CN113509956B - Molecular sieve catalyst, preparation method and application thereof - Google Patents
Molecular sieve catalyst, preparation method and application thereof Download PDFInfo
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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
- B01J29/80—Mixtures of different zeolites
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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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/088—Y-type faujasite
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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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Abstract
The invention provides a molecular sieve catalyst, which comprises the following components: 30-70 parts by mass of hydrogen-type ZSM-5 molecular sieve, 5-20 parts by mass of ultrastable Y-type zeolite and 5-40 parts by mass of adhesive; wherein rare earth element oxide is loaded in the ultrastable Y-type zeolite, and the loading amount of the rare earth element oxide is 0.1-5 parts by mass based on the mass of the rare earth element oxide. The present invention also provides a method of preparing the molecular sieve catalyst of the present invention comprising the steps of: mixing hydrogen-type ZSM-5 molecular sieve, ultrastable Y-type zeolite loaded with rare earth element oxide, adhesive, extrusion aid and peptizing agent, extruding, shaping, drying and calcining in air atmosphere to obtain the molecular sieve catalyst. The molecular sieve catalyst provided by the invention has high activity, stability, coking resistance and metal poisoning resistance.
Description
Technical Field
The invention belongs to the technical field of catalysts. In particular, the invention relates to a molecular sieve catalyst, a preparation method and application thereof.
Background
The products of the methanol synthesis reaction are closely related to the synthesis reaction conditions, such as reaction temperature, space velocity, hydrogen-carbon ratio, selectivity of the catalyst, component change of the reaction gas, trace impurities in the catalyst and activity of the catalyst, and can deviate the synthesis reaction from the main reaction direction to generate various byproducts with boiling points higher than that of methanol, and the mixture formed by the byproducts through a separation tower is commonly called fusel oil.
At present, the fusel oil recycling utilization rate is low. The fusel oil by-produced in the medium and small-sized methanol plants is simply treated and then is sent to a sewage treatment system, or is sent to other systems as fuel, or is sent to a coal preparation system for burning, and the fusel oil by-produced in the large-sized methanol plants is directly sold as a product at low price, so that the economic benefit of enterprises is greatly reduced.
In the prior art, catalytic conversion of fusel oil has been explored. For example, chinese patent No. 101811920A discloses a method for preparing low-carbon olefin on a silicoaluminophosphate molecular sieve catalyst under the condition of co-feeding methanol and fusel oil, wherein the reaction condition is 400-550 ℃ and 0.01-0.3 MPa; CN105384593a discloses a process for producing olefins on ZSM-5 molecular sieve catalysts using methanol and fusel oil co-feed at a reaction condition of 350 ℃ to 550 ℃ and 0.1MPa to 0.3MPa.
However, since the fusel oil has a complex composition, it contains C in addition to methanol and water 2 + Mechanical impurities and trace amounts of metal impurities (e.g., copper-based catalysts and iron-containing impurities) entrained from the production system are also present (Zhang Zifeng, zhang Fanjun, published by methanol production technology, chemical industry publishers, 2007). Therefore, when a single-component ZSM-5 type catalyst or an SAPO type molecular sieve is used as a catalyst, and fusel oil and methanol are used for feeding together, the catalyst has the risks of rapid coking and poisoning deactivation.
Thus, there remains a need to provide molecular sieve catalysts and methods of making for the conversion of fusel oils to olefins. According to the characteristics of fusel oil, the catalyst needs to have high raw material adaptability, high catalytic activity, high coking resistance, high metal poisoning resistance and high stability. Meanwhile, the catalyst is required to be capable of being applied and popularized in a large scale to improve the economical efficiency of preparing olefin by converting fusel oil.
Disclosure of Invention
It is therefore an object of the present invention to provide a molecular sieve catalyst for the conversion of fusel oils to olefins which has high activity, stability, coking resistance and metal poisoning resistance. It is another object of the present invention to provide a process for preparing the molecular sieve catalyst.
The above object of the present invention is achieved by the following technical solutions.
