CN113526520B - Phosphorus modified ZSM-5 molecular sieve and preparation method thereof - Google Patents
Phosphorus modified ZSM-5 molecular sieve and preparation method thereof Download PDFInfo
- Publication number
- CN113526520B CN113526520B CN202010283413.0A CN202010283413A CN113526520B CN 113526520 B CN113526520 B CN 113526520B CN 202010283413 A CN202010283413 A CN 202010283413A CN 113526520 B CN113526520 B CN 113526520B
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- phosphorus
- ppm
- ratio
- area
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a phosphorus modified ZSM-5 molecular sieve which is characterized in that, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 1. The phosphorus modified ZSM-5 molecular sieve is obtained by performing phosphorus modification treatment on a hydrogen type ZSM-5 molecular sieve by adopting a phosphorus compound containing solution by adopting an impregnation method; the catalyst is prepared by carrying out hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water. The molecular sieve has the advantages of full coordination of phosphorus and framework aluminum, full protection of the framework aluminum, good hydrothermal and activity stability, excellent cracking conversion rate and high yield of low-carbon olefin.
Description
Technical Field
The invention relates to a modified ZSM-5 molecular sieve and a preparation method thereof, and further relates to a phosphorus modified ZSM-5 molecular sieve and a preparation method thereof.
Background
ZSM-5 molecular sieves were a widely used catalytic material developed in 1972 by Mobil corporation, USA. The ZSM-5 molecular sieve has a three-dimensional crossed pore channel structure, wherein the pore channel along the axial direction a is a straight pore, the cross section dimension of the pore channel is 0.54 multiplied by 0.56nm and is approximate to a circle, and the pore channel along the axial direction b is a Z-shaped pore, the cross section dimension of the pore channel is 0.51 multiplied by 0.56nm and is oval. The ZSM-5 molecular sieve has the pore opening composed of ten-membered rings and the size between that of the small-pore zeolite and that of the large-pore zeolite, thereby having unique shape-selective catalysis. The ZSM-5 molecular sieve has the characteristics of unique pore channel structure, good shape-selective catalysis and isomerization performance, high thermal and hydrothermal stability, high specific surface area, wide silicon-aluminum ratio variation range, unique surface acidity and lower carbon content, is widely used as a catalyst and a catalyst carrier, and is successfully used in production processes of alkylation, isomerization, disproportionation, catalytic cracking, gasoline preparation from methanol, olefin preparation from methanol and the like. The 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 sieve was applied to catalytic cracking process as an octane number promoter for catalytic cracking, aiming at improving the octane number of catalytic cracking gasoline and the selectivity of low-carbon olefin. US3758403, the first report on the use of ZSM-5 molecular sieves as active components for propylene production, together with REY as active components of FCC catalysts, and US5997728, the use of ZSM-5 molecular sieves without any modification as an aid for propylene production, however, they all disclose propylene yields that are not high. The HZSM-5 molecular sieve has good shape-selective performance and isomerization performance, but has the defects of poor hydrothermal stability, easy inactivation under harsh high-temperature hydrothermal conditions and reduced catalytic performance.
In the 80 s of the 20 th century, mobil company found that phosphorus can improve the hydrothermal stability of a ZSM-5 molecular sieve, and the phosphorus modifies the ZSM-5 molecular sieve to improve the yield of low-carbon olefin. It is conventional to contain a phosphorus activated ZSM-5 additive which selectively converts primary cracking products (e.g., gasoline olefins) to C3 and C4 olefins. After being synthesized, the ZSM-5 molecular sieve is modified by introducing a proper amount of inorganic phosphorus compound, and can stabilize framework aluminum under harsh hydrothermal conditions.
CN106994364A discloses a method for modifying a ZSM-5 molecular sieve, which comprises mixing a phosphorus-containing compound selected from one or more of phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate with a ZSM-5 molecular sieve with high alkali metal ion content to obtain a mixture containing P and P 2 O 5 At least 0.1wt% of the mixture, drying the mixture, calcining, subjecting to an ammonium exchange step and a water washing step to reduce the alkali metal ion content to below 0.10wt%, and then subjecting to drying and hydrothermal aging at 400-1000 ℃ and 100% steam. 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 a ZSM-5 molecular sieve, which comprises the steps ofThe method comprises the following steps: synthesizing → filtering → ammonium exchange → drying → roasting to obtain ZSM-5 molecular sieve, then modifying the ZSM-5 molecular sieve by phosphoric acid, and then drying and roasting to obtain the phosphorus modified HZSM-5 molecular sieve, wherein P is 2 O 5 The loading is generally in the range from 1 to 7% by weight.
Although the ZSM-5 molecular sieve is modified by adopting a proper amount of inorganic phosphide, 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 paraffin cracking and the higher selectivity of light olefins are achieved, the excessive inorganic phosphide is used for modifying the ZSM-5 molecular sieve, so that the pore channels of the molecular sieve are blocked, the pore volume and the specific surface area are reduced, and a large amount of strong B acid centers are occupied. In addition, in the prior art, phosphoric acid or ammonium phosphate salts can generate phosphorus species in different aggregation states by self-polymerization in the roasting process, phosphorus is insufficiently coordinated with framework aluminum, the utilization efficiency of phosphorus is low, and phosphorus modification does not always obtain a satisfactory hydrothermal stability improvement result. Therefore, a new technology is urgently needed to promote the coordination of phosphorus and framework aluminum, improve the hydrothermal stability of the phosphorus-modified ZSM-5 molecular sieve and further improve the cracking activity.
Disclosure of Invention
Based on a large number of experiments, the inventor finds that the phosphorus modified ZSM-5 molecular sieve obtained by treating under a certain condition and adopting pressurized hydrothermal roasting has physicochemical characteristics different from those of the conventional phosphorus-containing ZSM-5 molecular sieve, can improve the utilization efficiency of phosphorus, and improves the hydrothermal stability of the molecular sieve. Based on this, the present invention was made.
Therefore, one of the purposes of the invention is to provide a phosphorus modified ZSM-5 molecular sieve which is different from the prior art aiming at the problems of the prior art such as unsatisfactory hydrothermal stability and the like; the invention also aims to provide a preparation method of the phosphorus modified ZSM-5 molecular sieve.
