CN113526519B - Phosphorus-containing hierarchical pore ZSM-5 molecular sieve and preparation method thereof - Google Patents
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Abstract
The invention discloses a phosphorus-containing hierarchical pore ZSM-5 molecular sieve 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 17h of hydrothermal aging at 800 ℃ under the condition of 100 percent of water vapor 3 In a TPD (thermoplastic vulcanizate) pattern, the proportion of the area of the strong acid center peak occupying the area of the total acid center peak at the desorption temperature of more than 200 ℃ is more than or equal to 45 percent, and the TPD pattern has higher strong acid center retention. The molecular sieve can increase the yield of low-carbon olefin in the high-yield liquefied gas and produce high-added-value products.
Description
Technical Field
The invention relates to a phosphorus-containing ZSM-5 molecular sieve and a preparation method thereof, in particular to a phosphorus-containing hierarchical pore 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 of America. The ZSM-5 molecular sieve has a three-dimensional crossed pore channel structure, 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 approximately circular, 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, which first reported the use of ZSM-5 molecular sieves as the active component for propylene production, along with REY as the active component of FCC catalysts, and US5997728, which disclosed the use of ZSM-5 molecular sieves without any modification as an aid for propylene production, however, they all disclosed that propylene yield was 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 the ZSM-5 molecular sieve, and meanwhile, 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 ZSM-5 molecular sieve by phosphorus, which comprises mixing one or more phosphorus-containing compounds selected from phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate and ammonium phosphate with ZSM-5 molecular sieve with high alkali metal ion content to obtain P-containing phosphorus 2 O 5 At least 0.1wt% of the mixture, drying, calcining, ammonium exchange step and water washing step to reduce the alkali metal ion content to below 0.10wt%, drying, and hydrothermal aging at 400-1000 deg.C and 100% steamAnd (4) a step of formation. 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 following steps: synthesizing → filtering → ammonium exchanging → drying → roasting to obtain ZSM-5 molecular sieve, then modifying the ZSM-5 molecular sieve with phosphoric acid, drying and roasting to obtain the HZSM-5 molecular sieve modified by phosphorus, wherein, P is P 2 O 5 The loading is generally in the range from 1 to 7% by weight.
The hierarchical pore ZSM-5 molecular sieve is a ZSM-5 molecular sieve containing micropores and mesopores, and various hierarchical pore ZSM-5 molecular sieves with mesopore pore canals are prepared by a hard template method, a soft template method, an acid-base post-treatment method and the like.
Although the multistage pore 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 multistage pore 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 hierarchical pore 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-containing hierarchical pore ZSM-5 molecular sieve obtained by phosphorus modification treatment and pressurized hydrothermal roasting under certain conditions has physicochemical characteristics different from those of the conventional phosphorus-containing hierarchical pore ZSM-5 molecular sieve, 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 was made.
Therefore, one of the purposes of the present invention is to provide a phosphorus-containing hierarchical pore ZSM-5 molecular sieve which is different from the physicochemical characteristics of the prior art and aims to solve the problems of the prior art such as unsatisfactory hydrothermal stability; the other purpose is to provide a preparation method of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve.
In order to achieve one of the purposes of the invention, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is characterized in that n1/n2 is less than or equal to 0.08 in surface XPS elemental analysis, 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 0.07 or less, more preferably 0.06 or less. 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.
Furthermore, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve of the invention, 27 in the Al MAS-NMR spectrum, the ratio of the peak area of resonance signal of framework aluminum species coordinated with phosphorus with chemical shift of 39 + -3 ppm to the peak area of resonance signal of four-coordination framework aluminum species with chemical shift of 54ppm + -3 ppm is not less than 1, preferably the area ratio is not less than 8, more preferably not less than 12. 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.
Furthermore, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is subjected to hydrothermal aging for 17 hours at the temperature of 800 ℃ under the condition of 100 percent of water vapor, and then NH 3 In the TPD map, the proportion of the area of the strong acid central peak at the desorption temperature of more than 200 ℃ to the area of the total acid central peak is more than or equal to 45 percent, the preferable range is more than or equal to 50 percent, the more preferable range is more than or equal to 60 percent, and the most preferable range is 60 percent80 percent to the total weight of the steel. The phosphorus-containing hierarchical pore ZSM molecular sieve has higher strong acid center retention degree after hydrothermal aging for 17 hours at 800 ℃ under the condition of 100 percent of water vapor, thereby having higher cracking activity.
When the phosphorus and the aluminum are 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.
In order to achieve the second object of the present invention, the present invention further provides a preparation method of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, which is characterized in that the preparation method comprises: contacting a phosphorus-containing compound solution with a hydrogen-type hierarchical pore ZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product; in the hydrogen-type hierarchical pore ZSM-5 molecular sieve, the proportion of the mesopore volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the hydrogen-type multi-stage hole ZSM-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 after the phosphorus-containing compound, the hydrogen-type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten, the mixture is kept for at least 0.1 hour at the temperature of between 0 and 150 ℃; the atmosphere environment has an apparent pressure of 0.01-1.0Mpa and contains 1-100% of water vapor.
