CN114225958A - Catalytic cracking catalyst for producing more propylene and preparation method thereof - Google Patents
Catalytic cracking catalyst for producing more propylene and preparation method thereof Download PDFInfo
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- CN114225958A CN114225958A CN202111669405.0A CN202111669405A CN114225958A CN 114225958 A CN114225958 A CN 114225958A CN 202111669405 A CN202111669405 A CN 202111669405A CN 114225958 A CN114225958 A CN 114225958A
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- molecular sieve
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- catalytic cracking
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- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 74
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 238000003756 stirring Methods 0.000 claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 37
- 239000011574 phosphorus Substances 0.000 claims abstract description 37
- 239000002808 molecular sieve Substances 0.000 claims abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 230000004048 modification Effects 0.000 claims abstract description 28
- 238000012986 modification Methods 0.000 claims abstract description 28
- 239000012452 mother liquor Substances 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 19
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 19
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 19
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000000465 moulding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- -1 phosphorus compound Chemical class 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium nitrate Inorganic materials [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 238000009718 spray deposition Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 14
- 230000032683 aging Effects 0.000 description 11
- 239000003921 oil Substances 0.000 description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004230 steam cracking Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention provides a catalytic cracking catalyst for producing more propylene and a preparation method thereof; the preparation method comprises the following steps: a) sequentially carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve to obtain a modified molecular sieve; b) mixing a binder and water to obtain precursor slurry, and sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition to obtain propylene catalyst mother liquor; c) molding and roasting the propylene catalyst mother liquor obtained in the step b) to obtain the catalytic cracking propylene catalyst with high yield. Compared with the prior art, the preparation method provided by the invention adopts the hydrogen type ZSM-5 molecular sieve as the raw material, and the modification treatment is carried out by matching with specific steps, so that the overall good interaction is realized, and the prepared catalytic cracking propylene-yielding catalyst has high propylene yield and propylene selectivity, has good hydrothermal stability, and can be better used in the petrochemical catalytic cracking field.
Description
Technical Field
The invention relates to the technical field of petroleum catalytic cracking, in particular to a catalytic cracking catalyst for producing more propylene and a preparation method thereof.
Background
Propylene is used as an important chemical raw material, and the demand of the market for propylene is increasing along with the development of national economy in recent years. At present, domestic propylene mainly comes from naphtha steam cracking and heavy oil catalytic cracking, and due to the fact that crude oil in China is heavy, the increasing propylene demand is difficult to meet by adopting naphtha steam cracking. Compared with the steam cracking process, the catalytic cracking process for producing propylene has the advantages of heavy raw materials, high ratio of propylene to ethylene, low production cost and the like, and the catalytic cracking process for increasing the yield of propylene becomes a great hotspot of the development of the catalytic cracking technology.
The propylene catalyst used in catalytic cracking can greatly improve the yield of propylene, wherein the hydrogen type ZSM-5 molecular sieve plays a main role; however, molecular sieves are structurally unstable and are highly susceptible to deactivation under the hydrothermal conditions of catalytic cracking. Therefore, it is necessary to provide a propylene catalyst which produces a large amount of propylene and has good hydrothermal stability.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalytic cracking propylene production catalyst and a preparation method thereof, and the catalytic cracking propylene production catalyst provided by the present invention has high propylene yield and propylene selectivity, and good hydrothermal stability.
The invention provides a preparation method of a catalytic cracking catalyst for producing more propylene, which comprises the following steps:
a) sequentially carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve to obtain a modified molecular sieve;
b) mixing a binder and water to obtain precursor slurry, and sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition to obtain propylene catalyst mother liquor;
c) molding and roasting the propylene catalyst mother liquor obtained in the step b) to obtain the catalytic cracking propylene catalyst with high yield.
Preferably, the particle size of the hydrogen type ZSM-5 molecular sieve in the step a) is nano-scale, and the silica-alumina ratio is 20-100.