In the context of the present invention, the term "silica to alumina molar ratio" (silica alumina molar ratio, SAR) generally refers to the molar ratio of elemental silicon to elemental aluminum in a material such as a molecular sieve.
In the context of the present invention, the term "ultrastable Y-type zeolite" may also be referred to as "USY zeolite" which may be obtained from a Y-type zeolite by ultrastable treatment using techniques known in the art, or may be used directly as a commercially available ultrastable Y-type zeolite.
In a first aspect, the present invention provides a molecular sieve catalyst comprising the following components: 30-70 parts by mass of hydrogen-type ZSM-5 molecular sieve, 5-20 parts by mass of ultrastable Y-type zeolite and 5-40 parts by mass of adhesive;
wherein rare earth element oxide is loaded in the ultrastable Y-type zeolite, and the loading amount of the rare earth element oxide is 0.1-5 parts by mass based on the mass of the rare earth element oxide.
Preferably, in the molecular sieve catalyst of the present invention, the hydrogen form ZSM-5 molecular sieve has a silica to alumina molar ratio of from 30 to 500, more preferably from 50 to 100.
Preferably, in the molecular sieve catalyst of the present invention, the ultrastable Y-type zeolite has a silica to alumina molar ratio of 3 to 30, more preferably 5 to 10.
Preferably, in the molecular sieve catalyst of the present invention, the rare earth element in the rare earth element oxide is one or more of La, ce, Y, pr, nb and Sm.
Preferably, in the molecular sieve catalyst according to the present invention, the rare earth element oxide is supported in an amount of 0.1 to 2 parts by mass based on the mass of the rare earth element oxide.
Preferably, in the molecular sieve catalyst according to the present invention, the binder is one or more of activated alumina, pseudo-boehmite, kaolin and clay.
In a second aspect, the present invention provides a process for preparing the molecular sieve catalyst of the present invention comprising the steps of:
mixing hydrogen-type ZSM-5 molecular sieve, ultrastable Y-type zeolite loaded with rare earth element oxide, adhesive, extrusion aid and peptizing agent, extruding, shaping, drying and calcining in air atmosphere to obtain the molecular sieve catalyst.
Preferably, in the method of the present invention, the ultrastable Y-type zeolite loaded with rare earth element oxide is prepared by a method comprising the steps of:
(1) Impregnating the ultrastable Y-type zeolite with an aqueous solution of a soluble compound of a rare earth element, and then drying and roasting to obtain a precursor;
(2) And carrying out hydrothermal aging treatment on the precursor, and then naturally cooling in protective gas to obtain the ultrastable Y-type zeolite loaded with rare earth element oxide.
In the present invention, the ultrastable Y-type zeolite can be impregnated by methods known in the art, for example, huang Zhongtao, geng Jianming, industrial catalysis (second edition), beijing: the isovolumetric impregnation method described in the chemical industry press 2006. In some embodiments, the USY zeolite is impregnated using an isovolumetric impregnation process for a period of 8 to 12 hours.
In the method of the present invention, the soluble compound of a rare earth element is a nitrate, sulfate, chloride or the like of a metal element. The aqueous solution of the soluble compound of a rare earth element is prepared by dissolving the soluble compound of a rare earth element in deionized water.
Preferably, in the method of the present invention, the firing in the step (1) is performed under the following conditions: the roasting temperature is 500-550 ℃ and the roasting time is 5-10 hours.
Preferably, in the method of the present invention, the hydrothermal aging treatment in the step (2) is performed under the following conditions: the hydrothermal aging temperature is 650-800 ℃, and the hydrothermal aging time is 5-10 hours.
Preferably, in the method of the present invention, the protective gas in the step (2) is nitrogen, helium or argon.
Preferably, in the method of the present invention, the binder is one or more of activated alumina, pseudo-boehmite, and kaolin and clay.
Preferably, in the method of the present invention, the extrusion aid is one or more of graphite powder, sesbania powder, oxalic acid, citric acid, glycerol and stearic acid.