In order to realize one of the purposes of the invention, the invention provides a phosphorus modified ZSM-5 molecular sieve which is characterized in that, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with the chemical shift of 39 +/-3 ppm to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is not less than1。
27 In Al MAS-NMR, a resonance signal at a chemical shift of 39. + -. 3ppm indicates a skeletal aluminum species coordinated to phosphorus (phosphorus-stabilized skeletal aluminum, i.e., distorted four-coordinate skeletal aluminum); a chemical shift of 54 ppm. + -.3 ppm of the resonance signal indicates a four-coordinate framework aluminum species. In the present invention, the first and second liquid crystal display panels, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal at a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal at a chemical shift of 54 ppm. + -.3 ppm is preferably not less than 5, more preferably not less than 10, and the most preferred ratio is 12 to 25.
In the surface XPS elemental analysis of the molecular sieve, n1/n2 is less than or equal to 0.1, wherein n1 represents the mole number of phosphorus, and n2 represents the total mole number of silicon and aluminum. Preferably, n1/n2 is 0.09 or less, more preferably, n1/n2 is 0.08 or less, and most preferably, n1/n2 is 0.04 to 0.07. The characterization parameters show that the content of surface phosphorus species in the molecular sieve is reduced, and also show that the surface phosphorus species are more migrated to the molecular sieve body phase, namely the numerical value of n1/n2 shows that the phosphorus species are dispersed on the surface of the molecular sieve and migrated from the surface of the ZSM-5 molecular sieve to the crystal, and the smaller the numerical value is, the content of the surface phosphorus species is reduced, the phosphorus species are well dispersed and migrated inwards, so that the hydrothermal stability of the molecular sieve is better.
When the phosphorus and the aluminum are both counted by mol, the content of the phosphorus in the molecular sieve 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 molecular sieve of the invention undergoes hydrothermal aging at 800 ℃ and 100% steam for 17h, and then NH 3 In a TPD (thermoplastic polymer-bound-silica) map, the proportion of the area of the strong acid center peak occupying the total acid center peak area at the desorption temperature of more than 200 ℃ is more than or equal to 40 percent, which shows that the molecular sieve has higher strong acid center retention after 17 hours of hydrothermal aging under the conditions of 800 ℃ and 100 percent of water vapor, so that the molecular sieve has higher cracking activity. Preferably, the specific gravity is 42% or more, more preferably 45% or more, and most preferably 48% to 85%.
In order to achieve the second object of the present invention, the present invention provides a method for preparing a phosphorus-modified ZSM-5 molecular sieve, the method comprising: contacting a phosphorus-containing compound solution with an HZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the HZSM-5 molecular sieve with the temperature of 0-150 ℃ are mixed and contacted for at least 0.1 hour at the basically same temperature by adopting an impregnation method, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and beaten and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01-1.0 Mpa and contains 1-100% of water vapor.
In the preparation method of the invention, the HZSM-5 molecular sieve is a microporous ZSM-5 molecular sieve for reducing sodium to Na by ammonium exchange 2 O<0.1wt% is obtained, and the silicon-aluminum ratio (the molar ratio of silicon oxide to aluminum oxide, the same applies hereinafter) is more than or equal to 10, and usually is 10 to 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 phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenyl ethyl phosphonium bromide, triphenyl butyl phosphonium bromide, triphenyl benzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium and 1, 3-xylene 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 first mode of contact is to 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 an impregnation method. 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 ℃, so as to obtain a better effect, i.e., the phosphorus species are better dispersed, the phosphorus is easier to migrate into the HZSM-5 molecular sieve crystal to be combined with the framework aluminum, the coordination degree of the phosphorus and the framework aluminum is further improved, and finally, the hydrothermal stability of the molecular sieve is improved. The substantially same temperature means that the temperature difference between the aqueous solution of the phosphorus-containing compound and the HZSM-5 molecular sieve is within +/-5 ℃. For example, the aqueous solution of the phosphorus-containing compound is heated to a temperature of 80 ℃ and the HZSM-5 molecular sieve is heated to a temperature of 75 to 85 ℃.
In the preparation method, the second mode of contact is to mix the phosphorus-containing compound, the HZSM-5 molecular sieve and water and then keep the mixture at 0-150 ℃ for at least 0.1 hour. For example, the mixture is maintained at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, preferably, in order to obtain better effect, i.e., to achieve better dispersion of phosphorus species, easier migration of phosphorus into molecular sieve crystals to bind with framework aluminum, further increase the coordination degree of phosphorus and framework aluminum, and finally improve the hydrothermal stability of the molecular sieve, the mixture of the phosphorus-containing compound, the HZSM-5 molecular sieve and water is maintained at a higher temperature range of 40 ℃ or higher for 0.1 hour, for example, a temperature range of 50 to 150 ℃, more preferably a temperature range of 70 to 130 ℃.
In the preparation method, when the phosphorus-containing compound is counted by phosphorus and the HZSM-5 molecular sieve is counted by aluminum, the molar ratio of the phosphorus-containing compound to the HZSM-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 0.2 to 1.5. The weight ratio of the water sieve to 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 environment of externally applied pressure and externally added water. The atmospheric environment is obtained by externally applying pressure and water, and preferably has a superficial pressure of 0.1 to 0.8MPa, more preferably a superficial pressure of 0.3 to 0.6MPa, preferably 30 to 100% water vapor, more preferably 60 to 100% water vapor. The external pressure is applied to the hydrothermal roasting treatment of the prepared material from the outside, and for example, the external pressure may be applied by introducing an inert gas from the outside to maintain a certain back pressure. The amount of the externally added water is based on the condition that the atmosphere contains 1-100% of water vapor. The step of hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.
The preparation method provided by the invention promotes the migration of surface phosphorus species to a ZSM-5 molecular sieve bulk phase; in the phosphorus modified ZSM-5 molecular sieve provided by the invention, phosphorus and framework aluminum are fully coordinated, the framework aluminum is fully protected, the molecular sieve has excellent hydrothermal stability, for example, the molecular sieve has higher crystallization retention after 17 hours of hydrothermal aging under the conditions of 800 ℃ and 100% of water vapor, and in n-tetradecane cracking, main indexes are improved relative to a comparison sample, for example, higher conversion rate and liquefied gas yield are improved, and meanwhile, the yield of trienes (ethylene, propylene and butylene) is greatly improved.
Drawings
FIG. 1 is a diagram of sample PSZ1-1 27 Al MAS-NMR spectrum.
FIG. 2 shows NH of sample PSZ1-1 after hydrothermal aging at 800 deg.C under 100% water vapor for 17h 3 -TPD spectrum.
