CN111072046A - Method for preparing ZSM-5 molecular sieve by using catalytic cracking waste catalyst - Google Patents
Method for preparing ZSM-5 molecular sieve by using catalytic cracking waste catalyst Download PDFInfo
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- CN111072046A CN111072046A CN201911365451.4A CN201911365451A CN111072046A CN 111072046 A CN111072046 A CN 111072046A CN 201911365451 A CN201911365451 A CN 201911365451A CN 111072046 A CN111072046 A CN 111072046A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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- 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
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention relates to a method for preparing a ZSM-5 molecular sieve by using a catalytic cracking spent catalyst, which comprises the following steps: s101: firstly, mixing and uniformly stirring a catalytic cracking waste catalyst, sodium hydroxide and water; s102: adding a silica sol solution into the sample obtained in the step S101 and uniformly stirring; s103: heating the sample obtained in the step S102 to 178-182 ℃ and standing for crystallization; s104: and cooling the sample obtained in the step S103 to room temperature, carrying out suction filtration, washing the sample to be neutral by using deionized water, and drying the sample to obtain the ZSM-5 molecular sieve. The method for preparing the ZSM-5 molecular sieve by using the catalytic cracking waste catalyst solves the problem of large-scale discharge of the catalytic cracking waste catalyst, realizes high-efficiency and quick utilization of the waste catalyst, and has good commercial prospect.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to a method for preparing a ZSM-5 molecular sieve by using a catalytic cracking waste catalyst.
Background
Fluid Catalytic Cracking (FCC) of petroleum is a process of Cracking heavy oil into C1-C4 gas, gasoline, diesel oil and the like at a temperature of 700-800 ℃, and is the most important secondary processing process of crude oil in the petroleum refining process. In the modern petroleum refining industry, catalytic cracking is an important component, and is especially important in the Chinese oil refining industry. About 70% of gasoline production tasks in China are completed by a catalytic cracking process. Heavy oil generates a large amount of catalytic cracking spent catalyst each year in the process of being catalytically cracked into light oil. In 2016, China puts catalytic cracking waste catalysts into HW50 waste catalyst hazardous wastes in the national hazardous wastes list, and the waste catalysts cannot be freely buried, even if the landfill cost is extremely high.
In the FCC process, metal ions such as nickel (Ni), iron (Fe), and vanadium (V) contained in the feedstock oil are deposited on the FCC catalyst surface, which leads to catalyst poisoning and deactivation, and coking, carbon deposition, and mechanical abrasion impact are also one of the causes of catalyst deactivation. The main component of the deactivated FCC catalyst is SiO2And Al2O3And also contains a small amount of Ni, Fe, V, Na and other elements. The traditional method for treating the waste catalyst is a landfill method. The landfill method can cause resource waste and also can cause serious pollution to soil, underground water and atmosphere, direct discharge of catalytic cracking waste catalysts is forbidden by the regulation of many countries, and corresponding restriction measures are provided in China. In addition to landfill, there are two general types of treatment. The first kind is to perform catalytic cracking on waste catalyst mainly by means of demetalization regeneration, magnetic separation and other technological stepsReviving or screening, and then reusing for recovering and reusing the FCC unit. Such processes have the advantage of saving catalyst while reducing environmental pollution, but have limited metal removal rates and are expensive and have limited application ranges. However, the method has an unobvious treatment effect on the waste catalyst with high pollution degree and serious structural damage, and cannot completely solve the treatment problem of the catalytic cracking waste catalyst. The other method combines the structure and chemical properties of the catalytic cracking waste catalyst, such as the molecular sieve structure and Ni, Fe, V and the like which are good catalytic hydrogenation active components, and applies the catalytic cracking waste catalyst to the aspects of hydrogenation catalysts, catalyst carriers, cracking catalysts, molecular sieves, adsorbents and the like, so that the catalytic cracking waste catalyst can be recycled, and has higher application value in the aspects of economy and environmental protection. Chinese patent CN109305688A discloses a method for synthesizing NaA type molecular sieve material by catalytic cracking waste catalyst, which takes catalytic cracking waste catalyst as raw material, and prepares NaA type molecular sieve by adding sodium carbonate, sodium silicate, sodium hydroxide, sodium aluminate and other raw materials. Chinese patent CN108190910A discloses a method for preparing a Y-type molecular sieve by microwave heating a waste catalyst, which is characterized in that the waste catalyst is used as an aluminum source after demetallization and reactivation, and the Y-type molecular sieve is prepared by microwave under the condition of adding a silicon source, a sodium source, water and a guiding agent. The method not only can solve the problem of large-scale discharge of the waste catalyst, but also realizes the efficient and rapid utilization of the waste catalyst. However, at present, no patent for preparing the ZSM-5 molecular sieve by using the catalytic cracking waste catalyst as the raw material is seen.