Preferably, the phosphorus modification process in step a) is specifically as follows:
soaking a hydrogen type ZSM-5 molecular sieve in a phosphorus compound solution with equal mass and concentration of 0.2-10 wt%, uniformly stirring at room temperature, drying, and roasting at 520-560 ℃ for 2-4 h to obtain a phosphorus modified molecular sieve; the phosphorus-containing compound is P2O5。
Preferably, the metal modification process in the step a) is specifically as follows:
dipping the hydrogen type ZSM-5 molecular sieve modified by phosphorus in a metal compound solution with the same mass and the concentration of 0.5 wt% -8 wt%, uniformly stirring at room temperature, drying, and roasting at 520-560 ℃ for 2-4 h to obtain the modified molecular sieve; the metal compound is selected from Zn (NO)3)2、Ce(NO3)3Or Mg (NO)3)2。
Preferably, the binder in step b) is an aluminum sol; the mass ratio of the binder to the water is 1: (4-5).
Preferably, the step b) of sequentially adding kaolin, pseudoboehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition specifically comprises the following steps:
adding kaolin into the precursor slurry, stirring for 0.5-1.5 h at the rotating speed of 300-500 r/min, adding pseudo-boehmite, stirring for 0.4-0.6 h at the rotating speed of 300-500 r/min, adding hydrochloric acid with the concentration of 30-40 wt%, stirring for 0.5-1.5 h at the rotating speed of 300-500 r/min, finally adding the modified molecular sieve obtained in the step a), and stirring for 1-2 h at the rotating speed of 300-500 r/min to obtain the propylene catalyst mother liquor.
Preferably, the mass ratio of the precursor slurry, kaolin, pseudoboehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) is (60-100): (10-20): (4-6): 1: (15-20).
Preferably, the forming in step c) is spray forming.
Preferably, the roasting temperature in the step c) is 520-560 ℃ and the roasting time is 2-4 h.
The invention also provides a catalytic cracking catalyst for producing more propylene, which is prepared by the preparation method of the technical scheme.
The invention provides a catalytic cracking catalyst for producing more propylene and a preparation method thereof; the preparation method comprises the following steps: a) sequentially carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve to obtain a modified molecular sieve; b) mixing a binder and water to obtain precursor slurry, and sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition to obtain propylene catalyst mother liquor; c) molding and roasting the propylene catalyst mother liquor obtained in the step b) to obtain the catalytic cracking propylene catalyst with high yield. Compared with the prior art, the preparation method provided by the invention adopts the hydrogen type ZSM-5 molecular sieve as the raw material, and the modification treatment is carried out by matching with specific steps, so that the overall good interaction is realized, and the prepared catalytic cracking propylene-yielding catalyst has high propylene yield and propylene selectivity, has good hydrothermal stability, and can be better used in the petrochemical catalytic cracking field.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a catalytic cracking catalyst for producing more propylene, which comprises the following steps:
a) sequentially carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve to obtain a modified molecular sieve;
b) mixing a binder and water to obtain precursor slurry, and sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition to obtain propylene catalyst mother liquor;
c) molding and roasting the propylene catalyst mother liquor obtained in the step b) to obtain the catalytic cracking propylene catalyst with high yield.
Firstly, carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve in sequence to obtain a modified molecular sieve. In the invention, the particle size of the hydrogen type ZSM-5 molecular sieve is preferably nano-scale, and the silicon-aluminum ratio is preferably 20-100, and more preferably 50. The source of the hydrogen type ZSM-5 molecular sieve is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the present invention, the process of phosphorus modification is preferably specifically:
soaking a hydrogen type ZSM-5 molecular sieve in a phosphorus compound solution with equal mass and concentration of 0.2-10 wt%, uniformly stirring at room temperature, drying, and roasting at 520-560 ℃ for 2-4 h to obtain a phosphorus modified molecular sieve;
more preferably:
soaking a hydrogen type ZSM-5 molecular sieve in a phosphorus compound solution with equal mass and concentration of 1 wt%, uniformly stirring at room temperature, drying, and roasting at 540 ℃ for 3h to obtain the phosphorus modified molecular sieve.