The hierarchical pore means that the hierarchical pore contains both micropores and mesopores. In the preparation method, the hydrogen type hierarchical pore ZSM-5 molecular sieve Na is adopted 2 O<0.1wt%, the proportion of the volume of mesopores (2 nm-50 nm) to the total pore volume is more than 10%, usually 10-90%, and the average pore diameter is 2-20 nm. The silica to alumina ratio (molar ratio of silica to alumina) is in the range of 10 or more, usually 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, 1,3-xylene bis triethyl phosphonium, and the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
In the preparation method, the contact is carried out by contacting the aqueous solution of the phosphorus-containing compound with the hydrogen type hierarchical pore ZSM-5 molecular sieve at the temperature of 0-150 ℃ for at least 0.1 hour at the basically same temperature by using 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 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 basically same temperature means that the temperature difference between the water solution of the phosphorus-containing compound and the hydrogen type hierarchical pore ZSM-5 molecular sieve is +/-5 ℃; for example, the temperature of the aqueous solution of the phosphorus-containing compound is 80 ℃ and the hydrogen-type hierarchical pore ZSM-5 molecular sieve is heated to 75-85 ℃.
In the preparation method of the invention, the contact can also be kept for at least 0.1 hour at 0-150 ℃ after mixing the phosphorus-containing compound, the hydrogen-type hierarchical pore ZSM-5 molecular sieve and water. For example, the mixture is maintained at a normal temperature range of 0 to 30 ℃ for at least 0.1 hour, preferably, for obtaining better effect, i.e., for achieving 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 mixture is maintained at a higher temperature range of 40 ℃ or more 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 hydrogen-type multi-stage hole ZSM-5 molecular sieve is counted by aluminum, the molar ratio of the phosphorus-containing compound to the hydrogen-type multi-stage hole 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 to 1.3. 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 atmosphere is obtained by applying pressure to the outside and adding water to the outside, 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 to 100 percent of water vapor. The step of the hydrothermal roasting treatment is carried out at 200-800 ℃, preferably 300-500 ℃.
The preparation method of the invention promotes the surface phosphorus species to migrate to the hierarchical pore ZSM-5 molecular sieve body phase. The phosphorus-containing hierarchical pore ZSM-5 molecular sieve provided by the invention has the advantages that the coordination of phosphorus and skeleton aluminum is sufficient, the skeleton aluminum is sufficiently protected, and the excellent hydrothermal stability is realized, for example, the higher crystallization retention degree is realized after 17 hours of hydrothermal aging under the condition of 800 ℃ and 100% water vapor; the phosphorus-containing hierarchical pore ZSM-5 molecular sieve has excellent n-tetradecane catalytic cracking activity, improves the main technical indexes such as conversion rate, liquefied gas yield, propylene yield, total butylene yield and the like, increases the yield of low-carbon olefins, has high liquefied gas yield, and produces more products with high added values.
Drawings
FIG. 1 shows the sample PAZ-1 27 Al MAS-NMR spectrum.
FIG. 2 shows NH of PAZ-1 sample after hydrothermal aging at 800 deg.C under 100% steam for 17h 3 -TPD spectrum.
FIG. 3 is a sample PBZ-1 27 Al MAS-NMR spectrum.
FIG. 4 is a graph showing comparative samples D1-1 27 Al MAS-NMR spectrum.
FIG. 5 shows comparative sample D1-1 after hydrothermal aging at 800 deg.C under 100% water vapor for 17hNH of (2) 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.
X-ray photoelectron spectroscopy (XPS) was used to analyze the surface of molecular sieves and examine the migration of phosphorus compounds using an ESCALB 250 model X-ray photoelectron spectrometer from Thermo Fisher-VG. The instrument parameters are as follows: the excitation source was a monochromatized AlK α X-ray of 150W power, the charge shift was corrected by the C1s Peak (284.8 eV) from the contaminated carbon, and the parameters of each Peak were determined by integration after subtracting the background of the Shirley line using XPS Peak Avantage 4.15 software.
The X-ray diffraction (XRD) pattern was measured on a Nippon Denshi 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 (degree)/min. The ZSM-5 molecular sieve synthesized by the method of example 1 in CN1056818C is used as a standard sample, and the crystallinity of the molecular sieve is determined to be 100%. The relative crystallinity is expressed by percentage of the ratio of the sum of the peak areas of five characteristic diffraction peaks with the 2 theta of 22.5-25.0 degrees of the X-ray diffraction (XRD) spectrum of the obtained product and a standard sample of the hierarchical porous ZSM-5 molecular sieve.
The nitrogen adsorption desorption curve was measured on a Micromeritics company ASAP 2420 adsorption apparatus. The sample is degassed in vacuum at 100 ℃ and 300 ℃ for 0.5h and 6h respectively, N2 adsorption and desorption tests are carried out at 77.4K, the adsorption quantity and the desorption quantity of the purified sample to nitrogen under different specific pressures are tested, and an N2 adsorption-desorption isothermal curve is obtained. The BET specific surface area is calculated by using a BET formula, the micropore area is calculated by using t-plot, and the pore size distribution is calculated by using BJH.