Disclosure of Invention
One object of the present invention is to propose a method for preparing a ZSM-5 molecular sieve using a catalytic cracking spent catalyst.
The invention discloses a method for preparing a ZSM-5 molecular sieve by using a catalytic cracking spent catalyst, which comprises the following steps: s101: firstly, mixing and uniformly stirring a catalytic cracking waste catalyst, sodium hydroxide and water; s102: adding a silica sol solution into the sample obtained in the step S101 and uniformly stirring; s103: heating the sample obtained in the step S102 to 178-182 ℃ and standing for crystallization; s104: and cooling the sample obtained in the step S103 to room temperature, carrying out suction filtration, washing the sample to be neutral by using deionized water, and drying the sample to obtain the ZSM-5 molecular sieve.
The method for preparing the ZSM-5 molecular sieve by using the catalytic cracking waste catalyst solves the problem of large-scale discharge of the catalytic cracking waste catalyst, realizes high-efficiency and quick utilization of the waste catalyst, and has good commercial prospect.
In addition, the method for preparing the ZSM-5 molecular sieve by using the catalytic cracking spent catalyst can also have the following additional technical characteristics:
further, in the step S101, the catalytic cracking waste catalyst is 0.6 to 1.8 parts by weight, the sodium hydroxide is 0.2 to 0.3 parts by weight, and the water is 7.5 to 8 parts by weight.
Further, in the step S102, the mass percentage of the silica sol in the silica sol solution is 38% to 42%; the weight portion of the silica sol solution is 2.5 to 3.
Further, in the step S103, the standing crystallization time is 8 to 30 hours.
Further, in the step S104, the drying temperature is 78 to 82 ℃.
Further, in the step S101, the stirring time is 8 to 15 min.
Further, in the step S102, the stirring time is 25min to 35 min.
The invention also aims to provide the ZSM-5 molecular sieve prepared by the method.
The invention also aims to provide the application of the ZSM-5 molecular sieve in the field of catalysts.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an XRD spectrum of the product of example 1;
FIG. 2 is an SEM image of the product of example 1;
FIG. 3 is an XRD spectrum of the product of example 2;
FIG. 4 is an SEM image of the product of example 2;
FIG. 5 is an XRD spectrum of the product of example 3;
FIG. 6 is an SEM image of the product of example 3;
FIG. 7 is an XRD spectrum of the product of example 4;
fig. 8 is an SEM image of the product of example 4.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The invention provides a method for preparing a ZSM-5 molecular sieve by using a catalytic cracking spent catalyst, which comprises the following steps:
(1) firstly, mixing the catalytic cracking waste catalyst with sodium hydroxide and water, and stirring for 8-15 min. Wherein, the weight portion of the catalytic cracking waste catalyst is 0.6 to 1.8, the weight portion of the sodium hydroxide is 0.2 to 0.3, and the weight portion of the water is 7.5 to 8.
(2) And (2) adding a silica sol solution into the sample obtained in the step (1) and stirring for 25-35 min. In the silica sol solution, the mass percent of the silica sol is 38-42%; the weight portion of the silica sol solution is 2.5 to 3.