In the present invention, the phosphorus-containing compound is preferably P2O5. The source of the phosphorus-containing compound is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the metal modification process is preferably specifically:
dipping the hydrogen type ZSM-5 molecular sieve modified by phosphorus in a metal compound solution with the same mass and the concentration of 0.5 wt% -8 wt%, uniformly stirring at room temperature, drying, and roasting at 520-560 ℃ for 2-4 h to obtain the modified molecular sieve;
more preferably:
and (3) soaking the hydrogen type ZSM-5 molecular sieve modified by the phosphorus in a metal compound solution with the same mass and the concentration of 2 wt%, uniformly stirring at room temperature, drying, and roasting at 540 ℃ for 3h to obtain the modified molecular sieve.
In the present invention, the metal compound is preferably selected from Zn (NO)3)2、Ce(NO3)3Or Mg (NO)3)2. The source of the metal compound is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
According to the invention, the phosphorus modification and the metal modification are adopted, so that the specific metal shows the effect of enhancing the thermal stability and the hydrothermal stability of the molecular sieve in the molecular sieve, and after entering the inside of the molecular sieve crystal after the phosphorus modification, the specific metal ions can form a complex with framework oxygen, so that the framework dealumination phenomenon of the molecular sieve under the hydrothermal condition is inhibited, and the thermal stability and the hydrothermal stability of the framework structure of the molecular sieve are enhanced.
After the modified molecular sieve is obtained, the invention mixes the binder with water to obtain precursor slurry, and then sequentially adds kaolin, pseudo-boehmite, hydrochloric acid and the obtained modified molecular sieve under the stirring condition to obtain propylene catalyst mother liquor. In the present invention, the binder is preferably an alumina sol; commercially available or self-made products well known to those skilled in the art may be used. In the present invention, the mass ratio of the binder to water is preferably 1: (4-5), more preferably 1: 4.5.
in the invention, the preferable process of sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition is as follows:
adding kaolin into the precursor slurry, stirring for 0.5-1.5 h at the rotating speed of 300-500 r/min, adding pseudo-boehmite, stirring for 0.4-0.6 h at the rotating speed of 300-500 r/min, adding hydrochloric acid with the concentration of 30-40 wt%, stirring for 0.5-1.5 h at the rotating speed of 300-500 r/min, finally adding the modified molecular sieve obtained in the step a), and stirring for 1-2 h at the rotating speed of 300-500 r/min to obtain propylene catalyst mother liquor;
more preferably:
adding kaolin into the precursor slurry, stirring for 1h at the rotating speed of 400r/min, adding pseudo-boehmite, stirring for 0.5h at the rotating speed of 400r/min, adding hydrochloric acid with the concentration of 37 wt%, stirring for 1h at the rotating speed of 400r/min, finally adding the modified molecular sieve obtained in the step a), and stirring for 1.5h at the rotating speed of 400r/min to obtain the propylene catalyst mother liquor. The sources of the kaolin, pseudoboehmite and hydrochloric acid are not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used.
In the invention, the mass ratio of the precursor slurry, kaolin, pseudoboehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) is preferably (60-100): (10-20): (4-6): 1: (15-20), more preferably (75-80): (13-15): 5: 1: (17.5-18).
After the propylene catalyst mother liquor is obtained, the obtained propylene catalyst mother liquor is molded and roasted to obtain the catalytic cracking propylene catalyst with high yield. In the present invention, the molding is preferably spray molding; the catalyst particles are formed by high-temperature spray centrifugal equipment well known to those skilled in the art.
In the present invention, the temperature of the roasting is preferably 520 ℃ to 560 ℃, more preferably 540 ℃; the roasting time is preferably 2 to 4 hours, and more preferably 3 hours.
The preparation method provided by the invention adopts the hydrogen type ZSM-5 molecular sieve as the raw material, and the modification treatment is carried out by matching with specific steps, so that the better interaction of the whole is realized, and the prepared catalytic cracking propylene-productive catalyst has higher propylene yield and propylene selectivity, has good hydrothermal stability, and can be better used in the petrochemical catalytic cracking field.
