CN113509955A - Cobalt-based molecular sieve catalyst and preparation method and application thereof - Google Patents
Cobalt-based molecular sieve catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cobalt-based molecular sieve catalyst, and a preparation method and application thereof, and belongs to the field of catalysts for preparing propylene by propane dehydrogenation. Mixing a silicon source, a template agent, a cobalt source, an additive and water, carrying out hydrothermal crystallization to obtain a suspension, centrifuging to obtain a solid, and washing, drying and roasting to obtain the cobalt-based molecular sieve catalyst. The Co-based molecular sieve has the advantages of large specific surface area, good hydrothermal stability and the like, and compared with the catalyst prepared by the traditional impregnation method, the catalyst prepared by the method has higher propane dehydrogenation activity and stability, and has the advantages of simple preparation process, lower cost, environmental friendliness and higher industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts for preparing propylene by propane dehydrogenation, and particularly relates to a cobalt-based molecular sieve catalyst with a transition metal Co implanted into a molecular sieve framework, a preparation method of the cobalt-based molecular sieve catalyst, and application of the cobalt-based molecular sieve catalyst in reaction for preparing propylene by propane dehydrogenation.
Background
Propylene is an important petrochemical basic raw material second only to ethylene, and is mainly used for producing polypropylene, propylene oxide, butanol-octanol, acrylonitrile, acrylic acid and the like. The traditional propylene production process mainly comes from the fluid catalytic cracking and steam cracking of naphtha, light diesel and the like. Due to the defects of high energy consumption and the like in the steam cracking process, the demand of the market for propylene downstream derivatives is rapidly increased, the traditional propylene production method cannot meet the demand, and the development of propylene production technologies is correspondingly accelerated, such as a propane dehydrogenation technology (PDH), a Methanol To Olefin (MTO) technology, a Fischer-Tropsch synthesis to olefin (FTO) technology, a low-carbon olefin catalysis to propylene (OCP) technology and the like. The PDH technology has the advantages of simple process route, low energy consumption, safety, environmental protection and the like, and simultaneously, as the shale gas and natural gas exploration technology is mature, the price of propane is reduced, so that the PDH technology is a route with great prospect and competitiveness, and becomes one of technologies which are vigorously developed by vast researchers and petrochemical enterprises.
Pt group and CrOxThe catalyst has excellent propane dehydrogenation performance, is the most studied catalyst for propane anaerobic dehydrogenation at present, but is limited by the cost of Pt-series noble metal catalysts and the environmental pollution caused by Cr-series catalysts. Meanwhile, Pt particles of the Pt-based catalyst are easy to agglomerate in the reaction process, so that the catalyst is deactivated. There is therefore an urgent need to develop a low-cost, high-activity and high-stability catalyst for direct dehydrogenation of propane. Subsequent research by researchers has developed inexpensive and environmentally friendly catalysts including metal oxides MOx (V, Ga, Zr, In, Zn, Fe, Co, etc.) and non-metallic catalysts carbides, nitrides, carbon materials, etc., but still cannot achieve both high catalytic activity and low catalyst deactivation rates.
Co metal is used as a metal with abundant reserves and low toxicity,moselage et al [ ACS Catal., 2016, 6, 498.]Early discovery of Co-based catalysts was effective in activating C-H bonds. Then researchers load Co on different carriers to prepare Co/SiO2[ J. Catal., 2015, 322, 24.]、CoAl2O4[ ChemCatChem, 2017, 9, 3330]、Co-ZSM-5[ J. Phys. Chem. B, 2001, 105, 1176]、Co/γ-Al2O3[ J. Catal., 2020, 381, 482.]And Sibeta [ J. Catal., 2020, 383, 77]It is considered that Co is effective as a Lewis acid center for activating dehydrogenation of propane to produce propylene. CN111589449 adopts a hydrothermal method to synthesize Co/Al2O3The catalyst is found to have higher propane dehydrogenation activity and stability. The current research reports that the selectivity of the product propylene in the propane dehydrogenation reaction of the Co-based catalyst cannot be achieved>99 percent, and the catalyst has low service life stability and is easy to deactivate, and the main reasons are two aspects: on the one hand, the active center of Co ions is in H during the reaction process2Co with lower valence state and even metallic state Co are easily reduced in reducing atmosphere, thus leading to the aggregation of Co active center and promoting the cracking of propane to generate by-products such as methane, ethane, ethylene, carbon deposition and the like; on the other hand catalyst supports (e.g. amorphous SiO)2And HZSM-5, etc.) itself strong bransted acid promotes the propane cracking to form carbon deposits to deactivate the catalyst.
