, the ratio of the phosphorus to the aluminum is 0.01-2; the metal is selected from one or more of VIII, IIB, VIIB, IIIA, IVA and lanthanide metals.
2. The molecular sieve of claim 1, wherein n1/n2 is less than or equal to 0.07.
3. The molecular sieve of claim 1, wherein n1/n2 is less than or equal to 0.06.
4. The molecular sieve of claim 1, wherein n1/n2 is 0.02 to 0.05.
5. The molecular sieve according to claim 1, wherein the ratio of the mesoporous volume to the total pore volume is more than 10%, and the average pore diameter is 2-20 nm.
6. A molecular sieve according to claim 1, wherein, 27 in Al MAS-NMR, the ratio of the resonance signal peak area with the chemical shift of 39+ -3 ppm to the resonance signal peak area with the chemical shift of 54 ppm+ -3 ppm is not less than 8.
7. A molecular sieve as claimed in claim 6, wherein, 27 In Al MAS-NMR, the ratio of the resonance signal peak area with the chemical shift of 39+ -3 ppm to the resonance signal peak area with the chemical shift of 54 ppm+ -3 ppm is not less than 12.
8. A molecular sieve as claimed in claim 7, wherein, 27 in Al MAS-NMR, the ratio of the resonance signal peak area with a chemical shift of 39.+ -.3 ppm to the resonance signal peak area with a chemical shift of 54 ppm.+ -.3 ppm is 14 to 25.
9. The molecular sieve of claim 1, which has an NH after a hydrothermal aging at 800 ℃ under 100% steam conditions for 17 hours 3 In the TPD spectrum, the specific gravity of the strong acid center peak area with the desorption temperature of more than 200 ℃ to the total acid center peak area is more than or equal to 45 percent.
10. The molecular sieve of claim 9, having an NH of after a hydrothermal aging at 800 ℃ under 100% steam conditions for 17 hours 3 In the TPD spectrum, the specific gravity of the area of the strong acid center peak with the desorption temperature of more than 200 ℃ to the total acid center peak area is more than or equal to 50 percent.
11. The molecular sieve of claim 10, having an NH of after a hydrothermal aging at 800 ℃ under 100% steam conditions for 17 hours 3 In the TPD spectrum, the desorption temperature is 200 DEG CThe proportion of the area of the center peak of the strong acid to the area of the center peak of the total acid is more than or equal to 60 percent.
12. The molecular sieve of claim 11, having an NH of after a hydrothermal aging at 800 ℃ under 100% steam conditions for 17 hours 3 In the TPD spectrum, the specific gravity of the strong acid center peak area with the desorption temperature of more than 200 ℃ to the total acid center peak area is 60-80 percent.
13. The molecular sieve of claim 1, wherein the ratio of phosphorus to aluminum is 0.1 to 1.5 when both are calculated on a molar basis.
14. The molecular sieve of claim 13, wherein the ratio of phosphorus to aluminum is 0.2 to 1.5 when both are calculated on a molar basis.
15. The molecular sieve of claim 1, wherein the metal is selected from one or more of Fe, co, ni, zn, mn, ga, sn, la, ce.
16. A molecular sieve according to claim 1 or 15 wherein the metal is present in an amount of from 0.1 to 10% by weight as oxide.