27 The analysis of the Al MAS-NMR spectrum was carried out on a Bruker AVANCE III 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-degree pulling chamfer angle), the magic angle rotating speed is 12kHz, and the delay time is 1s. 27 The characteristic peak 1 at 54 + -3 pp m is attributed to the four-coordinate framework aluminum, and the characteristic peak 2 at 39 + -3 ppm is attributed to the phosphorus-stabilized framework aluminum (distortion four) in the Al MAS-NMR spectrumCoordination framework aluminum). And each peak area is calculated by adopting an integration method after peak-splitting fitting is carried out on the characteristic peak.
Temperature programmed desorption analysis (NH) 3 TPD) characterization was carried out 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 (the flow rate of the high-purity He. is 50 mL/min), raising the temperature to 600 ℃ at the speed 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 Switching the-He mixed gas into high-purity He carrier gas, and purging for 1h to desorb material resources and adsorb ammonia; 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 the spectrum resolution of the peak pattern.
Example 1A
Example 1A illustrates a phosphorus-containing, hierarchical pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 18.5g of diammonium hydrogen phosphate in 60g of deionized water, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve (provided by Qilu division, china petrochemical catalyst, inc., with a relative crystallinity of 88.6 percent and a silica/alumina molar ratio of 20.8) 2 The content of O is 0.017 percent by weight, and the specific surface area is 373m 2 (g), the total pore volume is 0.256ml/g, the mesoporous volume is 0.119ml/g, the average pore diameter is 5.8nm, the same is applied below), the mixture is immersed at 20 ℃ for 2 hours, dried in an oven at 110 ℃, externally applied with pressure and added with water, and treated at 450 ℃, 0.4Mpa and 60% of water vapor atmosphere for 0.5 hour, and the obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample is marked as PAZ-1.
Example 1B
Example 1B illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
The process is the same as the process of example 1A, except that diammonium hydrogen phosphate, a hydrogen-type hierarchical pore ZSM-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-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-1.
Comparative examples 1 to 1
Comparative examples 1-1 illustrate the current industry conventional process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 1A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 3 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D1-1.
Comparative examples 1 to 2
Comparative examples 1-2 illustrate comparative samples of phosphorus-containing hierarchical pore ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination. The difference from example 1A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D1-2.
The XPS elemental analysis data for the surfaces of PAZ-1, PBZ-1, D1-1 and D1-2 are shown in Table 1-1.
XRD crystallinity and BET pore parameters of PAZ-1, PBZ-1, D1-1 and D1-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 1-2.
Of PAZ-1, PBZ-1, D1-1 27 The MAS-NMR spectra of Al are shown in FIG. 1, FIG. 3, FIG. 4, and D1-2, respectively 27 The Al MAS-NMR spectrum is characterized by the same figure 4, in which different treatment conditions have a great influence on the coordination degree of phosphorus and framework aluminum, chemical shifts are attributed to four-coordinate framework aluminum at 54ppm, and four-coordinate framework aluminum which is attributed to phosphorus-stabilized combination of phosphorus and aluminum is a characteristic peak at 39 ppm. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 1-3.
NH of PAZ-1 and D1-1 after being treated by 100 percent of water vapor at 800 ℃ and hydrothermal aging for 17 hours 3 the-TPD spectra are shown in FIG. 2 and FIG. 5, respectively, NH of PBZ-1 and D1-2 3 TPD spectra are characterized as in figures 2 and 5, respectively; the specific gravity data of the strong acid central peak area accounting for the total acid central peak area at desorption temperature above 200 ℃ are shown in tables 1-4.
After PAZ-1, PBZ-1, D1-1 and D1-2 are subjected to hydrothermal aging treatment at 800 ℃ for 17h with 100% of water vapor, n-tetradecane cracking evaluation is carried out. Micro-reverse evaluation conditions: 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
Tables 1 to 2
As can be seen from tables 1-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 6 percent at most, and the hydrothermal stability is obviously improved.
Tables 1 to 3
Tables 1 to 4
| Sample name | The ratio of the strong acid central peak area to the total acid central peak area |
| PAZ-1 | 45％ |
| PBZ-1 | 52％ |
| D1-1 | 16％ |
| D1-2 | 24％ |
Tables 1 to 5
| PAZ-1 | PBZ-1 | D1-1 | D1-2 | |
| Material balance/m% | ||||
| Dry gas | 4.2 | 4.0 | 5.1 | 3.6 |
| Liquefied gas | 45.5 | 44.4 | 32.1 | 32.0 |
| Gasoline (gasoline) | 18.4 | 20.0 | 31.80 | 34.9 |
| Diesel oil | 26.1 | 25.1 | 28.0 | 23.7 |
| M% of main product in cracked gas | ||||
| Ethylene | 3.4 | 3.3 | 3.2 | 3.0 |
| Propylene (PA) | 18.2 | 16.0 | 12.0 | 13.4 |
| Total butene | 13.1 | 13.9 | 5.6 | 6.6 |
| Conversion/m% | 72.1 | 73.5 | 64.3 | 66.2 |
Example 2A
Example 2A illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 18.5g of diammonium hydrogen phosphate in 120g of deionized water, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking at 20 ℃ for 2 hours by adopting a soaking method, drying in an oven at 110 ℃, externally applying pressure and adding water, and treating for 2h at 600 ℃, 0.4Mpa and 50% of water vapor atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, wherein the sample is marked as PAZ-2.