The invention also provides a catalytic cracking catalyst for producing more propylene, which is prepared by the preparation method of the technical scheme. After the catalytic cracking catalyst for producing more propylene is obtained, the catalytic cracking performance of the catalytic cracking catalyst for producing more propylene before and after aging is evaluated by adopting a fixed fluidized bed. In the invention, the ageing is preferably basket hydrothermal ageing, and the conditions of the basket hydrothermal ageing are preferably as follows: the temperature is 700-800 ℃, the time is 4-17 h, the water inlet speed is 1-3 g/min, and the optimization is as follows: aging at 750 ℃ for 10h, and feeding water at a rate of 2 g/min.
In the present invention, the fixed fluidized bed evaluation conditions are preferably: the raw oil is wax oil, the amount of the catalyst is 150 g-200 g, the reaction temperature is 520-560 ℃, the catalyst-oil ratio is 4-5, the water inflow is 6 g/min-10 g/min, and the preferable ratio is as follows: the raw oil is wax oil, the catalyst amount is 200g, the reaction temperature is 520 ℃, the catalyst-oil ratio is 5, and the water inflow is 8 g/min.
In the evaluation of the fixed fluidized bed, the catalytic cracking propylene production-increasing catalyst provided by the invention has good propylene selection and high propylene yield, and more importantly, the hydrothermal stability is greatly improved, so that the propylene catalyst with good hydrothermal stability is provided for the market.
The invention provides a catalytic cracking catalyst for producing more propylene and a preparation method thereof; the preparation method comprises the following steps: a) sequentially carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve to obtain a modified molecular sieve; b) mixing a binder and water to obtain precursor slurry, and sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition to obtain propylene catalyst mother liquor; c) molding and roasting the propylene catalyst mother liquor obtained in the step b) to obtain the catalytic cracking propylene catalyst with high yield. Compared with the prior art, the preparation method provided by the invention adopts the hydrogen type ZSM-5 molecular sieve as the raw material, and the modification treatment is carried out by matching with specific steps, so that the overall good interaction is realized, and the prepared catalytic cracking propylene-yielding catalyst has high propylene yield and propylene selectivity, has good hydrothermal stability, and can be better used in the petrochemical catalytic cracking field.
To further illustrate the present invention, the following examples are provided for illustration. The raw materials used in the following examples of the present invention are all commercially available; wherein, the particle size of the hydrogen type ZSM-5 molecular sieve is less than 100nm (nanometer level), and the silica-alumina ratio is 50.
Example 1
(1) 200g of alumina sol was weighed and dissolved in 900g of deionized water under stirring to obtain a mixed solution A.
(2) 195g of kaolin is weighed and dissolved in the mixed solution A under the stirring condition, and the mixed solution B is obtained after stirring for 1 hour at the speed of 400 r/min.
(3) 70g of pseudoboehmite is weighed and added into the mixed solution B, and the mixed solution C is obtained after stirring for 0.5h at the speed of 400 r/min.
(4) 14g of hydrochloric acid with the concentration of 37 wt% is added into the mixed solution C, and the mixed solution D is obtained after stirring for 1h at the speed of 400 r/min.
(5) Weighing 250g of zinc-phosphorus modified molecular sieve, adding the zinc-phosphorus modified molecular sieve into the mixed solution D, and stirring at 400r/min for 1.5h to obtain propylene catalyst mother liquor; the preparation method of the zinc-phosphorus modified molecular sieve comprises the following steps: hydrogen type ZSM-5 molecular sieve is immersed in 1 wt% phosphoric acid solution (P)2O5) Stirring uniformly at room temperature, drying, and roasting at 540 ℃ for 3h to obtain the phosphorus modified molecular sieve; then the phosphorus modified molecular sieve is soaked in Zn (NO) with the mass concentration of 2wt percent3)2And uniformly stirring the solution, drying, and roasting at 540 ℃ for 3h to obtain the zinc-phosphorus modified molecular sieve.