The existing preparation of Co-based molecular sieve is mainly prepared by an impregnation method and an ion exchange method, wherein the active center of Co ions is in H during the reaction process2The catalyst is easy to be reduced into Co with lower valence state or even Co in metal state in reducing atmosphere, thus leading to the aggregation of Co active center, promoting the cracking of propane, generating by-products such as methane, ethane, ethylene and carbon deposition, and reducing the catalytic performance and stability. Therefore, the preparation of isolated stable Co-based active site catalysts is a difficult point of research. Few reports on direct synthesis of cobalt-based molecular sieves have been made, one of the most important reasons being OH in the basic synthesis environment of molecular sieves-Easily react with cobalt salt precursor to generate Co (OH)xPrecipitating, and inhibiting Co from entering the molecular sieve framework. Therefore, a key problem of direct hydrothermal synthesis of Co-based molecular sieves is how to avoid Co in an alkaline hydrothermal synthesis environment2+Precipitating to enable Co to enter the molecular sieve boneIn a shelf.
The invention realizes the synthesis and preparation of Co-based molecular sieves with different topological structures by adjusting hydrothermal synthesis conditions, including template agent types and additive types. The principle is that complexing agent and Co are introduced into a synthesis system2+In combination, avoid Co (OH)2Generating a precipitate, so that Co successfully enters a molecular sieve framework and one-step direct hydrothermal synthesis of a Co-based molecular sieve is realized; the synthesis of Co-based molecular sieves with different topological structures (MFI, MWW and BEA) is realized by modulating the type of the template agent.
Disclosure of Invention
The invention aims to provide a cobalt-based molecular sieve catalyst and a preparation method and application thereof, the prepared Co-based molecular sieve has the advantages of large specific surface area, good hydrothermal stability and the like, is applied to the reaction of preparing propylene by propane dehydrogenation, has higher propane dehydrogenation activity and stability, and has the advantages of simple preparation process, lower cost, environmental friendliness and higher industrial application prospect.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt-based molecular sieve catalyst comprises the following steps: mixing a silicon source, a template agent, a cobalt source, an additive and water, carrying out hydrothermal crystallization to obtain a suspension, centrifuging to obtain a solid, and washing, drying and roasting to obtain the cobalt-based molecular sieve catalyst.
Preferably, the silicon source is one or more of tetraethyl silicate, silica sol and fuming silica gel; the cobalt source is selected from cobalt nitrate, cobalt chloride, cobalt sulfate, [ Co (NH)3)6 3+]、Co(CN)6 4-、Co(SCN)4 2-One or more of; the template agent is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide and piperidine; the additive is one or more of ammonia water, aminocarboxylic acid compounds (such as ethylene diamine tetraacetic acid, nitrilotriacetic acid, diethylene triamine pentaacetic acid and salts thereof), hydroxycarboxylic acid compounds (such as citric acid, tartaric acid, gluconic acid and salts thereof), and hydroxyaminocarboxylic acid compounds (such as hydroxyethyl ethylenediamine triacetic acid and dihydroxyethyl glycine).
Preferably, the order of addition: mixing a silicon source, a template agent and water to obtain a solution A, mixing an additive, a cobalt source and water to obtain a solution B, and slowly adding the solution B into the solution A.
Preferably, a hydrolysis step and an alcohol removing step can be added before hydrothermal treatment, wherein the hydrolysis temperature is 40-60 ℃, and the time is 2-5 h; the alcohol removing temperature is 80 ℃, and the time is 3 h; the hydrothermal crystallization temperature is 120-.
Preferably, the molar ratio of each material is Co: si: template agent: additive: h2O=0.005-0.032：1.0：0.25-0.50：0.02-0.15：40。
The cobalt-based molecular sieve catalyst prepared by the preparation method is used for the reaction of preparing propylene by propane dehydrogenation.