FIG. 3 shows a comparative sample DBZ1-1 27 Al MAS-NMR spectrum.
FIG. 4 shows NH of a comparative sample DBZ1-1 after hydrothermal aging at 800 deg.C under 100% water vapor for 17h 3 -TPD spectrum.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
The X-ray diffraction (XRD) pattern was measured on a Japanese pharmacological TTR-3 powder X-ray diffractometer. The instrument parameters are as follows: copper target (tube voltage 40kV, tube current 250 mA), scintillation counter, step width 0.02 degree, scanning speed 0.4 (°)/min. The ZSM-5 molecular sieve synthesized by the method of example 1 in CN1056818C is taken as a standard sample, and the crystallinity of the molecular sieve is determined to be 100%. The relative crystallinity is expressed in percentage by the ratio of the sum of the peak areas of five characteristic diffraction peaks between 22.5 and 25.0 degrees in terms of 2 theta of the X-ray diffraction spectra of the obtained product and the standard sample.
27 The analysis of the Al MAS-NMR spectrum was carried out on a Bruker AVANCE model III 600 WB spectrometer. The instrument parameters are as follows: the diameter of the rotor is 4mm, the resonance frequency spectrum is 156.4MHz, the pulse width is 0.4 mus (corresponding to 15 DEG pulling chamfer angle), the magic angle rotation speed is 12kHz, and the delay time is 1s. 27 The characteristic peak 1 at 54 +/-3 pp m of the Al MAS-NMR spectrum is assigned to fourCoordination framework aluminum, characteristic peak 2 at 39 ± 3ppm was assigned to phosphorus-stabilized framework aluminum (distorted four-coordination framework aluminum). And each peak area is calculated by adopting an integration method after peak-splitting fitting is carried out on the characteristic peak.
X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of molecular sieves and to examine the migration of phosphorus compounds, using an ESCALB 250 type X-ray photoelectron spectrometer from Thermo Fisher-VG. The instrument parameters are as follows: the excitation source was a monochromatized AlK α X-ray at 150W power, with the charge shift corrected for the C1s peak (284.8 eV) from the contaminating carbon.
Temperature programmed desorption analysis (NH) 3 TPD) characterization using an AutoChen II temperature programmed adsorption apparatus from Micromeritics. Weighing 0.1-0.2 g of sample, putting the sample into a quartz adsorption tube, introducing carrier gas (high purity He. Flow rate is 50 mL/min), raising the temperature to 600 ℃ at the rate of 20 ℃/min, keeping the temperature for 2h, and removing water and air adsorbed on the sample; reducing the temperature to 100 ℃ at the speed of 20 ℃/min, and keeping the temperature for 30min; switching the carrier gas to NH 3 Keeping the temperature for 30min by using-He mixed gas to ensure that the sample is saturated by absorbing ammonia; reacting NH 3 The mixed gas of the-He and the ammonia is switched into high-purity He carrier gas, and the mixed gas is purged for 1h to desorb the ammonia through material resources; then the temperature is raised to 600 ℃ at the speed of 10 ℃/min, and a temperature programmed desorption curve is obtained. The desorbed ammonia is detected by a thermal conductivity cell. Converting the temperature programmed desorption curve into NH 3 After the desorption rate-temperature curve, the acid center density data is obtained by spectrum resolution of the peak pattern.
Examples 1 to 1
Examples 1-1 illustrate the phosphorus modified ZSM-5 molecular sieve and process of the present invention.
Dissolving 16.2g diammonium hydrogen phosphate (analytically pure, the same below) in 60g deionized water, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 113g HZSM-5 molecular sieve (provided by Qilu division, petrochemical catalyst, china) with a relative crystallinity of 91.1% and a silica/alumina molar ratio of 24.1, adding sodium hydroxide (Na) to the solution, and mixing the solution with sodium hydroxide (Na) to obtain a mixed solution 2 O content of 0.039 wt% and specific surface area of 353m 2 Per g, total pore volume of 0.177ml/g, the same applies below), modified by immersion, immersed for 2 hours at 20 deg.C, dried in an oven at 110 deg.C, externally pressurized and added with water, at 500 deg.C, 0.5MPa, 50%And (3) treating for 0.5h in a steam atmosphere to obtain a phosphorus modified ZSM-5 molecular sieve sample, and marking as PSZ1-1.
Examples 1 to 2
Examples 1-2 illustrate phosphorus modified ZSM-5 molecular sieves and methods of the invention.
The process is the same as the process of the example 1-1, except that diammonium phosphate, HZSM-5 molecular sieve and water are mixed and beaten into slurry, and the temperature is raised to 100 ℃ and kept for 2 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample is marked as PSZ1-2.
Comparative examples 1 to 1
Comparative examples 1-1 illustrate the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as in example 1-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as DBZ1-1.
Comparative examples 1 to 2
Comparative examples 1-2 illustrate comparative samples of phosphorus modified ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination.
The same as in example 1-1 except that the firing conditions were atmospheric pressure (apparent pressure: 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was designated DBZ1-2.
XRD crystallinity of PSZ1-1, PSZ1-2, DBZ1-1 and DBZ1-2 before and after being respectively treated with 100 percent of water vapor and 17h of hydrothermal aging at 800 ℃ is shown in a table 1-1.
Of PSZ1-1 and DBZ1-1 27 The Al MAS-NMR spectra are shown in FIGS. 1 and 3, respectively, for PSZ1-2 and DBZ1-2 27 The Al MAS-NMR spectrum is characterized by 1 and 3, respectively, in which the chemical shift is ascribed to the four-coordinate framework aluminum at 54ppm and the chemical shift is ascribed to the four-coordinate framework aluminum in which phosphorus is bonded to aluminum (phosphorus-stabilized framework aluminum) at 39 ppm. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in the table 1-2.
The surface XPS elemental analysis data for PSZ1-1, PSZ1-2, DBZ1-1, and DBZ1-2 are shown in tables 1-3.
NH of PSZ1-1 subjected to hydrothermal aging for 17 hours under the conditions of 800 ℃ and 100% of water vapor 3 The TPD spectrum is shown in FIG. 2. Comparative sample DBZ1-1 was subjected to 800 deg.CNH after 17h of hydrothermal aging under the condition of 100% of water vapor 3 The TPD spectrum is shown in FIG. 4. NH of PSZ1-1, PSZ1-2, DBZ1-1, DBZ1-2 3 In a TPD (temperature dependent gas detector) graph, specific gravity data of the area of the strong acid center peak occupying the total acid center peak area at the desorption temperature of more than 200 ℃ are shown in tables 1 to 4.