(6) And (3) spray-forming the propylene catalyst mother liquor, and roasting at 540 ℃ for 3h to obtain the catalytic cracking propylene catalyst with high yield.
Example 2
The preparation process provided in example 1 was used with the difference that: replacing a zinc-phosphorus modified molecular sieve with a cerium-phosphorus modified molecular sieve to obtain a catalytic cracking propylene catalyst with high yield; the preparation method of the cerium-phosphorus modified molecular sieve comprises the following steps: hydrogen type ZSM-5 molecular sieve is immersed in 1 wt% phosphoric acid solution (P)2O5) Stirring uniformly at room temperature, drying, and roasting at 540 ℃ for 3h to obtain the phosphorus modified molecular sieve; then the phosphorus modified molecular sieve is soaked in Ce (NO) with the mass concentration of 2wt percent3)3And uniformly stirring the solution, drying, and roasting at 540 ℃ for 3h to obtain the cerium-phosphorus modified molecular sieve.
Example 3
The preparation process provided in example 1 was used with the difference that: replacing a zinc-phosphorus modified molecular sieve with a magnesium-phosphorus modified molecular sieve to obtain a catalytic cracking propylene catalyst with high yield; the preparation method of the magnesium-phosphorus modified molecular sieve comprises the following steps: hydrogen type ZSM-5 molecular sieve is immersed in 1 wt% phosphoric acid solution (P)2O5) Stirring uniformly at room temperature, drying, and roasting at 540 ℃ for 3h to obtain the phosphorus modified molecular sieve; then the phosphorus modified molecular sieve is soaked in Mg (NO) with the mass concentration of 2wt percent3)2And uniformly stirring the solution, drying, and roasting at 540 ℃ for 3h to obtain the magnesium-phosphorus modified molecular sieve.
Comparative example 1
The preparation process provided in example 1 was used with the difference that: the catalyst is obtained by replacing a zinc-phosphorus modified molecular sieve with a hydrogen type ZSM-5 molecular sieve.
Comparative example 2
The preparation process provided in example 1 was used with the difference that: replacing a zinc-phosphorus modified molecular sieve with a phosphorus modified molecular sieve to obtain a catalyst; the preparation method of the phosphorus modified molecular sieve comprises the following steps: hydrogen type ZSM-5 molecular sieve is immersed in 1 wt% phosphoric acid solution (P)2O5) And (4) uniformly stirring at room temperature, drying, and roasting at 540 ℃ for 3h to obtain the phosphorus modified molecular sieve.
Evaluating the catalytic cracking performance of the catalytic cracking propylene-production-increasing catalyst prepared in the examples 1-3 and the catalytic cracking performance of the catalyst prepared in the comparative examples 1-2 before and after aging by using a fixed fluidized bed; the ageing adopts hanging basket hydrothermal ageing, the ageing is carried out for 10 hours at 750 ℃, and the water inlet rate is 2 g/min; the fixed fluidized bed evaluation conditions were: the raw oil is wax oil, the catalyst amount is 200g, the reaction temperature is 520 ℃, the catalyst-oil ratio is 5, and the water inflow is 8 g/min. The performance data are shown in table 1.