The invention has the beneficial effects that:
(1) the invention successfully implants Co into a molecular sieve framework to synthesize the Co-based molecular sieve catalyst, and has the advantages of large specific surface area, good hydrothermal stability and the like.
(2) The prepared Co-based molecular sieve catalyst has the advantages of reducing resistance and H temperature of 800 DEG C2No significant reduction peaks in TPR indicate that Co enters the molecular sieve framework at this time.
(3) Compared with the traditional Co-based molecular sieve catalyst, the prepared Co-based molecular sieve catalyst has high dehydrogenation catalytic performance, propylene selectivity and catalyst stability in the propane dehydrogenation reaction; less carbon deposition was found to be present in the catalyst after the reaction by thermogravimetric analysis.
(4) The preparation process is simple, the cost is low, the preparation method is environment-friendly, and the industrial application prospect is high.
Drawings
Fig. 1 is an XRD pattern of the cobalt-based molecular sieve catalyst prepared in example 1.
FIG. 2 is a TEM image of the cobalt-based molecular sieve catalyst prepared in example 1.
Fig. 3 is a TEM image of the cobalt-based molecular sieve catalyst prepared in comparative example 1.
FIG. 4 is a BET plot of the cobalt-based molecular sieve catalyst prepared in example 1.
Fig. 5 is a graph of the catalytic life of the cobalt-based molecular sieve catalyst prepared in example 1.
FIG. 6 shows H for cobalt-based molecular sieve catalysts prepared in example 1 and comparative example 12-a TPR map.
Fig. 7 is a TG profile of cobalt-based molecular sieve catalysts prepared in example 1 and comparative example 1.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Tetraethyl orthosilicate TEOS is used as a silicon source, tetrapropylammonium hydroxide TPAOH is used as a template agent; cobalt nitrate is used as Co source, and ammonia water is used as additive. And adding the mixture of the Co salt and the additive into the mixed solution of the silicon source, the water and the template agent, hydrolyzing for 2h at 50 ℃, and removing alcohol for 2h at 80 ℃ to obtain a precursor A. The molar ratio of each material is 1.0SiO2：0.016Co：0.40TPAOH：40H2O：0.096NH3. And crystallizing the solution A in a hydrothermal kettle at the high temperature of 170 ℃ for 4 days to obtain a suspension B. And cooling and centrifuging the suspension to obtain a solid C. And (3) washing, drying (at 100 ℃ for 12h) and roasting (at 1 ℃/min to 600 ℃ for 5h) the C to obtain the prepared Co-based catalyst Co-S-1-HTS, wherein an analysis product XRD is shown in figure 1 and is a typical MFI structure, Co particles do not appear in a TEM picture, and surface Co is highly dispersed and enters a molecular sieve framework. The dehydrogenation performance of the product propane is shown in Table 1, and the product propane is pretreated for 2h from room temperature in a 5% hydrogen atmosphere at a heating rate of 5 ℃/min at 600 ℃, and then a mixture of propylene and hydrogen is introduced for reaction after the temperature is reduced to 550 ℃. C3H8:H2Ar is in a molar ratio of 1:1:38, and the total flow rate is 40 mL/min. The conversion of propane was 20.4% over 0.5h and reached 19.9% after 30h of reaction. The selectivity of propylene is improved from 99.3% to 99.5%.
Example 2
Tetraethyl orthosilicate TEOS is used as a silicon source, tetrapropylammonium hydroxide TPAOH is used as a template agent; cobalt nitrate is a Co source, and disodium Ethylene Diamine Tetraacetate (EDTA) is an additive. Adding the mixture of Co salt and additive into the mixed solution of silicon source, water and template agent, hydrolyzing at 50 deg.C for 2h, and removing alcohol at 80 deg.C for 2h to obtainTo precursor a. The molar ratio of each material is 1.0SiO2：0.020Co：0.40TPAOH：40H2O: 0.080 EDTA. And crystallizing the solution A in a hydrothermal kettle at the high temperature of 170 ℃ for 5 days to obtain a suspension B. And cooling and centrifuging the suspension to obtain a solid C. And (3) washing, drying (12 h at 100 ℃) and roasting (5 h from 1 ℃/min to 600 ℃) the C to obtain the prepared Co-based catalyst Co-S-1-HTS. The dehydrogenation performance of the product propane is shown in Table 1, and the product propane is pretreated for 2h from room temperature in a 5% hydrogen atmosphere at a heating rate of 5 ℃/min at 600 ℃, and then a mixture of propylene and hydrogen is introduced for reaction after the temperature is reduced to 550 ℃. C3H8:H2Ar is in a molar ratio of 1:1:38, and the total flow rate is 40 mL/min. The conversion of propane was 22.4% over 0.5h and reached 22.0% after 30h of reaction. The selectivity of propylene is improved from 99.0% to 99.4%.