Example 2B
Example 2B illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
The process is the same as the process of example 2A, except that diammonium hydrogen phosphate, a hydrogen-type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and the slurry is heated to 70 ℃ and kept for 2 hours. And (4) recording an obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample as PBZ-2.
Comparative example 2-1
Comparative example 2-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 2A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D2-1.
Comparative examples 2 to 2
Comparative examples 2-2 illustrate comparative samples of phosphorus-containing hierarchical pore ZSM-5 molecular sieves obtained by atmospheric hydrothermal calcination.
The difference from example 2A is that the calcination conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and designated D2-2.
The surface XPS elemental analysis data of PAZ-2, PBZ-2, D2-1 and 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 deg.C with 100% water vapor for 17h are shown in Table 2-2.
Of PAZ-2, PBZ-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D2-1, D2-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 2-3.
NH of PAZ-2 and PBZ-2 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of-TPD spectrum characterized by the same pattern as in FIGS. 2, D2-1, D2-2 3 The characteristics of the TPD spectrogram are shown in the same figure 5, and the proportion data of the strong acid center peak area accounting for the total acid center peak area at the desorption temperature of more than 200 ℃ are shown in tables 2 to 4.
The PAZ-2, PBZ-2, D2-1 and D2-2 are subjected to hydrothermal aging treatment at 800 ℃ for 17h with 100% of water vapor, and then subjected to n-tetradecane cracking evaluation, and the evaluation data are shown in tables 2-5.
TABLE 2-1
Tables 2 to 2
As can be seen from the table 2-2, after the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 9 percent at most, and the hydrothermal stability is obviously improved.
Tables 2 to 3
Tables 2 to 4
Tables 2 to 5
| PAZ-2 | PBZ-2 | D2-1 | D2-2 | |
| Material balance/m% | ||||
| Dry gas | 4.2 | 5.2 | 5.0 | 3.6 |
| Liquefied gas | 36.4 | 41.3 | 31.6 | 32.5 |
| Gasoline (gasoline) | 27.0 | 24.0 | 32.8 | 23.2 |
| Diesel oil | 26.2 | 23.3 | 25.81 | 34.5 |
| M% of main product in cracked gas | ||||
| Ethylene | 3.2 | 4.1 | 3.1 | 2.7 |
| Propylene (PA) | 15.5 | 16.0 | 11.5 | 13.8 |
| Total butene | 7.8 | 9.2 | 5.8 | 7.6 |
| Conversion/m% | 73.0 | 75.8 | 65.0 | 66.4 |
Example 3A
Example 3A illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 11.8g of phosphoric acid in 60g of deionized water at normal temperature, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking for 4 hours at 20 ℃ by adopting a soaking method, drying in an oven at 110 ℃, and treating for 2 hours at 430 ℃ under 0.4Mpa in a 100% water vapor atmosphere to obtain the phosphorus-modified hierarchical pore ZSM-5 molecular sieve, wherein the molecular sieve is marked as PAZ-3.
Example 3B
Example 3B illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
The same materials, proportioning, drying and calcining as in example 3A except that the phosphorus-containing aqueous solution at 80 ℃ was mixed and contacted with the hydrogen-type multi-stage pore ZSM-5 molecular sieve heated to 80 ℃ for 4 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve is marked as PBZ-3.
Comparative example 3-1
Comparative example 3-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 3A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D3-1.
Comparative examples 3 and 2
Comparative example 3-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 3A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D3-2.
The XPS elemental analysis data for the surfaces of PAZ-3, PBZ-3, D3-1 and D3-2 are shown in Table 3-1.
XRD crystallinity and BET pore parameters of PAZ-3, PBZ-3, D3-1 and D3-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 3-2.
Of PAZ-3, PBZ-3 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D3-1, D3-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in tables 3-3.
NH of PAZ-3 and PBZ-3 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of TPD spectrum characterized by the same pattern as in FIGS. 3, D3-1, D3-2 3 The TPD spectrum is characterized as in figure 5, 27 the data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 3-3.
NH of PAZ-3, PBZ-3, D3-1 and D3-2 after 100 percent of water vapor and 17h of hydrothermal aging treatment at 800 DEG C 3 The specific gravity data of the strong acid central peak area accounting for the total acid central peak area in the TPD spectrogram at the desorption temperature of more than 200 ℃ are shown in tables 3-4.
After PAZ-3, PBZ-3, D3-1 and D3-2 are subjected to hydrothermal aging treatment at 800 ℃ for 17 hours with 100% of water vapor, n-tetradecane cracking evaluation is carried out, and the evaluation data are shown in tables 3-5.