PSZ-1, PSZ1-2, DBZ1-1 and DBZ1-2 are subjected to n-tetradecane hydrocarbon cracking evaluation, and the micro-inverse evaluation conditions are as follows: the molecular sieve loading is 2g, 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 below). The evaluation data are shown in tables 1 to 5.
TABLE 1-1
As can be seen from the table 1-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystallization retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystallization retention is obviously higher than that of a comparison sample, and the crystallization retention is at least improved by 5 percent.
Tables 1 to 2
Tables 1 to 3
Tables 1 to 4
Tables 1 to 5
| PSZ1-1 | PSZ1-2 | DBZ1-1 | DBZ1-2 | |
| Material balance/m% | ||||
| Dry gas | 3.6 | 3.4 | 4.2 | 3.8 |
| Liquefied gas | 34.1 | 36.5 | 31.5 | 32.9 |
| Gasoline (R) and its preparation method | 32.9 | 31.5 | 34.1 | 35.1 |
| Diesel oil | 26.2 | 27.6 | 27.8 | 25.8 |
| M% of main product in the cracked gas | ||||
| Ethylene (CO) process | 2.9 | 2.9 | 2.6 | 2.9 |
| Propylene (PA) | 13.6 | 14.3 | 11.2 | 12.2 |
| Total butene | 7.6 | 7.7 | 5.6 | 6.5 |
| Conversion/m% | 70.4 | 73.6 | 66.8 | 68.9 |
Example 2-1
Example 2-1 illustrates the phosphorus modified ZSM-5 molecular sieve and process of the present invention.
Dissolving 16.2g of diammonium phosphate in 120g of deionized water at 50 ℃, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting a dipping method, dipping for 2h at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 2h at 600 ℃, 0.5Mpa and 30% steam atmosphere to obtain a phosphorus-modified ZSM-5 molecular sieve sample, wherein the sample is marked as PSZ-2.
Examples 2 to 2
Examples 2-2 illustrate the phosphorus modified ZSM-5 molecular sieves and methods of the present invention.
The method is the same as the method of the material preparation, the proportioning, the drying and the roasting in the embodiment 2-1, and is characterized in that diammonium phosphate, HZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 70 ℃ and kept for 2 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated as PSZ2-2.
Comparative example 2 to 1
Comparative example 2-1 illustrates the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as in example 2-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as DBZ-2-1.
Comparative examples 2 to 2
Comparative example 2-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The same as in example 2-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was designated DBZ-2-2.
The XRD crystallinity of PSZ2-1, PSZ2-2, DBZ-2-1 and DBZ-2-2 before and after the treatment of 800 ℃ with 100% water vapor and 17h hydrothermal aging is shown in Table 2-1.
Of PSZ1-2 and PSZ2-2 27 The MAS-NMR spectrum of Al has the characteristics of FIG. 1, of DBZ2-1 and DBZ2-2 27 Al MASThe NMR spectrum is characteristic of FIG. 3. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in the table 2-2.
The surface XPS elemental analysis data of PSZ2-1, PSZ2-2, DBZ2-1, DBZ2-2 are shown in Table 2-3, NH 3 The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ in the TPD spectrum are shown in tables 2 to 4.
PSZ2-1, PSZ2-2, DBZ2-1 and DBZ2-2 were evaluated for cracking of n-tetradecane, and the evaluation data are shown in tables 2 to 5.
TABLE 2-1
As can be seen from the table 2-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 4 percentage points.
Tables 2 to 2
Tables 2 to 3
Tables 2 to 4
Tables 2 to 5
| PSZ2-1 | PSZ2-2 | DBZ2-1 | DBZ2-2 | |
| Material balance/m% | ||||
| Dry gas | 3.5 | 3.1 | 4.3 | 3.8 |
| Liquefied gas | 36.5 | 37.5 | 30.0 | 33.0 |
| Gasoline (gasoline) | 31.1 | 30.7 | 34.8 | 35.4 |
| Diesel oil | 24.7 | 23.8 | 27.5 | 25.9 |
| M% of main product in cracked gas | ||||
| Ethylene | 2.7 | 2.9 | 2.3 | 2.7 |
| Propylene polymer | 13.2 | 14.0 | 10.2 | 12.0 |
| Total butenes | 9.2 | 9.7 | 5.2 | 6.4 |
| Conversion/m% | 70.0 | 74.3 | 66.0 | 67.3 |
Example 3-1
Example 3-1 illustrates the phosphorus-modified ZSM-5 molecular sieves and methods of the invention
Dissolving 10.4g of phosphoric acid in 60g of deionized water at normal temperature, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 4 hours at 20 ℃, drying in an oven at 110 ℃, externally applying pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 400 ℃, 0.3Mpa and 100% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ3-1.
Example 3-2
Example 3-2 illustrates the phosphorus modified ZSM-5 molecular sieve and method of the present invention.
The procedure of the preparation, proportioning, drying and calcination of the same materials as in example 3-1 was repeated except that the aqueous solution of the phosphorus-containing compound at 80 ℃ was mixed with the HZSM-5 molecular sieve heated to 80 ℃ and contacted for 4 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated as PSZ3-2.
Comparative example 3-1
Comparative example 3-1 illustrates the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as in example 3-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as DBZ3-1.
Comparative examples 3 and 2
Comparative example 3-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.
The same as in example 3-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). And obtaining a phosphorus modified ZSM-5 molecular sieve comparison sample, and marking the sample as DBZ3-2.
XRD crystallinity of PSZ3-1, PSZ3-2, DBZ3-1 and DBZ3-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 3-1.
Of PSZ-3 and PSZ3-2 27 The MAS-NMR spectra of Al have the features of FIG. 1, DBZ3-1 and DBZ3-2, respectively 27 The MAS-NMR spectrum of Al is the same as that of FIG. 3. 27 Peak area ratio of Al MAS-NMR spectrumThe data are shown in Table 3-2.
The surface XPS elemental analysis data of PSZ3-1, PSZ3-2, DBZ3-1, DBZ3-2 are shown in Table 3-3, NH 3 The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at desorption temperatures above 200 ℃ in the TPD spectrum are shown in tables 3-4.