Example 3
Taking silica sol as a silicon source and piperidine as a template agent; cobalt nitrate is a Co source, and disodium Ethylene Diamine Tetraacetate (EDTA) is an additive. And adding the mixture of Co salt and EDTA into the mixed solution of the silicon source, the water and the template agent, and stirring for 2 hours at room temperature to obtain a precursor A. The molar ratio of each material is 1.0SiO2：0.010Co：0.5PI：40H2O: 0.05 EDTA. And crystallizing the solution A in a hydrothermal kettle at the high temperature of 170 ℃ for 7 days to obtain a suspension B. And cooling and centrifuging the suspension to obtain a solid C. And (2) washing, drying (12 h at 100 ℃) and roasting (roasting at 1 ℃/min to 600 ℃ for 5h) the C to obtain the prepared Co-based catalyst Co-MWW-HTS, wherein the dehydrogenation reaction performance of the product propane is shown in table 1, the product is pretreated for 2h at the heating rate of 5 ℃/min and 600 ℃ from room temperature in a 5% hydrogen atmosphere, and then a mixture of propylene and hydrogen is introduced for reaction when the temperature is reduced to 550 ℃. C3H8:H2Ar is in a molar ratio of 1:1:38, and the total flow rate is 40 mL/min. The conversion of propane was 23.5% over 0.5h and reached 22.5% after 30h of reaction. The selectivity of propylene is improved from 99.2% to 99.4%.
Example 4
Tetraethyl orthosilicate TEOS is used as a silicon source, tetrapropylammonium hydroxide TPAOH is used as a template agent; cobalt nitrate is used as a Co source, and sodium citrate is used as an additive. Adding the mixture of Co salt and additive into the mixed solution of silicon source, water and template agent, hydrolyzing at 60 deg.C for 2 hr, and removing impurities at 80 deg.CAnd (5) carrying out alcohol for 2h to obtain a precursor A. The molar ratio of each material is 1.0SiO2：0.020Co：0.40TPAOH：40H2O: 0.100 parts of sodium citrate. And crystallizing the solution A in a hydrothermal kettle at the high temperature of 170 ℃ for 4 days to obtain a suspension B. And cooling and centrifuging the suspension to obtain a solid C. And (3) washing, drying (12 h at 100 ℃) and roasting (5 h from 1 ℃/min to 600 ℃) the C to obtain the prepared Co-based catalyst Co-S-1-HTS. The dehydrogenation performance of the product propane is shown in Table 1, and the product propane is pretreated for 2h from room temperature in a 5% hydrogen atmosphere at a heating rate of 5 ℃/min at 600 ℃, and then a mixture of propylene and hydrogen is introduced for reaction after the temperature is reduced to 550 ℃. C3H8:H2Ar is in a molar ratio of 1:1:38, and the total flow rate is 40 mL/min. The conversion of propane was 23.4% over 0.5h and reached 23.0% after 30h of reaction. The selectivity of propylene is improved from 99.2% to 99.6%.