TABLE 3-1
TABLE 3-2
As can be seen from the table 3-2, after the phosphorus-containing hierarchical porous ZSM-5 molecular sieve is subjected to hydrothermal aging treatment at 800 ℃, 100% of water vapor and 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 11 percentage points at most, and the hydrothermal stability is obviously improved.
Tables 3 to 3
Tables 3 to 4
Tables 3 to 5
| PAZ-3 | PBZ-3 | D3-1 | D3-2 | |
| Material balance/m% | ||||
| Dry gas | 4.8 | 5.5 | 3.6 | 4.8 |
| Liquefied gas | 39.5 | 51.0 | 30.4 | 31.6 |
| Gasoline (gasoline) | 29.3 | 25.7 | 35.9 | 33.2 |
| Diesel oil | 19.4 | 11.1 | 26.6 | 27.6 |
| M% of main product in cracked gas | ||||
| Ethylene | 3.8 | 4.6 | 2.8 | 3.3 |
| Propylene (PA) | 15.0 | 17.5 | 13 | 12.5 |
| Total butene | 9.4 | 13.5 | 6.2 | 6.5 |
| Conversion/m% | 79.2 | 87.0 | 65.9 | 66.8 |
Example 4A
Example 4A illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 9.3g of diammonium hydrogen phosphate in 120g of deionized water at normal temperature, stirring for 0.5h to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking for 2 hours at 20 ℃ by adopting a soaking method, drying in an oven at 110 ℃, and treating for 2h at 350 ℃, 0.2Mpa and 100% steam atmosphere to obtain the phosphorus-containing hierarchical pore ZSM-5 molecular sieve, wherein the molecular sieve is marked as PAZ-4.
Example 4B
Example 4B illustrates a phosphorus-containing, multistage pore ZSM-5 molecular sieve and process of the present invention.
The material and the mixture ratio are the same as those of the example 4A, except that diammonium hydrogen phosphate, a hydrogen type hierarchical pore ZSM-5 molecular sieve and water are mixed and beaten into slurry, and then the temperature is raised to 70 ℃ and the slurry is kept for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-4.
Comparative example 4-1
Comparative example 4-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 1A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D4-1.
Comparative examples 4 to 2
Comparative example 4-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 1A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D4-2.
The XPS elemental analysis data for the surfaces of PAZ-4, PBZ-4, D4-1 and 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 deg.C with 100% water vapor for 17h are shown in Table 4-2.
Of PAZ-4, PBZ-4 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D4-1, D4-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in tables 4-3.
NH of PAZ-4 and PBZ-4 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of-TPD spectrum characterized by the same pattern as in FIGS. 2, D4-1 and D4-2 3 The characteristics of the TPD spectrogram are as shown in figure 5, and 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 ℃ are shown in a table 4-4.
After PAZ-4, PBZ-4, D4-1 and D4-2 are subjected to hydrothermal aging treatment at 800 ℃ for 17h with 100% of water vapor, n-tetradecane cracking evaluation is carried out, and the evaluation data are shown in tables 4-5.
TABLE 4-1
TABLE 4-2
As can be seen from the table 4-2, after the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is subjected to hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical pore ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 15 percent at most, and the hydrothermal stability is obviously improved.
Tables 4 to 3
Tables 4 to 4
Tables 4 to 5
| PAZ-4 | PBZ-4 | D4-1 | D4-2 | |
| Material balance/m% | ||||
| Dry gas | 4.8 | 5.8 | 4.9 | 4.9 |
| Liquefied gas | 51.1 | 49.7 | 31.9 | 34.0 |
| Gasoline (gasoline) | 23.8 | 32.2 | 40.8 | 31.7 |
| Diesel oil | 14.3 | 5.4 | 16.3 | 25.4 |
| M% of main product in cracked gas | ||||
| Ethylene | 3.95 | 4.7 | 3.9 | 3.4 |
| Propylene (PA) | 17.5 | 17.1 | 13.5 | 13.0 |
| Total butene | 15.2 | 12.6 | 5.4 | 6.7 |
| Conversion/m% | 83.7 | 93.4 | 73.1 | 74.0 |
Example 5A
Example 5A illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 9.7g of trimethyl phosphate in 80g of deionized water at 90 ℃, stirring for 1h to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 8 hours at 20 ℃, drying in an oven at 110 ℃, and carrying out pressurized hydrothermal roasting treatment for 4h at 500 ℃, 0.6Mpa and 40% of steam atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, which is marked as PAZ-5.
Example 5B
Example 5B illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
The procedure of the preparation, mixing, drying and calcination of the same materials as in example 5A is carried out except that trimethyl phosphate, hydrogen-type hierarchical porous ZSM-5 molecular sieve and water are mixed and made into slurry, and then the slurry is heated to 120 ℃ and kept for 8 hours. And marking the obtained phosphorus modified hierarchical pore ZSM-5 molecular sieve as PBZ-5.
Comparative example 5-1
Comparative example 5-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 5A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical pore ZSM-5 molecular sieve comparison sample is marked as D5-1.
Comparative examples 5 to 2
Comparative example 5-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 5A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparison sample of the ZSM-5 molecular sieve containing phosphorus was obtained and was designated as D5-2.