Preferably, in the method of the invention, the extrusion aid is used in an amount of 1 to 5% of the total mass of the molecular sieve catalyst.
Preferably, in the method of the present invention, the peptizing agent is one or more of nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, acetic acid and malonic acid.
Preferably, in the method of the present invention, the peptizing agent is in the form of a solution having a mass concentration of 10 to 30%.
Preferably, in the method of the present invention, the ratio of the total mass of the hydrogen-form ZSM-5 molecular sieve, the ultrastable Y-type zeolite loaded with rare earth metal oxide and the binder to the volume of the peptizing agent solution is 1:1-1.8g/ml.
Preferably, in the method of the present invention, the calcination is performed under the following conditions: the calcination temperature is 500-700 ℃ and the calcination time is 4-10h.
In a third aspect, the present invention provides the use of the molecular sieve catalyst of the present invention or the molecular sieve catalyst prepared by the process of the present invention in the conversion of fusel oil to produce olefins.
The invention has the following beneficial effects:
(1) The molecular sieve catalyst provided by the invention contains rare earth modified ultrastable Y-type zeolite, wherein the ultrastable Y-type zeolite has the characteristics of small cell contraction, good acid center control, low coke content and the like. After the rare earth modification is adopted, the ultrastable Y-type zeolite has high activity and strong metal pollution resistance, and meanwhile, the molecular sieve catalyst has high coking resistance and metal poisoning resistance, and the defect of short service life of the catalyst in the prior art is overcome.
(2) The molecular sieve catalyst of the invention contains two active components, namely rare earth modified ultrastable Y-type zeolite and ZSM-5 molecular sieve. Wherein the ultra-stable Y-type zeolite takes an octahedral zeolite cage as a main framework structure, the maximum orifice of the ultra-stable Y-type zeolite is a 12-membered ring, and the diameter of the maximum pore canal is about 0.7-0.9nm; and ZSM-5 is a 10-membered ring, and the maximum pore structure is 0.53-0.56nm. The multistage pore canal of the molecular sieve catalyst of the invention ensures that the catalyst has good mass transfer and diffusion performance on one hand, and on the other hand, the multistage pore canal of the molecular sieve catalyst ensures that macromolecular high-carbon products in fusel oil can be transferred into an active center to be converted into olefin, thereby overcoming the defect that a single pore canal structure in the catalyst in the prior art is easy to block and easy to coke and inactivate.
(3) Compared with the prior art, the molecular sieve catalyst disclosed by the invention adopts two different active centers and molecular sieves with two different pore channel characteristics as active components, so that the adaptability of the catalyst to reaction raw materials is greatly improved in the reaction process of preparing olefin by converting fusel oil, and the catalyst has the characteristics of high activity, high olefin selectivity and high stability.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof.
Example 1
This example illustrates a molecular sieve catalyst for converting fusel oil to olefins and a method for preparing the same. Specifically, the preparation method of the molecular sieve catalyst comprises the following steps:
(1) Hydrothermally treating rare earth element oxide modified USY zeolite:
1.0g La (NO) was weighed out 3 ) 3 Dissolving in 10mL deionized water to obtain a solution, adding 10.0g USY zeolite (SAR 5 of catalyst plant of petrochemical company, lanzhou), soaking at room temperature for 10 hr, oven drying at 120deg.C, and calcining at 550deg.C for 5 hr to obtain La-loaded powder 2 O 3 USY zeolite of (a).
Loading La on the above 2 O 3 Is used for the sample of USY zeoliteIntroducing 120 deg.C saturated steam into a tube furnace, treating at 700 deg.C for 6 hr, and subjecting the sample to N 2 Cooling to room temperature in the atmosphere to obtain hydrothermally treated La 2 O 3 Modified USY zeolite.
(2) And (3) preparing a molecular sieve catalyst by molding and roasting:
weighing the water-heat treated La prepared in the step (1) 2 O 3 8.5g of modified zeolite, 20.0g of hydrogen ZSM-5 molecular sieve (SAR is 100 in Shanghai Fuxu molecular sieve plant), 9.0g of activated alumina (adhesive) and 1.0g of sesbania powder (extrusion aid) are uniformly mixed, 45.0mL of nitric acid solution (peptizer) with the mass percentage of 25% is added, extruded and molded, dried at 80 ℃ and baked at 550 ℃ for 5 hours, thus obtaining the target catalyst.