PSZ3-1, PSZ3-2, DBZ3-1 and DBZ3-2 were evaluated for cracking of n-tetradecane, and the evaluation data are shown in tables 3-5.
TABLE 3-1
As can be seen from the table 3-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystallization retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystallization retention is obviously higher than that of a comparison sample, and the crystallization retention is at least improved by 10 percent.
TABLE 3-2
Tables 3 to 3
Tables 3 to 4
Tables 3 to 5
| PSZ3-1 | PSZ3-2 | DBZ3-1 | DBZ3-2 | |
| Material balance/m% | ||||
| Dry gas | 4.1 | 3.9 | 3.9 | 3.7 |
| Liquefied gas | 42.4 | 43.0 | 31.8 | 34.1 |
| Gasoline (R) and its preparation method | 27.1 | 26.4 | 32.8 | 33.2 |
| Diesel oil | 24.7 | 23.6 | 27.9 | 25.6 |
| M% of main product in cracked gas | ||||
| Ethylene (CO) process | 3.5 | 3.4 | 2.7 | 2.9 |
| Propylene polymer | 15.7 | 16.3 | 11.4 | 12.8 |
| Total butenes | 12.2 | 13.0 | 6.1 | 7.7 |
| Conversion/m% | 72.7 | 75.0 | 64.8 | 65.9 |
Example 4-1
Example 4-1 illustrates the phosphorus modified ZSM-5 molecular sieve and process of the present invention.
Dissolving 8.1g of diammonium phosphate in 120g of deionized water at normal temperature, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating at 20 ℃ for 2 hours, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment at 300 ℃, 0.4Mpa and 100% steam atmosphere for 2h to obtain a phosphorus-modified ZSM-5 molecular sieve sample, wherein the sample is marked as PSZ4-1.
Example 4 to 2
Example 4-2 illustrates the phosphorus modified ZSM-5 molecular sieve and process of the present invention.
The procedure of the same materials, mixing, drying and calcining as in example 4-1 is different in that ammonium dihydrogen phosphate, HZSM-5 molecular sieve and water are mixed and made into slurry, and then the temperature is raised to 90 ℃ and kept for 2 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated as PSZ4-2.
Comparative example 4-1
Comparative example 4-1 illustrates the prior art process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as in example 4-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The comparative sample of phosphorus modified ZSM-5 molecular sieve obtained was designated DBZ4-1.
Comparative examples 4 to 2
Comparative example 4-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.
The same as in example 4-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of phosphorus modified ZSM-5 molecular sieve was obtained and was designated DBZ4-2.
XRD crystallinity of PSZ4-1, PSZ4-2, DBZ4-1 and DBZ4-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 4-1.
Of PSZ4-1 and PSZ4-2 27 The MAS-NMR spectra of Al have the features of FIG. 1, of DBZ-4-1 and DBZ-4-2, respectively 27 The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 4-2.
The surface XPS elemental analysis data of PSZ4-1, PSZ4-2, DBZ4-1, DBZ4-2 are shown in Table 4-3, NH 3 The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ in the TPD spectrum are shown in the table 4-4.
PSZ4-1, PSZ4-2, DBZ4-1 and DBZ4-2 were evaluated for cracking of n-tetradecane, and the evaluation data are shown in tables 4-5.
TABLE 4-1
As can be seen from the table 4-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystallization retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystallization retention is obviously higher than that of a comparison sample, and the crystallization retention is at least improved by 15 percent.
TABLE 4-2
Tables 4 to 3
Tables 4 to 4
Tables 4 to 5
| PSZ4-1 | PSZ4-2 | DBZ4-1 | DBZ4-2 | |
| Material balance/m% | ||||
| Dry gas | 5.3 | 3.9 | 3.5 | 4.3 |
| Liquefied gas | 46.7 | 49.0 | 26.8 | 25.7 |
| Gasoline (gasoline) | 27.7 | 26.5 | 34.3 | 34.8 |
| Diesel oil | 18.6 | 17.3 | 25.4 | 29.3 |
| M% of main product in cracked gas | ||||
| Ethylene | 4.7 | 4.5 | 2.5 | 3.1 |
| Propylene polymer | 16.3 | 16.9 | 10.2 | 9.5 |
| Total butene | 12.1 | 12.4 | 6.3 | 5.2 |
| Conversion/m% | 80.7 | 84.9 | 65.7 | 65.0 |
Example 5-1
Example 5-1 illustrates a phosphorus modified ZSM-5 molecular sieve and process of the invention.
Dissolving 8.5g of trimethyl phosphate in 80g of deionized water at 90 ℃, stirring for 1h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 8h at 20 ℃, drying in an oven at 110 ℃, externally applying pressure and adding water, and carrying out pressurized hydrothermal roasting treatment for 4h at 500 ℃, 0.8Mpa and 80% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ5-1.
Example 5-2
Example 5-2 illustrates the phosphorus modified ZSM-5 molecular sieve and process of the present invention.
The procedure of the same materials, mixing ratios, drying and calcination as in example 5-1 was repeated except that trimethyl phosphate, HZSM-5 molecular sieve and water were mixed and slurried, and the temperature was raised to 120 ℃ and maintained for 8 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated as PSZ5-2.
Comparative example 5-1
Comparative example 5-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as example 5-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as DBZ5-1.
Comparative examples 5 and 2
Comparative example 5-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by hydrothermal calcination at atmospheric pressure.
The same as in example 5-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). And obtaining a phosphorus modified ZSM-5 molecular sieve comparison sample, and marking the sample as DBZ5-2.
XRD crystallinity of PSZ5-1, PSZ5-2, DBZ5-1 and DBZ5-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 5-1.
Of PSZ5-1 and PSZ5-2 27 The MAS-NMR spectrum of Al has the characteristics of FIG. 1, of DBZ5-1 and DBZ5-2 27 The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 5-2.
Surface XPS elemental analysis data of PSZ5-1, PSZ5-2, DBZ5-1, and DBZ5-2See tables 5-3, NH 3 The specific gravity data of the area of the strong acid central peak occupying the total acid central peak area at desorption temperatures above 200 ℃ in the TPD spectrum are shown in tables 5-4.
PSZ5-1, PSZ5-2, DBZ-5-1 and DBZ-5-2 were evaluated for cracking of n-tetradecane, and the evaluation data are shown in tables 5 to 5.
TABLE 5-1
As can be seen from Table 5-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystal retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystal retention is obviously higher than that of a contrast sample, and the crystal retention is improved by at least 5 percent.