The XPS elemental analysis data for the surfaces of PAZ-5, PBZ-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 deg.C with 100% water vapor for 17h are shown in Table 5-2.
Of PAZ-5, PBZ-5 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D5-1, D5-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The peak area ratio data of the Al MAS-NMR spectrum are shown in Table 5-3.
NH of PAZ-5 and PBZ-5 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of the same pattern as that of FIG. 2, D5-1, D5-2 of TPD spectrum 3 The characteristics of a TPD spectrogram are the same as those of figure 5, and the desorption temperature is 200 DEG CThe specific gravity data of the area of the strong acid central peak relative to the area of the total acid central peak are shown in Table 5-4.
PAZ-5, PBZ-5, D5-1 and D5-2 were subjected to hydrothermal aging treatment at 800 ℃ for 17 hours with 100% steam and then subjected to n-tetradecane cracking evaluation, and the evaluation data are shown in tables 5 to 5.
TABLE 5-1
TABLE 5-2
As can be seen from Table 5-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystal retention and Kong Canshu retention, the crystal retention and the pore parameters are obviously compared with a sample, the crystal retention is improved by 14 percent at most, and the hydrothermal stability is obviously improved.
Tables 5 to 3
Tables 5 to 4
Tables 5 to 5
| PAZ-5 | PBZ-5 | D5-1 | D5-2 | |
| Material balance/m% | ||||
| Dry gas | 4.7 | 5.5 | 4.9 | 5.3 |
| Liquefied gas | 42.5 | 46.7 | 32.1 | 39.1 |
| Gasoline (R) and its preparation method | 31.8 | 35.8 | 31.0 | 28.7 |
| Diesel oil | 5.1 | 6.1 | 30.0 | 25.0 |
| M% of main product in cracked gas | ||||
| Ethylene | 3.9 | 4.6 | 3.0 | 3.9 |
| Propylene (PA) | 15.4 | 16.2 | 11.6 | 14.4 |
| Total butene | 10.1 | 11.2 | 5.0 | 9.1 |
| Conversion/m% | 78.8 | 84.8 | 71.9 | 73.5 |
Example 6A
Example 6A illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 13.2g of boron phosphate in 100g of deionized water at 100 ℃, stirring for 3h to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, soaking for 2h at 20 ℃ by adopting a soaking method, drying in an oven at 110 ℃, and carrying out pressurized hydrothermal roasting treatment for 4h at 350 ℃, 0.4Mpa and 60% steam atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, wherein the sample is marked as PAZ-6.
Example 6B
Example 6B illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
The same materials and mixture ratio as in example 6A, except that boron phosphate, hydrogen type multi-stage hole 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 obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve is marked as PBZ-6.
Comparative example 6-1
Comparative example 6-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 6A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D6-1.
Comparative examples 6 to 2
Comparative example 6-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 6A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparative sample of the phosphorous containing ZSM-5 molecular sieve was obtained and was designated D6-2.
The XPS elemental analysis data for the surfaces of PAZ-6, PBZ-6, D6-1 and D6-2 are shown in Table 6-1.
XRD crystallinity and BET pore parameters of PAZ-6, PBZ-6, D6-1 and D6-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 6-2.
Of PAZ-6, PBZ-6 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D6-1, D6-2 27 The Al MAS-NMR spectrum has the characteristics of FIG. 4. 27 The peak area ratio data of the Al MAS-NMR spectrum is shown inTables 6 to 3.
NH of PAZ-6 and PBZ-6 treated by 100 percent of water vapor at 800 ℃ and 17 hours of hydrothermal aging 3 NH of-TPD spectrum characterized by the same pattern as in FIGS. 2, D6-1 and D6-2 3 The characteristics of the TPD spectrogram are as shown in figure 5, and 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 ℃ are shown in a table 6-4.
PAZ-6, PBZ-6, D6-1 and D6-2 were subjected to hydrothermal aging treatment at 800 ℃ for 17 hours with 100% steam and then subjected to n-tetradecane cracking evaluation, and the evaluation data are shown in tables 6 to 5.
TABLE 6-1
TABLE 6-2
As can be seen from Table 6-2, after hydrothermal aging treatment at 800 ℃ and 100% of water vapor for 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystal retention and Kong Canshu retention, the crystal retention and the pore parameters are obviously compared with a sample, the crystal retention is improved by 8 percent at most, and the hydrothermal stability is obviously improved.
Tables 6 to 3
Tables 6 to 4
Tables 6 to 5
Example 7A
Example 7A illustrates a phosphorus-containing, hierarchical pore ZSM-5 molecular sieve and process of the present invention.
Dissolving 16.3g of triphenyl phosphine in 80g of deionized water, stirring for 2 hours to obtain a phosphorus-containing aqueous solution, adding the phosphorus-containing aqueous solution into 108g of a hydrogen-type hierarchical pore ZSM-5 molecular sieve, modifying by adopting an impregnation method, impregnating for 4 hours at 20 ℃, drying in an oven at 110 ℃, and carrying out pressurized hydrothermal roasting treatment for 2 hours at 600 ℃, 1.0Mpa and 50% of water vapor atmosphere to obtain a phosphorus-containing hierarchical pore ZSM-5 molecular sieve sample, which is marked as PAZ-7.