Examples 2 to 6
Referring to example 1, a molecular sieve catalyst of different composition was prepared for conversion of fusel oil to olefins. The preparation materials and part of the conditions for the molecular sieve catalysts of examples 2-6 are shown in Table 1. In addition, in the preparation step of the rare earth element oxide modified USY zeolite by hydrothermal treatment, saturated steam at 150 ℃ is introduced, and the mixture is treated for 8 hours at 750 ℃; and in the roasting step of the molecular sieve catalyst, extruding strips, drying at 100 ℃ and roasting at 550 ℃ for 8 hours to obtain the target catalyst.
Table 1 examples 2 to 6 catalyst raw material ratios and preparation conditions
Comparative example 1
The single-active component catalyst formed by the ZMS-5 molecular sieve comprises the following steps:
28.5g of hydrogen ZSM-5 molecular sieve (SAR of 100 in Shanghai Fu molecular sieve Co., ltd.), 9.0g of active alumina (adhesive) and 1.0g of sesbania powder (extrusion aid) are weighed, evenly mixed, 45.0mL of nitric acid solution (peptizer) with the mass percent of 25% is added, extruded, molded, dried at 80 ℃ and baked at 550 ℃ for 5 hours, thus obtaining the target catalyst.
Comparative example 2
A one-component catalyst molded by SAPO-34 molecular sieve comprises the following steps:
28.5g of SAPO-34 molecular sieve (Si: P: al=0.2:1:1, new material Co., ltd.), 9.0g of activated alumina (binder) and 1.0g of sesbania powder (extrusion aid) are weighed, evenly mixed, 45.0mL of nitric acid solution (peptizer) with the mass percentage of 25% is added, extruded and molded, dried at 80 ℃ and baked at 550 ℃ for 5 hours, thus obtaining the target catalyst.
Comparative example 3
A bi-component molecular sieve catalyst prepared from USY molecular sieve which is not modified by rare earth and H-ZSM-5. Specifically, the preparation method of the molecular sieve catalyst comprises the following steps:
8.5g of USY zeolite (catalyst factory of Lanzhou petrochemical company, SAR is 5), 20.0g of hydrogen-type ZSM-5 molecular sieve (Shanghai Fuxu molecular sieve factory, SAR is 100), 9.0g of active alumina (adhesive) and 1.0g of sesbania powder (extrusion aid) are weighed, evenly mixed, 45.0mL of nitric acid solution (peptizing agent) with the mass percentage of 25% is added, extruded, molded, dried at 80 ℃ and baked at 550 ℃ for 5 hours, thus obtaining the target catalyst.
Evaluation of catalytic Performance
The catalysts prepared in examples 1 and 3 and comparative examples 1, 2 and 3 were evaluated for catalytic performance using a fixed bed flow reactor. The catalyst loading per evaluation was 3.0g, and fusel oil as a byproduct of a methanol plant was used as a raw material (composition shown in Table 2), and the liquid hourly space velocity was 2h at 500 ℃ －1 The total pressure of the system is 0.1MPa. The products were analyzed on-line by gas chromatography with an HP-PLOT-Q column, all of which were finally normalized, expressed as mass content of carbon-based, and the reaction results are shown in Table 3.
TABLE 2 composition and content of fusel
TABLE 3 evaluation of product selectivity and stability of catalysts
As is clear from the results of Table 3, the catalysts of examples 1 and 3 achieve high yields of lower olefins, ethylene, propylene and butene (C 2 ＝ +C 3 ＝ +C 4 ＝ The sum of the selectivities) and higher stability (namely the time from 100% to 90% of the initial conversion rate in the table), which indicates that the catalyst prepared by the technology has higher activity, low-carbon olefin selectivity, coking resistance and metal poisoning resistance.