TABLE 5-2
Tables 5 to 3
Tables 5 to 4
Tables 5 to 5
| PSZ5-1 | PSZ5-2 | DBZ5-1 | DBZ5-2 | |
| Material balance/m% | ||||
| Dry gas | 3.5 | 3.5 | 4.3 | 3.5 |
| Liquefied gas | 36.6 | 36.9 | 23.8 | 25.3 |
| Gasoline (gasoline) | 30.2 | 30.0 | 37.2 | 33.2 |
| Diesel oil | 27.9 | 26.9 | 28.5 | 26.1 |
| M% of main product in the cracked gas | ||||
| Ethylene | 2.7 | 2.7 | 3.3 | 2.5 |
| Propylene polymer | 13.4 | 14.0 | 9.0 | 10.0 |
| Total butene | 10.1 | 10.7 | 5.8 | 6.1 |
| Conversion/m% | 68.0 | 68.7 | 63.2 | 65.1 |
Example 6-1
Example 6-2 illustrates a phosphorus modified ZSM-5 molecular sieve and method of the present invention.
Dissolving 11.6g of boron phosphate in 100g of deionized water at 100 ℃, stirring for 3h to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 2h at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 4h at 400 ℃, 0.3Mpa and 100% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ6-1.
Example 6-2
Example 6-2 illustrates the phosphorus modified ZSM-5 molecular sieve and process of the present invention.
The procedure of the same materials, mixing, drying and calcining as in example 6-1 is different in that boron phosphate, HZSM-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 obtained phosphorus modified ZSM-5 molecular sieve sample was designated as PSZ6-2.
Comparative example 6-1
Comparative example 6-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as in example 6-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The obtained comparative sample of the phosphorus-modified ZSM-5 molecular sieve is marked as DBZ6-1.
Comparative examples 6 to 2
Comparative example 6-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The same as in example 6-1 except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). And obtaining a phosphorus modified ZSM-5 molecular sieve comparison sample, and recording the sample as DBZ6-2.
XRD crystallinity of PSZ6-1, PSZ6-2, DBZ6-1 and DBZ6-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 6-1.
Of PSZ6-1 and PSZ6-2 27 The MAS-NMR spectrum of Al has the characteristics of FIG. 1, of DBZ-6-1 and DBZ6-2 27 The Al MAS-NMR spectrum is characterized by the same features as in FIG. 3. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 6-2.
The surface XPS elemental analysis data of PSZ6-1, PSZ6-2, DBZ6-1, DBZ6-2 are shown in Table 6-3, NH 3 Strong acid with desorption temperature above 200 ℃ in TPD patternThe ratio of the central peak area to the total acid central peak area is shown in Table 6-4.
PSZ6-1, PSZ6-2, DBZ6-1 and DBZ6-2 were evaluated for cracking of n-tetradecane, and the evaluation data are shown in tables 6-5.
TABLE 6-1
As can be seen from the table 6-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystallization retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystallization retention is obviously higher than that of a comparison sample, and the crystallization retention is at least improved by 10 percent.
TABLE 6-2
Tables 6 to 3
Tables 6 to 4
Tables 6 to 5
| PSZ6-1 | PSZ6-2 | DBZ6-1 | DBZ6-2 | |
| Material balance/m% | ||||
| Dry gas | 4.2 | 4.0 | 2.8 | 3.9 |
| Liquefied gas | 41.4 | 41.9 | 27.8 | 29.8 |
| Gasoline (R) and its preparation method | 30.6 | 30.3 | 29.7 | 28.9 |
| Diesel oil | 22.0 | 21.9 | 36.6 | 34.2 |
| M% of main product in cracked gas | ||||
| Ethylene (CO) process | 3.4 | 3.5 | 2.0 | 3.2 |
| Propylene polymer | 15.1 | 15.4 | 11.7 | 12.8 |
| Total butene | 10.8 | 10.7 | 6.7 | 6.5 |
| Conversion/m% | 73.9 | 77.1 | 59.3 | 60.1 |
Example 7-1
Dissolving 14.2g of triphenyl phosphorus in 80g of deionized water at 100 ℃, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding 113g of HZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 4 hours at 20 ℃, drying in an oven at 110 ℃, applying pressure to the outside, adding water, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 600 ℃, 1.0Mpa and 30% of steam atmosphere to obtain the phosphorus-modified ZSM-5 molecular sieve, wherein the mark is PSZ7-1.
Example 7-2
Example 7-2 illustrates a phosphorus modified ZSM-5 molecular sieve and method of the present invention.
The same materials, proportioning, drying and calcining as in example 7-1, except that the aqueous solution of the phosphorus compound at 80 ℃ was mixed and contacted with the HZSM-5 molecular sieve heated to 80 ℃ for 4 hours. The obtained phosphorus modified ZSM-5 molecular sieve sample was designated as PSZ7-2.
Comparative example 7-1
Comparative example 7-1 illustrates the current industry conventional process and the resulting phosphorus modified ZSM-5 comparative sample.
The same as example 7-1 except that the firing conditions after impregnation and drying were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃. The comparative sample of phosphorus modified ZSM-5 molecular sieve obtained was designated DBZ7-1.
Comparative examples 7 and 2
Comparative example 7-2 illustrates a comparative sample of phosphorus modified ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The same as example 7-1, except that the firing conditions after impregnation and drying were atmospheric pressure (apparent pressure 0 MPa). And obtaining a phosphorus modified ZSM-5 molecular sieve comparison sample, and recording the sample as DBZ7-2.
XRD crystallinity of PSZ7-1, PSZ7-2, DBZ7-1 and DBZ7-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h is shown in Table 7-1.
PSZ-7 and PSZ7-2, respectively 27 The MAS-NMR spectrum of Al has the characteristics of FIG. 1, of DBZ7-1 and DBZ7-2 27 The MAS-NMR spectrum of Al is the same as that of FIG. 3. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 7-2.
The surface XPS elemental analysis data of PSZ7-1, PSZ7-2, DBZ7-1, and DBZ7-2 are shown in Table 7-3, NH of PSZ7-1, PSZ7-2, DBZ7-1, and DBZ7-2 3 In a TPD (temperature dependent gas detector) graph, the proportion of the strong acid center peak area to the total acid center peak area at the desorption temperature of more than 200 ℃ is shown in a table 7-4.