Example 7B
Example 7B illustrates a phosphorus-containing, multi-stage pore ZSM-5 molecular sieve and process of the present invention.
The same materials and proportions as in example 7A except that the 80 ℃ phosphorus-containing aqueous solution was mixed with the 80 ℃ hydrogen-type multi-stage pore ZSM-5 molecular sieve and contacted for 4 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve sample is marked as PBZ-7.
Comparative example 7-1
Comparative example 7-1 illustrates the prior art process and the resulting phosphorus containing hierarchical pore ZSM-5 comparative sample.
The same as example 7A except that the firing conditions were atmospheric pressure (apparent pressure 0 MPa) and air firing in a muffle furnace at 550 ℃ for 2 hours. The obtained phosphorus-containing hierarchical porous ZSM-5 molecular sieve comparison sample is marked as D7-1.
Comparative examples 7 to 2
Comparative example 7-2 illustrates a comparative sample of a phosphorus-containing hierarchical pore ZSM-5 molecular sieve obtained by atmospheric hydrothermal calcination.
The difference from example 7A is that the firing conditions were atmospheric pressure (apparent pressure 0 MPa). A comparison sample of the ZSM-5 molecular sieve containing phosphorus was obtained and was designated as D7-2.
The XPS elemental analysis data for the surfaces of PAZ-7, PBZ-7, D7-1, D7-2 are shown in Table 7-1.
XRD crystallinity and BET pore parameters of PAZ-7, PBZ-7, D7-1 and D7-2 before and after hydrothermal aging treatment at 800 deg.C with 100% water vapor for 17h are shown in Table 7-2.
Of PAZ-7, PBZ-7 27 The Al MAS-NMR spectrum has the characteristics of FIG. 1 and FIG. 3, respectively. Of D7-1, D7-2 27 Al MAS-NMR spectrum toolThere is the feature of fig. 4. 27 The data of the peak area ratio of the Al MAS-NMR spectrum are shown in Table 7-3.
NH of PAZ-7 and PBZ-7 treated by hydrothermal aging for 17 hours at 800 ℃ with 100 percent of water vapor 3 NH of the TPD spectrum with the same characteristics as those of FIG. 2, D7-1 and D7-2 3 The characteristics of the TPD spectrogram are as shown in figure 5, and 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 ℃ are shown in a table 7-4.
PAZ-7, PBZ-7, D7-1 and D7-2 were subjected to hydrothermal aging treatment at 800 ℃ for 17 hours with 100% steam and then subjected to n-tetradecane cracking evaluation, and the evaluation data are shown in Table 7-5.
TABLE 7-1
TABLE 7-2
As can be seen from the table 7-2, after the phosphorus-containing hierarchical porous ZSM-5 molecular sieve is subjected to hydrothermal aging treatment at 800 ℃, 100% of water vapor and 17 hours, the phosphorus-containing hierarchical porous ZSM-5 molecular sieve still has high crystallization retention and Kong Canshu retention, the crystallization retention and the pore parameters are obviously compared with a sample, the crystallization retention is improved by 12 percent at most, and the hydrothermal stability is obviously improved
Tables 7 to 3
Tables 7 to 4
Tables 7 to 5
| PAZ-7 | PBZ-7 | D7-1 | D7-2 | |
| Material balance/m% | ||||
| Dry gas | 4.7 | 4.8 | 4.4 | 6.3 |
| Liquefied gas | 42.5 | 48.6 | 38.3 | 39.6 |
| Gasoline (gasoline) | 31.8 | 29.7 | 29.7 | 31.9 |
| Diesel oil | 5.1 | 9.9 | 21.9 | 20.3 |
| M% of main product in cracked gas | ||||
| Ethylene | 3.9 | 4.2 | 3.2 | 4.3 |
| Propylene (PA) | 16.4 | 16.9 | 13.1 | 13.5 |
| Total butene | 10.1 | 13.1 | 9.2 | 8.8 |
| Conversion/m% | 81.8 | 85.4 | 70.4 | 71.3 |
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of 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 above embodiments, the various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations will not be further described in the present disclosure.
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 (25)
1. The phosphorus-containing hierarchical pore ZSM-5 molecular sieve 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; in the molecular sieve, the proportion of the mesopore volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm.
2. A molecular sieve according to claim 1 wherein said n1/n2 is 0.07 or less.
3. A molecular sieve according to claim 1 wherein said n1/n2 is 0.06.
4. The molecular sieve of claim 1, wherein said n1/n2 is 0.02 to 0.05.
5. Molecular sieve according to claim 1, characterized in that 27 Peak area of resonance signal in Al MAS-NMR at chemical shift of 39. + -.3 ppmThe ratio of the peak area of the resonance signal to the peak area of the resonance signal with the chemical shift of 54ppm +/-3 ppm is more than or equal to 1.