(3) Heating the sample obtained in the step (2) to 178-182 ℃ and standing for crystallization for 8-30 h.
(4) And (4) cooling the sample obtained in the step (3) to room temperature, carrying out suction filtration, washing the sample to be neutral by using deionized water, and drying the sample at the temperature of 78-82 ℃ to obtain the ZSM-5 molecular sieve.
The invention is described in detail below by means of specific examples:
example 1
1.5g of catalytic cracking spent catalyst was added to a beaker, followed by 0.2g of NaOH, followed by 7.7g H2O, and stirred at room temperature for 10 min. After stirring well, 2.70g of 40% silica sol was added dropwise, and stirring was continued at room temperature for 30 min. And transferring the reaction solution into a reaction kettle, and standing and crystallizing the reaction solution in an oven at 180 ℃ for 24 hours. After crystallization is finished, cooling the reaction liquid to room temperature, then carrying out suction filtration on the product, washing the product to be neutral by using deionized water, and drying the product at 80 ℃ to obtain a solid powder sample. The XRD pattern of the product is shown in figure 1. The synthesized product is ZSM-5 molecular sieve according to XRD spectrogram. SEM photograph of the product is shown in fig. 2.
Example 2
0.6g of a catalytic cracking waste catalyst, 0.2g of NaOH, 7.7g H2O and the mixture were added to a beaker and stirred at room temperature for 10 min. After stirring well, 2.70g of 40% silica sol was added dropwise, and stirring was continued at room temperature for 30 min. And transferring the reaction solution into a reaction kettle, and standing and crystallizing the reaction solution in an oven at 180 ℃ for 24 hours. After crystallization is finished, cooling the reaction liquid to room temperature, then carrying out suction filtration on the product, washing the product to be neutral by using deionized water, and drying the product at 80 ℃ to obtain a solid powder sample. The XRD pattern of the product is shown in figure 3. The XRD spectrogram shows that the synthesized product is a ZSM-5 molecular sieve. SEM photograph of the product is shown in fig. 4.
Example 3
1.8g of a catalytic cracking waste catalyst, 0.3g of NaOH, 9.32g H2O and the mixture was stirred at room temperature for 10 min. After stirring uniformly, 1.08g of white carbon black is slowly added, and stirring is continued for 30min at room temperature. And transferring the reaction solution into a reaction kettle, and standing and crystallizing the reaction solution in an oven at 180 ℃ for 24 hours. After crystallization is finished, cooling the reaction liquid to room temperature, then carrying out suction filtration on the product, washing the product to be neutral by using deionized water, and drying the product at 80 ℃ to obtain a solid powder sample. The XRD pattern of the product is shown in FIG. 5. The XRD spectrogram shows that the synthesized product is a ZSM-5 molecular sieve. See figure 6 for SEM photographs of the product.
Example 4
0.6g of a catalytic cracking spent catalyst, 0.2g of NaOH, 4.27g H2O and the mixture were added to a beaker and stirred at room temperature for 10 min. After stirring well, 5.64g of sodium silicate was added dropwise and stirring was continued at room temperature for 30 min. And transferring the reaction solution into a reaction kettle, and standing and crystallizing the reaction solution in an oven at 180 ℃ for 24 hours. After crystallization is finished, cooling the reaction liquid to room temperature, then carrying out suction filtration on the product, washing the product to be neutral by using deionized water, and drying the product at 80 ℃ to obtain a solid powder sample. The XRD pattern of the product is shown in FIG. 7. The XRD spectrogram shows that the synthesized product is a ZSM-5 molecular sieve. See figure 8 for SEM photographs of the product.