17. The molecular sieve of claim 16, wherein the metal is 0.2 to 5 wt% as oxide.
18. The process for preparing a phosphorus and metal containing, multi-pore ZSM-5 molecular sieve as claimed in claim 1, wherein one of the processes comprises: contacting phosphorus-containing compound solution and metal compound solution with hydrogen type hierarchical pore ZSM-5 molecular sieve, drying, and performing hydrothermal roasting treatment under external applied pressure and external water-added atmosphere environment to recover product; wherein, in the hydrogen type multistage pore ZSM-5 molecular sieve, the proportion of the mesoporous volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm; the contact is to mix and contact the aqueous solution of the phosphorus-containing compound and the metal compound with the hydrogen type multi-level hole ZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour at the same temperature by adopting an impregnation method, or the contact is to mix and slurry the phosphorus-containing compound, the metal compound, the hydrogen type multi-level hole ZSM-5 molecular sieve and water and then keep the mixture at the temperature of 0-150 ℃ for at least 0.1 hour; or,
The second method includes: contacting a solution containing a phosphorus compound with a hydrogen type hierarchical pore ZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under external applied pressure and external water added atmosphere to obtain a phosphorus containing ZSM-5 molecular sieve, and then soaking and roasting with a solution of a metal compound; the contact is to mix and contact the aqueous solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the HZSM-5 molecular sieve with the temperature of 0-150 ℃ for at least 0.1 hour by adopting an immersion method, or the contact is to mix and pulp the phosphorus-containing compound, the hydrogen-type hierarchical pore ZSM-5 molecular sieve and water and then keep the mixture at the temperature of 0-150 ℃ for at least 0.1 hour;
the apparent pressure of the atmosphere environment is 0.01-1.0 Mpa and contains 1-100% of water vapor.
19. The method of claim 18, wherein the phosphorus-containing compound is selected from an organic phosphide and/or an inorganic phosphide.
20. The process of claim 19 wherein said organophosphorus compound is selected from the group consisting of trimethyl phosphate, triphenylphosphine, trimethyl phosphite, tetrabutyl phosphine bromide, tetrabutyl phosphine chloride, tetrabutyl phosphine hydroxide, triphenylethyl phosphine bromide, triphenylbutyl phosphine bromide, triphenylbenzyl phosphine bromide, hexamethylphosphoric triamide, dibenzyldiethylphosphoric, 1, 3-xylylene bis triethyl phosphorus; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
21. The process of claim 18 wherein the phosphorus-containing compound is in the form of hydrogen, in terms of phosphorus, and the hydrogen form of the hierarchical pore ZSM-5 molecular sieve is in the form of aluminum, in a molar ratio of from 0.01 to 2.
22. The process of claim 18 wherein the phosphorus-containing compound is in the form of hydrogen, in terms of phosphorus, and the hydrogen form of the hierarchical pore ZSM-5 molecular sieve is in the form of aluminum, in a molar ratio of from 0.1 to 1.5.
23. The process of claim 18 wherein the phosphorus-containing compound is in the form of hydrogen, in terms of phosphorus, and the hydrogen form of the hierarchical pore ZSM-5 molecular sieve is in the form of aluminum, in a molar ratio of from 0.3 to 1.3.
24. The process of claim 18 wherein the contacting is carried out at 50 to 150 ℃ for 0.5 to 40 hours with a weight ratio of water to hydrogen form of the hierarchical pore ZSM-5 molecular sieve of 0.5 to 1.
25. The method of claim 24, wherein the contacting is performed at a temperature of 70 to 130 ℃.
26. The method of claim 18, wherein the atmospheric environment has an apparent pressure of 0.1 to 0.8Mpa and contains 30% to 100% water vapor; the step of the hydrothermal roasting treatment is carried out at 200-800 ℃.
27. The method of claim 26, wherein the atmospheric environment has an apparent pressure of 0.3 to 0.6Mpa.
28. The method of claim 26 wherein said atmosphere comprises 60 to 100% water vapor.
29. The method of claim 26, wherein the step of hydrothermally calcining is performed at 300-500 ℃.
30. The method of claim 18, wherein the metal compound is selected from the group consisting of VIII, IIB, VIIB, IIIA, IVA, water soluble salts of one or more of the lanthanide metals.
31. The method of claim 30, wherein the water soluble salt is selected from the group consisting of sulfate, nitrate and chloride.
32. The method of claim 31, wherein the water soluble salt is selected from the group consisting of ferric nitrate, cobalt nitrate, nickel nitrate, manganese nitrate, potassium nitrate, zinc sulfate, tin chloride, lanthanum nitrate, and cerium chloride.
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