Comparative example 1
Cobalt nitrate is impregnated into a pure Silicalite-1 molecular sieve, and a Co/S-1-IWI sample is obtained by drying and roasting, wherein a TEM (transmission electron microscope) is shown in the figure, and obvious Co species particles exist in the Co molecular sieve prepared by the impregnation method. The dehydrogenation performance of the product propane is shown in Table 1, and the product propane is pretreated for 2h from room temperature in a 5% hydrogen atmosphere at a heating rate of 5 ℃/min at 600 ℃, and then a mixture of propylene and hydrogen is introduced for reaction after the temperature is reduced to 550 ℃. C3H8:H2Ar is in a molar ratio of 1:1:38, and the total flow rate is 40 mL/min. The conversion of propane was 14.8% over 0.5h and reached 9.5% after 30h of reaction. The selectivity of propylene is improved from 96.8% to 98.5%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of a cobalt-based molecular sieve catalyst is characterized by comprising the following steps: mixing a silicon source, a template agent, a cobalt source, an additive and water, carrying out hydrothermal crystallization to obtain a suspension, centrifuging to obtain a solid, and washing, drying and roasting to obtain the cobalt-based molecular sieve catalyst.
2. The method of claim 1, wherein: the silicon source is one or more of tetraethyl silicate, silica sol and fuming silica gel; the cobalt source is selected from cobalt nitrate, cobalt chloride, cobalt sulfate, [ Co (NH)3)6 3+]、Co(CN)6 4-、Co(SCN)4 2-One or more of; the template agent is one or more of tetrapropylammonium hydroxide, tetraethylammonium hydroxide and piperidine; the additive is one or more of ammonia water, amino carboxylic acid compounds, hydroxyl carboxylic acid compounds and hydroxyl amino carboxylic acid compounds.
3. The method of claim 1, wherein: the charging sequence is as follows: mixing a silicon source, a template agent and water to obtain a solution A, mixing an additive, a cobalt source and water to obtain a solution B, and slowly adding the solution B into the solution A.
4. The method of claim 1, wherein: the hydrothermal crystallization temperature is 120-.
5. The method of claim 1, wherein: the molar ratio of the materials is Co: si: template agent: additive: h2O=0.005-0.032：1.0：0.25-0.50：0.02-0.15：40。
6. A cobalt-based molecular sieve catalyst prepared according to the preparation method of claim 1.
7. The use of a cobalt-based molecular sieve catalyst prepared according to the method of claim 1, wherein: the cobalt-based molecular sieve catalyst is used for the reaction of preparing propylene by propane dehydrogenation.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113830779A (en) * | 2021-10-25 | 2021-12-24 | 江西师范大学 | Preparation method and application of cobalt-containing Beta molecular sieve |
| CN114100668A (en) * | 2021-10-25 | 2022-03-01 | 江西师范大学 | Preparation method and application of cobalt-containing MFI molecular sieve |
| CN114367304A (en) * | 2021-12-28 | 2022-04-19 | 中国科学技术大学 | Composite molecular sieve, preparation method and application thereof |
| CN114984999A (en) * | 2022-07-05 | 2022-09-02 | 大连递铂科技发展有限公司 | Propane dehydrogenation catalyst with Silicalite-1 as carrier and preparation method thereof |
| CN115805097A (en) * | 2022-12-01 | 2023-03-17 | 中触媒新材料股份有限公司 | Large-grain Zn @ Silicalite-1 low-carbon alkane dehydrogenation catalyst and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110142755A1 (en) * | 2009-11-24 | 2011-06-16 | Basf Se | Process for the preparation of zeolites having b-cha structure |
| CN102838129A (en) * | 2012-09-14 | 2012-12-26 | 北京化工大学 | Mesoporous molecular sieves with crystal structures and preparation method of mesoporous molecular sieves |
| CN107694598A (en) * | 2017-09-30 | 2018-02-16 | 台州学院 | Mesopore molecular sieves of skeleton doping Co SBA 15 and preparation method thereof |
| CN111589449A (en) * | 2020-06-18 | 2020-08-28 | 南京工业大学 | Cobalt-based catalyst for propane dehydrogenation, preparation method and application |
| CN112295594A (en) * | 2020-11-11 | 2021-02-02 | 中国科学院宁波材料技术与工程研究所 | Packaging type molecular sieve metal catalyst and preparation method and application thereof |
-
2021
- 2021-04-28 CN CN202110462618.XA patent/CN113509955A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110142755A1 (en) * | 2009-11-24 | 2011-06-16 | Basf Se | Process for the preparation of zeolites having b-cha structure |
| CN102838129A (en) * | 2012-09-14 | 2012-12-26 | 北京化工大学 | Mesoporous molecular sieves with crystal structures and preparation method of mesoporous molecular sieves |
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