Claims (19)
1. Use of a molecular sieve catalyst in the preparation of olefins by conversion of fusel oil, wherein the molecular sieve catalyst comprises the following components: 30-70 parts by mass of hydrogen-type ZSM-5 molecular sieve, 5-20 parts by mass of ultrastable Y-type zeolite and 5-40 parts by mass of adhesive;
wherein rare earth element oxide is loaded in the ultrastable Y-type zeolite, and the loading amount of the rare earth element oxide is 0.1-5 parts by mass of the rare earth element oxide;
the rare earth element in the rare earth element oxide is one or more of La, ce, Y, pr, nb and Sm.
2. Use according to claim 1, wherein the hydrogen form ZSM-5 molecular sieve has a molar ratio of silicon to aluminium of 30-500.
3. Use according to claim 2, wherein the hydrogen form ZSM-5 molecular sieve has a molar ratio of silicon to aluminium of 50-100.
4. The use according to claim 1, wherein the ultrastable Y zeolite has a molar ratio of silica to alumina of 3 to 30.
5. The use according to claim 4, wherein the ultrastable Y zeolite has a molar ratio of silica to alumina of 5 to 10.
6. The use according to claim 1, wherein the rare earth element oxide is supported in an amount of 0.1 to 2 parts by mass based on the mass of the rare earth element oxide.
7. The use according to claim 1, wherein the binder is one or more of activated alumina, pseudo-boehmite, kaolin and clay.
8. The use of claim 1, wherein the molecular sieve catalyst is prepared by a process comprising the steps of:
mixing hydrogen-type ZSM-5 molecular sieve, ultrastable Y-type zeolite loaded with rare earth element oxide, adhesive, extrusion aid and peptizing agent, extruding, shaping, drying and calcining in air atmosphere to obtain the molecular sieve catalyst.
9. The use according to claim 8, wherein the ultrastable Y zeolite loaded with rare earth oxides is prepared by a process comprising the steps of:
(1) Impregnating the ultrastable Y-type zeolite with an aqueous solution of a soluble compound of a rare earth element, and then drying and roasting to obtain a precursor;
(2) And carrying out hydrothermal aging treatment on the precursor, and then naturally cooling in protective gas to obtain the ultrastable Y-type zeolite loaded with rare earth element oxide.
10. The use according to claim 9, wherein the firing in step (1) is performed under the following conditions: the roasting temperature is 500-550 ℃ and the roasting time is 5-10 hours.
11. The use according to claim 9, wherein the hydrothermal ageing treatment in step (2) is carried out under the following conditions: the hydrothermal aging temperature is 650-800 ℃, and the hydrothermal aging time is 5-10 hours.
12. The use according to claim 9, wherein the protective gas in step (2) is nitrogen, helium or argon.
13. The use according to claim 8, wherein the binder is one or more of activated alumina, pseudo-boehmite and kaolin and clay.
14. The use according to claim 8, wherein the extrusion aid is one or more of graphite powder, sesbania powder, oxalic acid, citric acid, glycerol and stearic acid.
15. The use according to claim 8, wherein the extrusion aid is used in an amount of 1-5% of the total mass of the molecular sieve catalyst.
16. The use according to claim 8, wherein the peptizing agent is one or more of nitric acid, hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, acetic acid and malonic acid.
17. Use according to claim 8, wherein the peptizing agent is in the form of a solution with a mass concentration of 10-30%.
18. Use according to claim 8, wherein the ratio of the total mass of hydrogen-form ZSM-5 molecular sieve, ultrastable Y-zeolite loaded with rare earth metal oxide and binder to the volume of peptizing agent solution is 1:1-1.8g/ml.
19. The use according to claim 8, wherein the calcination is performed under the following conditions: the calcination temperature is 500-700 ℃ and the calcination time is 4-10h.
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| 李栋藩等.稀土含量对超稳Y沸石的酸性及裂化的影响，《石油学报（石油化工）》.1990,第6卷(第1期),第1节第1段、第2节第2段. * |
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