6. A molecular sieve according to claim 5 wherein the ratio of the area of the resonance signal peak at a chemical shift of 39 ± 3ppm to the area of the resonance signal peak at a chemical shift of 54ppm ± 3ppm is at least 8.
7. A molecular sieve according to claim 6 wherein the ratio of the area under the resonance signal peaks at chemical shifts 39. + -.3 ppm to the area under the resonance signal peaks at chemical shifts 54. + -.3 ppm is not less than 12.
8. A molecular sieve according to claim 7 wherein the ratio of the area of the resonance signal peak at a chemical shift of 39 ± 3ppm to the area of the resonance signal peak at a chemical shift of 54ppm ± 3ppm is from 14 to 25.
9. The molecular sieve according to claim 1, characterized in that its NH after 17h hydrothermal aging at 800 ℃ under 100% water vapor conditions 3 In a TPD (thermoplastic vulcanizate) map, the proportion of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ is more than or equal to 45 percent.
10. The molecular sieve of claim 9, characterized in that its NH after 17h hydrothermal aging at 800 ℃ under 100% water vapor conditions 3 In a TPD (thermoplastic vulcanizate) map, the proportion of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ is more than or equal to 50 percent.
11. Molecular sieve according to claim 10, characterized in that its NH after 17h hydrothermal aging at 800 ℃ under 100% water vapor conditions 3 In a TPD (thermoplastic vulcanizate) map, the proportion of the area of the strong acid central peak occupying the total acid central peak area at the desorption temperature of more than 200 ℃ is more than or equal to 60 percent.
12. Molecular sieve according to claim 11, characterized in that its NH after 17h hydrothermal aging at 800 ℃ under 100% water vapor conditions 3 Strong acid center with desorption temperature above 200 ℃ in TPD mapThe specific gravity of the peak area accounts for 60-80% of the total acid center peak area.
13. The molecular sieve of 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 1, wherein the ratio of phosphorus to aluminum is 0.1 to 1.5, on a molar basis.
15. The molecular sieve of claim 1, wherein the ratio of phosphorus to aluminum, when both are in molar terms, is from 0.2 to 1.5.
16. The preparation method of the phosphorus-containing hierarchical pore ZSM-5 molecular sieve is characterized by comprising the following steps: contacting a phosphorus-containing compound solution with a hydrogen-type hierarchical pore ZSM-5 molecular sieve, drying, performing hydrothermal roasting treatment under the atmosphere environment of externally applied pressure and externally added water, and recovering a product; in the hydrogen-type hierarchical pore ZSM-5 molecular sieve, the proportion of the mesopore volume to the total pore volume is more than 10 percent, and the average pore diameter is 2-20 nm; the contact is that the water solution of the phosphorus-containing compound with the temperature of 0-150 ℃ and the hydrogen-type multi-stage hole ZSM-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 hydrogen-type multi-stage hole ZSM-5 molecular sieve and water are mixed and pulped and then are kept for at least 0.1 hour at the temperature of 0-150 ℃; the atmosphere environment has an apparent pressure of 0.01-1.0Mpa and contains 1-100% of water vapor.
17. The method of claim 16, wherein the phosphorus-containing compound is selected from the group consisting of organic phosphorus compounds and inorganic phosphorus compounds.
18. The process according to claim 17, wherein the organophosphate 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, hexamethylphosphoric triamide, dibenzyl diethyl phosphonium, 1,3-xylene bis triethyl phosphonium; the inorganic phosphide is selected from phosphoric acid, ammonium hydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate and boron phosphate.
19. The process of claim 16 wherein the phosphorus-containing compound is phosphorus and the hydrogen-form hierarchical pore ZSM-5 molecular sieve is aluminum in a molar ratio of 0.01 to 2.
20. The process of claim 19 wherein the phosphorus-containing compound is phosphorus and the hydrogen-form, multi-stage pore ZSM-5 molecular sieve is aluminum, in a molar ratio of 0.1 to 1.5.
21. The process according to claim 20, wherein the phosphorus-containing compound is phosphorus and the hydrogen-type hierarchical porous ZSM-5 molecular sieve is aluminum, and the molar ratio of the phosphorus-containing compound to the hydrogen-type hierarchical porous ZSM-5 molecular sieve is 0.3 to 1.3.
22. The process according to claim 16, wherein said contacting is carried out at a water sieve weight ratio of 0.5 to 1 and said contacting is carried out at 50 to 150 ℃ for 0.5 to 40 hours.
23. The method of claim 22, wherein said contacting is carried out at a temperature of 70 to 130 ℃.
24. The method of claim 16, wherein said atmosphere has a pressure of 0.1 to 0.8Mpa and contains 30 to 100% water vapor; the step of hydrothermal roasting treatment is carried out at 200-800 ℃.
25. The method of claim 24, wherein said atmosphere has a pressure of 0.3 to 0.6Mpa and contains 60 to 100% water vapor; the step of hydrothermal roasting treatment is carried out at 300-500 ℃.
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| CN202010283400.3A CN113526519B (en) | 2020-04-13 | 2020-04-13 | Phosphorus-containing hierarchical pore ZSM-5 molecular sieve and preparation method thereof |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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