TABLE 1 data of catalytic cracking Performance of the catalytic cracking catalyst prepared in examples 1 to 3 and the catalytic cracking catalyst prepared in comparative examples 1 to 2 before and after aging
As shown in the table 1, the distribution data of the catalytic cracking main products of the catalytic cracking catalyst prepared in the examples 1 to 3 and the catalytic cracking main products of the catalyst prepared in the comparative examples 1 to 2 before and after aging show that the liquefied gas yield and the propylene yield are both obviously improved by using the metal modified catalyst in the examples 1 to 3, and the liquefied gas is basically unchanged before and after the catalyst is aged, which indicates that the metal modified catalyst has good hydrothermal stability; wherein the propylene yield of the zinc modified catalyst in example 1 is improved by about 1.3% at most (note: the data is the data obtained by evaluating the existing fixed fluidized bed reactor in a laboratory, and the yield is not obtained by a large-scale riser reactor); the liquefied gas after the catalyst is aged in the comparative example 1 is reduced by 3.3%, and the liquefied gas after the catalyst is aged in the comparative example 2 is reduced by 1.2%, which shows that the catalytic cracking propylene-yielding catalyst prepared by the invention has obviously improved hydrothermal stability.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of a catalytic cracking propylene yield increasing catalyst comprises the following steps:
a) sequentially carrying out phosphorus modification and metal modification on a hydrogen type ZSM-5 molecular sieve to obtain a modified molecular sieve;
b) mixing a binder and water to obtain precursor slurry, and sequentially adding kaolin, pseudo-boehmite, hydrochloric acid and the modified molecular sieve obtained in the step a) under the stirring condition to obtain propylene catalyst mother liquor;
c) molding and roasting the propylene catalyst mother liquor obtained in the step b) to obtain the catalytic cracking propylene catalyst with high yield.
2. The preparation method of claim 1, wherein the hydrogen-type ZSM-5 molecular sieve in step a) has a nano-scale particle size and a silica-alumina ratio of 20-100.
3. The preparation method according to claim 1, wherein the phosphorus modification in step a) is specifically:
hydrogen type ZSM-5 molecular sieve is dipped in phosphorus compound solution with equal mass concentration of 0.2 wt% -10 wt%,stirring uniformly at room temperature, drying, and roasting at 520-560 ℃ for 2-4 h to obtain the phosphorus modified molecular sieve; the phosphorus-containing compound is P2O5。
4. The preparation method according to claim 1, wherein the metal modification in step a) is specifically:
dipping the hydrogen type ZSM-5 molecular sieve modified by phosphorus in a metal compound solution with the same mass and the concentration of 0.5 wt% -8 wt%, uniformly stirring at room temperature, drying, and roasting at 520-560 ℃ for 2-4 h to obtain the modified molecular sieve; the metal compound is selected from Zn (NO)3)2、Ce(NO3)3Or Mg (NO)3)2。
5. The method according to claim 1, wherein the binder in step b) is an aluminum sol; the mass ratio of the binder to the water is 1: (4-5).
6. The preparation method according to claim 1, wherein the sequential addition of kaolin, pseudoboehmite, hydrochloric acid and the modified molecular sieve obtained in step a) under stirring in step b) is specifically:
adding kaolin into the precursor slurry, stirring for 0.5-1.5 h at the rotating speed of 300-500 r/min, adding pseudo-boehmite, stirring for 0.4-0.6 h at the rotating speed of 300-500 r/min, adding hydrochloric acid with the concentration of 30-40 wt%, stirring for 0.5-1.5 h at the rotating speed of 300-500 r/min, finally adding the modified molecular sieve obtained in the step a), and stirring for 1-2 h at the rotating speed of 300-500 r/min to obtain the propylene catalyst mother liquor.
7. The preparation method according to claim 6, wherein the mass ratio of the precursor slurry, kaolin, pseudoboehmite, hydrochloric acid and the modified molecular sieve obtained in step a) is (60-100): (10-20): (4-6): 1: (15-20).
8. The method according to claim 1, wherein the forming in step c) is spray forming.
9. The preparation method according to claim 1, wherein the roasting temperature in step c) is 520-560 ℃ and the roasting time is 2-4 h.
10. A catalytic cracking catalyst for producing more propylene, which is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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| CN115025809A (en) * | 2022-07-14 | 2022-09-09 | 扬州晨化新材料股份有限公司 | Modified hzsm-5 molecular sieve composition for continuously synthesizing tertiary amine catalyst for polyurethane and preparation method thereof |
| CN115845906A (en) * | 2022-12-01 | 2023-03-28 | 黄河三角洲京博化工研究院有限公司 | Preparation method of catalyst for heavy oil to produce more light olefins and aromatic hydrocarbons |
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