PSZ7-1, PSZ7-2, DBZ7-1 and DBZ7-2 were evaluated for n-tetradecane cracking, and the evaluation data are shown in tables 7 to 5.
TABLE 7-1
As can be seen from the table 7-1, the phosphorus-modified ZSM-5 molecular sieve prepared by the method still has higher crystallization retention after being subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the crystallization retention is obviously higher than that of a comparison sample, and the crystallization retention is at least improved by 8 percent.
TABLE 7-2
Tables 7 to 3
Tables 7 to 4
Tables 7 to 5
| PSZ7-1 | PSZ7-2 | DBZ7-1 | DBZ7-2 | |
| Material balance/m% | ||||
| Dry gas | 4.4 | 4.2 | 3.4 | 4.2 |
| Liquefied gas | 35.1 | 35.7 | 28.7 | 31.7 |
| Gasoline (gasoline) | 33.6 | 32.6 | 31.3 | 30.9 |
| Diesel oil | 25.0 | 24.9 | 33.9 | 31.4 |
| M% of main product in the cracked gas | ||||
| Ethylene (CO) process | 3.4 | 3.3 | 2.7 | 4.2 |
| Propylene (PA) | 13.8 | 14.0 | 12.0 | 13.0 |
| Total butenes | 7.4 | 7.9 | 6.3 | 7.1 |
| Conversion/m% | 74.3 | 75.2 | 61.3 | 62.5 |
The preferred embodiments of the present disclosure are described in detail above with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details in the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of the various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present invention, as long as the combination does not depart from the spirit of the present disclosure.
Claims (26)
1. A phosphorus modified ZSM-5 molecular sieve is characterized in that, 27 in Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 1.
2. The molecular sieve of claim 1 wherein said 27 In Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 5.
3. A molecular sieve according to claim 1 wherein said 27 In Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is not less than 10.
4. The molecular sieve of claim 1 wherein said 27 In the Al MAS-NMR, the ratio of the peak area of the resonance signal with a chemical shift of 39. + -.3 ppm to the peak area of the resonance signal with a chemical shift of 54 ppm. + -.3 ppm is 12 to 25.
5. The molecular sieve of claim 1, wherein n1/n2 is 0.1 or less in surface XPS elemental analysis, wherein n1 represents the number of moles of phosphorus and n2 represents the total number of moles of silicon and aluminum.
6. A molecular sieve according to claim 5 wherein said n1/n2 is 0.09 or less.
7. A molecular sieve according to claim 6 wherein said n1/n2 is 0.08 or less.
8. The molecular sieve of claim 7 wherein said n1/n2 is from 0.04 to 0.07.
9. The molecular sieve of claim 1, wherein the molecular sieve has NH after 17 hours of hydrothermal aging at 800 ℃ under 100% steam conditions 3 In a TPD (temperature-dependent gas pressure detector) spectrum, the proportion of the area of the strong acid central peak to the area of the total acid central peak at the desorption temperature of more than 200 ℃ is more than or equal to 40 percent.
10. The molecular sieve of claim 9, wherein the desorption temperature is above 200 ℃, the ratio of the area of the strong acid central peak to the area of the total acid central peak is not less than 42%.
11. The molecular sieve of claim 10 wherein the desorption temperature is above 200 ℃ and the proportion of the area of the strong acid central peak to the area of the total acid central peak is not less than 45%.
12. The molecular sieve of claim 11, wherein the desorption temperature is above 200 ℃ and the ratio of the area of the strong acid central peak to the area of the total acid central peak is from 48% to 85%.
13. A molecular sieve according to claim 1 wherein the ratio of phosphorus to aluminum, when both are in molar terms, is from 0.01 to 2.
14. The molecular sieve of claim 13, wherein the ratio of phosphorus to aluminum is 0.1 to 1.5, on a molar basis.
15. A molecular sieve according to claim 14, wherein the ratio of phosphorus to aluminum, when both are in moles, is from 0.2 to 1.5.
16. The preparation method of the phosphorus modified ZSM-5 molecular sieve is characterized by comprising the following steps: contacting a phosphorus-containing compound solution with an HZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the HZSM-5 molecular sieve with the temperature of 0-150 ℃ are mixed and contacted for at least 0.1 hour at the basically same temperature by adopting an impregnation method, or the contact is that the phosphorus-containing compound, the HZSM-5 molecular sieve and water are mixed and beaten and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01-1.0 Mpa and contains 1-100% of water vapor.
17. The method according to claim 16, wherein the phosphorus-containing compound is selected from an organic phosphide and/or an inorganic phosphide.
18. The process according to claim 17, wherein the organic phosphorus compound is selected from the group consisting of trimethyl phosphate, triphenyl phosphorus, trimethyl phosphite, tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium hydroxide, triphenylethyl phosphonium bromide, triphenylbutyl phosphonium bromide, triphenylbenzyl phosphonium bromide, hexamethyl phosphoric triamide, dibenzyl diethyl phosphonium, 1, 3-xylene bis triethyl phosphonium, and the inorganic phosphorus compound is selected from the group consisting of phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, boron phosphate.
19. The method according to claim 16, wherein said HZSM-5 molecular sieve contains Na 2 O<0.1wt％。
20. The process according to claim 16, wherein the molar ratio of the phosphorus-containing compound to the HZSM-5 molecular sieve is 0.01 to 2.
21. The process according to claim 20, wherein the molar ratio of the phosphorus-containing compound calculated as phosphorus to the molecular sieve HZSM-5 calculated as aluminum is 0.1 to 1.5.
22. The process according to claim 21, wherein the molar ratio of the phosphorus-containing compound calculated as phosphorus to the molecular sieve HZSM-5 calculated as aluminum is 0.2 to 1.5.
23. The method of claim 16, wherein the contacting is performed at 50 to 150 ℃ for 0.5 to 40 hours with a water sieve weight ratio of 0.5 to 1.
24. The method of claim 23, wherein said contacting is carried out at a temperature of 70 to 130 ℃.
25. The method of claim 16, wherein said atmosphere has an apparent pressure of 0.1 to 0.8Mpa and contains 30 to 100% of water vapor; the hydrothermal roasting treatment is carried out at 200-800 ℃.