In conclusion, the method for preparing the ZSM-5 molecular sieve by using the catalytic cracking waste catalyst solves the problem of large-scale discharge of the catalytic cracking waste catalyst, realizes high-efficiency and quick utilization of the waste catalyst, and has good commercial prospect.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. A method for preparing a ZSM-5 molecular sieve by using a catalytic cracking spent catalyst is characterized by comprising the following steps:
s101: firstly, mixing and uniformly stirring a catalytic cracking waste catalyst, sodium hydroxide and water;
s102: adding a silica sol solution into the sample obtained in the step S101 and uniformly stirring;
s103: heating the sample obtained in the step S102 to 178-182 ℃ and standing for crystallization;
s104: and cooling the sample obtained in the step S103 to room temperature, carrying out suction filtration, washing the sample to be neutral by using deionized water, and drying the sample to obtain the ZSM-5 molecular sieve.
2. The method for preparing ZSM-5 molecular sieve as claimed in claim 1, wherein in step S101, the catalytic cracking spent catalyst is in the range of 0.6 to 1.8 parts by weight, the sodium hydroxide is in the range of 0.2 to 0.3 parts by weight, and the water is in the range of 7.5 to 8 parts by weight.
3. The method for preparing ZSM-5 molecular sieve according to claim 1, wherein in the step S102, the mass percentage of silica sol in the silica sol solution is 38% to 42%; the weight portion of the silica sol solution is 2.5 to 3.
4. The method for preparing ZSM-5 molecular sieve as claimed in claim 1, wherein in step S103, the standing crystallization time is 8-30 hours.
5. The method for preparing ZSM-5 molecular sieve as claimed in claim 1, wherein in step S104, the temperature for drying is 78-82 ℃.
6. The method for preparing ZSM-5 molecular sieve according to claim 1, wherein in the step S101, the stirring time is 8-15 min.
7. The method for preparing ZSM-5 molecular sieve as claimed in claim 1, wherein in step S102, the stirring time is 25min to 35 min.
8. A ZSM-5 molecular sieve prepared by the method of any one of claims 1 to 7.
9. Use of the ZSM-5 molecular sieve of claim 8 in the field of catalysts.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112093809A (en) * | 2020-08-13 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Waste catalyst treatment method, HZSM-5 molecular sieve, and preparation method and application thereof |
| CN115057453A (en) * | 2022-06-07 | 2022-09-16 | 福州大学 | Method for preparing SSZ-13 molecular sieve by using FCC (fluid catalytic cracking) waste catalyst and application thereof |
| CN116462208A (en) * | 2023-03-29 | 2023-07-21 | 河北欣芮再生资源利用有限公司 | Method for preparing ZSM-5 molecular sieve by using catalytic cracking dead catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368571B1 (en) * | 2000-01-28 | 2002-04-09 | Chk Group, Inc. | ZSM-5 made from siliceous ash |
| CN106938849A (en) * | 2016-12-13 | 2017-07-11 | 江苏天诺新材料科技股份有限公司 | The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst |
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- 2019-12-26 CN CN201911365451.4A patent/CN111072046A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6368571B1 (en) * | 2000-01-28 | 2002-04-09 | Chk Group, Inc. | ZSM-5 made from siliceous ash |
| CN106938849A (en) * | 2016-12-13 | 2017-07-11 | 江苏天诺新材料科技股份有限公司 | The method that the molecular sieves of ZSM 5 are synthesized using waste and old molecular sieve catalyst |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112093809A (en) * | 2020-08-13 | 2020-12-18 | 国家能源集团宁夏煤业有限责任公司 | Waste catalyst treatment method, HZSM-5 molecular sieve, and preparation method and application thereof |
| CN115057453A (en) * | 2022-06-07 | 2022-09-16 | 福州大学 | Method for preparing SSZ-13 molecular sieve by using FCC (fluid catalytic cracking) waste catalyst and application thereof |
| CN115057453B (en) * | 2022-06-07 | 2023-10-20 | 福州大学 | Method for preparing SSZ-13 molecular sieve by using FCC spent catalyst and application thereof |
| CN116462208A (en) * | 2023-03-29 | 2023-07-21 | 河北欣芮再生资源利用有限公司 | Method for preparing ZSM-5 molecular sieve by using catalytic cracking dead catalyst |
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