26. The method of claim 25, wherein said atmosphere has an apparent pressure of 0.3 to 0.6Mpa and contains 60 to 100% water vapor; the hydrothermal roasting treatment is carried out at 300-500 ℃.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010283413.0A CN113526520B (en) | 2020-04-13 | 2020-04-13 | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
| TW110113299A TW202146336A (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| JP2022562488A JP2023523559A (en) | 2020-04-13 | 2021-04-13 | Phosphorus-Containing/Phosphorus-Modified ZSM-5 Molecular Sieves, Cracking Aids and Cracking Catalysts Containing The Same, Methods Of Making The Same, And Methods Of Using The Same |
| US17/996,178 US20230202851A1 (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, cracking auxiliary and cracking catalyst containing the same, process of preparing the same, and use thereof |
| PCT/CN2021/086821 WO2021208884A1 (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| EP21788139.0A EP4137456A1 (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof |
| KR1020227039663A KR20230002699A (en) | 2020-04-13 | 2021-04-13 | Phosphorus-containing/phosphorus-modified ZSM-5 molecular sieve, thermal decomposition additive and thermal decomposition catalyst including the same, manufacturing method thereof and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010283413.0A CN113526520B (en) | 2020-04-13 | 2020-04-13 | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113526520A CN113526520A (en) | 2021-10-22 |
| CN113526520B true CN113526520B (en) | 2023-01-13 |
Family
ID=78087800
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010283413.0A Active CN113526520B (en) | 2020-04-13 | 2020-04-13 | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113526520B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116917234A (en) * | 2021-01-11 | 2023-10-20 | 中国石油化工股份有限公司 | Catalytic cracking agent of phosphorus-containing modified molecular sieve, preparation method and preparation system thereof, and application of catalytic cracking agent |
| CN115445571B (en) * | 2022-08-19 | 2024-01-05 | 瑞声光电科技(常州)有限公司 | Molecular sieve sound absorbing material, preparation method thereof and loudspeaker |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042229A (en) * | 1983-07-15 | 1985-03-06 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of aluminosilicate having zeolite structure |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7060864B2 (en) * | 2003-09-30 | 2006-06-13 | Saudi Basic Industries Corporation | Toluene methylation process |
| CN1915821A (en) * | 2006-09-06 | 2007-02-21 | 北京盛大京泰化学研究所 | Method for preparing phosphor modified ZSM-5 sieve |
| CN101428232B (en) * | 2007-11-08 | 2011-11-30 | 石大卓越科技股份有限公司 | Process for producing ZSM-5 molecular sieve |
| CN104998681B (en) * | 2014-04-24 | 2018-02-23 | 中国石油化工股份有限公司 | A kind of assistant for calalytic cracking for improving low-carbon olefin concentration and preparation method thereof |
| CN106395853A (en) * | 2015-07-27 | 2017-02-15 | 中国石油化工股份有限公司 | Phosphorus-containing ZSM-5 molecular sieve, preparation method and applications thereof |
| CN106607081B (en) * | 2015-10-21 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of organic phosphorus compound modified zsm-5 zeolite |
| CN106994364B (en) * | 2016-01-25 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of method of phosphorous modified ZSM-5 molecular sieve |
| CN108439428B (en) * | 2018-03-30 | 2019-11-08 | 山东多友科技有限公司 | A kind of multi-stage porous ZSM-5 molecular sieve of P Modification and preparation method thereof |
-
2020
- 2020-04-13 CN CN202010283413.0A patent/CN113526520B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6042229A (en) * | 1983-07-15 | 1985-03-06 | ヘキスト・アクチエンゲゼルシヤフト | Manufacture of aluminosilicate having zeolite structure |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113526520A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112657547B (en) | Method for preparing low-carbon olefin by using phosphorus-containing hierarchical pore ZSM-5/Y composite molecular sieve | |
| CN108726535B (en) | Preparation method of phosphorus modified ZSM-5 molecular sieve with hierarchical pores | |
| CN113526520B (en) | Phosphorus modified ZSM-5 molecular sieve and preparation method thereof | |
| CN107971003B (en) | Catalytic cracking auxiliary agent containing phosphorus-containing and metal-loaded Beta molecular sieve and preparation method thereof | |
| CN113526519B (en) | Phosphorus-containing hierarchical pore ZSM-5 molecular sieve and preparation method thereof | |
| CN113526522B (en) | Phosphorus modified MFI structure molecular sieve and preparation method thereof | |
| CN111068752B (en) | MFI structure molecular sieve rich in mesopores and preparation method thereof | |
| CN114471676B (en) | Cracking auxiliary agent | |
| CN114715911B (en) | Multistage hole ZSM-5 molecular sieve containing phosphorus and metal and preparation method thereof | |
| CN111068758B (en) | Mesoporous-rich phosphorus-and-rare earth-containing MFI structure molecular sieve and preparation method thereof | |
| WO2022148471A1 (en) | Catalytic cracking agent containing phosphorus modified molecular sieve, and preparation method therefor, preparation system thereof and use thereof | |
| CN113526521B (en) | Molecular sieve composite of phosphorus modified ZSM-5 and Y | |
| CN114505093B (en) | Catalytic cracking auxiliary agent and preparation method and application thereof | |
| CN114715910B (en) | Phosphorus and metal modified ZSM-5 molecular sieve and preparation method thereof | |
| CN114762836A (en) | Preparation method and preparation system of catalytic cracking catalyst containing phosphorus-modified MFI structure molecular sieve | |
| CN114425430B (en) | Catalytic cracking catalyst | |
| CN114749208B (en) | Catalytic cracking catalyst | |
| CN114713277A (en) | Modified silicon-aluminum molecular sieve with MFI structure and preparation method thereof | |
| WO2021208885A1 (en) | Phosphorus-modified mfi-structured molecular sieve, catalytic cracking auxiliary agent and catalytic cracking catalyst containing phosphorus-modified mfi-structured molecular sieve, and preparation method therefor | |
| CN111056562B (en) | SAPO-34 molecular sieve, synthetic method and application thereof, and method for preparing olefin from methanol | |
| CN114425432B (en) | Cracking catalyst, preparation method and application | |
| EP0133591B1 (en) | Process for the preparation of an aromatic hydrocarbon mixture | |
| CN114505092B (en) | Catalytic cracking auxiliary agent, preparation method and hydrocarbon oil catalytic cracking method | |
| WO2021208884A1 (en) | Phosphorus-containing/phosphorus-modified zsm-5 molecular sieve, pyrolysis additive and pyrolysis catalyst containing same, preparation method therefor and application thereof | |
| CN114762831A (en) | Preparation method and preparation system of catalytic cracking auxiliary agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |