CN109847793B - Method for synthesizing ZSM-5 molecular sieve based non-supported hydrogenation catalyst by eutectic method - Google Patents
Method for synthesizing ZSM-5 molecular sieve based non-supported hydrogenation catalyst by eutectic method Download PDFInfo
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Abstract
The unsupported hydrogenation catalyst has no carrier, so that it is difficult to introduce acid component, and the invention provides a method for synthesizing ZSM-5 molecular sieve based unsupported hydrogenation catalyst by eutectic process. Firstly, synthesizing a ZSM-5 molecular sieve nanocluster solution with a nanoscale, then introducing the solution into a bimetallic NiMo composite oxide suspension with a layered structure, and embedding an acidic ZSM-5 molecular sieve component into a layered composite metal oxide precursor by a hydrothermal co-crystallization technology to obtain a bifunctional unsupported hydrogenation catalyst with a certain acidity. The specific surface area, pore volume and pore diameter of the ZSM-5 molecular sieve based non-supported catalyst prepared by the invention are greatly improved, and compared with a pure non-supported catalyst, the modified non-supported catalyst has higher hydrogenation ring-opening activity.
Description
Technical Field
The invention relates to a preparation method for synthesizing a ZSM-5 molecular sieve based non-supported hydrogenation catalyst by an eutectic method. In particular, the invention relates to an unsupported catalyst with a ZSM-5 molecular sieve component and a preparation method thereof.
Background
In the modern society, the world industry is developing at a rapid speed, petroleum is taken as industrial blood and plays an irreplaceable role in the development of socioeconomic performance, so that the exploitation pace of petroleum is accelerated, the quality of petroleum in the market is poorer and poorer, the content of impurities such as sulfur, nitrogen, polycyclic aromatic hydrocarbon and the like is higher and higher, and if the crude oil is taken as a processing raw material of diesel oil and gasoline, the quality of products can be reduced to a great extent, so that the diesel oil contains a large amount of impurities such as high molecular sulfur, nitrogen compounds and polycyclic aromatic hydrocarbon, and the substances can generate a large amount of polluting gases by combustion, seriously pollute the environment where people live and damage the body health of people.
Under such a severe situation, it is very critical to develop a high performance hydrogenation catalyst, and the conventional hydrodesulfurization catalyst is mainly a supported catalyst, which is widely favored due to its affordable price and better hydrogenation effect, but the desulfurization effect is more difficult to further improve because the loading of the active component greatly limits the desulfurization activity, so that the unsupported catalyst starts to enter into industrial production, and in 2001, three companies, Exxon Mobil, Akzo Nobel and Nippon Ketjen, have developed an unsupported catalyst together, and the unsupported catalyst is the most different between the supported catalyst and the unsupported catalyst, and the hydrodesulfurization catalyst mainly comprises the active component, has higher concentration of the active metal, and thus exhibits higher catalytic activity than the supported catalyst. However, the disadvantages of the non-supported catalyst appear in production, mainly reflected in that the catalyst is weak in acidity, low in strength, low in specific surface area, easy to aggregate active components and the like, so that the application of the existing industrial production is not mature, and the problems are solved.
If the cracking performance of the unsupported hydrogenation catalyst is further improved on the basis of higher hydrogenation activity of the unsupported hydrogenation catalyst, so that aromatic hydrocarbons are subjected to moderate cracking while being hydrogenated, more naphthenic hydrocarbons with side chains are generated, which has important value for improving the cetane number of diesel oil, and in order to achieve the aim, the unsupported hydrogenation catalyst needs to be modified to improve the acidity of the unsupported hydrogenation catalyst so as to improve the cracking performance of the unsupported hydrogenation catalyst.
The catalysts with hydrocracking function disclosed in chinese patents CN200810117102.6, CN200710012770.8, CN00109747.4, etc. load the hydrogenation active component on the carrier such as molecular sieve, alumina, etc., or mechanically mix the hydrogenation active component with the molecular sieve to impart acidity thereto, but these methods are often limited by low loading capacity, uneven acidity, clogging of the carrier channels, etc., and thus a good effect cannot be obtained. The introduction of a hydrogenation active component in the synthesis process of the molecular sieve is also studied, but the method is not easy to form a hydrogenation active phase and cannot achieve a good hydrogenation effect. It is important to introduce acidity into the unsupported catalyst in a suitable manner.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method for synthesizing a ZSM-5 molecular sieve based unsupported hydrogenation catalyst by a eutectic method, so that the two components are fully combined in the crystallization process, and the aim of endowing proper acidity in the unsupported hydrogenation catalyst is fulfilled.
The invention researches and synthesizes a bimetal composite oxide with a layered structure, and ZSM-5 molecular sieve nanoclusters in a nanoscale are embedded into a layered composite oxide precursor by a hydrothermal crystallization technology, so that the finally prepared non-supported catalyst has stronger hydrogenation activity and proper acidity.
The catalyst of the invention comprises the following specific preparation steps:
(1) firstly, synthesizing a precursor of the ZSM-5 molecular sieve in an alkali metal ion-free system. Taking stoichiometric tetrapropylammonium hydroxide (TPAOH) in a beaker according to a certain proportion, adding a proper amount of aluminum isopropoxide, stirring and clarifying, slowly adding tetraethyl orthosilicate (TEOS) and deionized water, continuously stirring for a certain time to clarify the mixture again to obtain a ZSM-5 molecular sieve precursor stock solution, filling the precursor stock solution into a crystallization kettle, and crystallizing at 90-180 ℃ for 2-10 hours to obtain the ZSM-5 molecular sieve nanocluster.
(2) Adding ammonium molybdate and nickel nitrate into a three-neck flask containing deionized water according to the molar ratio of nickel to molybdenum of 1-2: 1, stirring and heating to enable the mixture to become clear, adding ammonia water when the temperature reaches 90-100 ℃, stopping dropwise adding when the solution becomes clear again, and stirring and reacting the solution at the constant temperature of 90-100 ℃ for 2-20 hours to obtain an unsupported NiMo catalyst precursor suspension.
(3) Mixing a certain amount of ZSM-5 molecular sieve nanoclusters with the unsupported NiMo catalyst precursor suspension, stirring for 5-10 hours, filling the mixture into a crystallization kettle, crystallizing at 90-180 ℃ for 10-24 hours under a stirring state, taking out, filtering, washing with water, and drying the product at 60-100 ℃ for 10-24 hours to obtain ZSM-5 molecular sieve based unsupported NiMo catalyst precursor powder.
(4) The catalyst precursor powder can be formed by a conventional forming method, such as tabletting, extruding and the like, and is roasted for 3-5 hours at the temperature of 300-550 ℃ to obtain the ZSM-5 molecular sieve based non-supported NiMo catalyst.
The molar ratio of materials of the synthetic molecular sieve precursor stock solution is as follows: 1.0SiO2:0.003～0.005Al2O3:0.45～0.5TPAOH:30～40H2And O. The non-supported hydrogenation catalyst with acidity prepared by the invention can be used for hydrofining and hydrogenation ring-opening reaction of petroleum fractions, aromatic hydrocarbons and the like. The process according to the invention is further illustrated by the following examples:
drawings
FIG. 1 shows the pyridine infrared (Py-IR) spectrum of a ZSM-5 molecular sieve based unsupported hydrogenation catalyst prepared by the present invention.
FIG. 2 NH of ZSM-5 molecular sieve based non-supported hydrogenation catalyst prepared by the invention3-TPD map.
The specific implementation mode is as follows:
comparative example
Weighing 43.62 g of nickel nitrate and 17.66 g of ammonium molybdate, respectively dissolving, sequentially adding into a three-neck flask, stirring and heating to enable the mixture to become clear, slowly adding ammonia water when the temperature reaches 93 ℃, enabling the solution to become turbid firstly, stopping dropwise adding when the ammonia water is continuously added to become clear, reacting the solution at 93 ℃ for 10 hours to obtain green unsupported catalyst precursor suspension, filtering, washing and drying the product at 100 ℃ for 12 hours to obtain unsupported NiMo catalyst precursor powder. The precursor powder is formed by tabletting and is roasted for 4 hours at 350 ℃ to obtain the non-supported NiMo catalyst which is marked as Cat-0.
Example 1
Weighing 45.76 g of tetrapropylammonium hydroxide (TPAOH) into a beaker, adding 0.42 g of aluminum isopropoxide, stirring for clarification, slowly dripping 42.52 g of tetraethyl orthosilicate (TEOS) and 97.70 g of deionized water, continuously stirring, clarifying the mixture again to obtain a ZSM-5 molecular sieve precursor stock solution, crystallizing the ZSM-5 molecular sieve precursor stock solution in a crystallization kettle at 160 ℃ for 3 hours, and taking out to obtain a ZSM-5 molecular sieve nanocluster solution A.
Weighing 43.62 g of nickel nitrate and 17.66 g of ammonium molybdate, respectively dissolving, sequentially adding into a three-neck flask, stirring and heating to enable the mixture to become clear, slowly adding ammonia water when the temperature reaches 93 ℃, enabling the solution to become turbid firstly, stopping dropwise adding when the ammonia water is continuously dropwise added to become clear, and then reacting the solution at 93 ℃ for 10 hours to obtain a green unsupported catalyst precursor suspension B.
And (3) putting 60mL (4 g on a dry basis) of the solution A into a beaker, then mixing 107mL (6.0 g on a dry basis) of the solution B to obtain a mixture C, stirring the mixture C for 6 hours, then putting the mixture C into a crystallization kettle, crystallizing the mixture C at 160 ℃ for 12 hours under a stirring state, taking out the mixture C, and drying the product at 100 ℃ for 12 hours to obtain modified unsupported NiMo catalyst precursor powder. The precursor powder is formed by tabletting and is roasted for 4 hours at 350 ℃ to obtain the non-supported NiMo catalyst which is marked as Cat-1.
Example 2
Weighing 45.76 g of tetrapropylammonium hydroxide (TPAOH) into a beaker, adding 0.42 g of aluminum isopropoxide, stirring for clarification, slowly dripping 42.52 g of tetraethyl orthosilicate (TEOS) and 97.70 g of deionized water, continuously stirring, clarifying the mixture again to obtain a ZSM-5 molecular sieve precursor stock solution, crystallizing the ZSM-5 molecular sieve precursor stock solution in a crystallization kettle at 160 ℃ for 3 hours, and taking out to obtain a ZSM-5 molecular sieve nanocluster solution A.
Weighing 43.62 g of nickel nitrate and 17.66 g of ammonium molybdate, respectively dissolving, sequentially adding into a three-neck flask, stirring and heating to enable the mixture to become clear, slowly adding ammonia water when the temperature reaches 93 ℃, enabling the solution to become turbid firstly, stopping dropwise adding when the ammonia water is continuously dropwise added to become clear, and then reacting the solution at 93 ℃ for 10 hours to obtain a green unsupported catalyst precursor suspension B.
And (3) putting 60mL (dry basis is 4 g) of A solution into a beaker, then mixing 165mL (dry basis is 9.3 g) of B with the A solution to obtain a mixture C, stirring the mixture C for 6 hours, then putting the mixture C into a crystallization kettle, crystallizing the mixture C at 160 ℃ for 12 hours under a stirring state, taking out the mixture C, and drying the product at 100 ℃ for 12 hours to obtain modified unsupported NiMo catalyst precursor powder. The precursor powder is formed by tabletting and is roasted for 4 hours at 350 ℃ to obtain the non-supported NiMo catalyst which is marked as Cat-2.
Example 3
Weighing 45.76 g of tetrapropylammonium hydroxide (TPAOH) into a beaker, adding 0.42 g of aluminum isopropoxide, stirring for clarification, slowly dripping 42.52 g of tetraethyl orthosilicate (TEOS) and 97.70 g of deionized water, continuously stirring, clarifying the mixture again to obtain a ZSM-5 molecular sieve precursor stock solution, crystallizing the ZSM-5 molecular sieve precursor stock solution in a crystallization kettle at 160 ℃ for 3 hours, and taking out to obtain a ZSM-5 molecular sieve nanocluster solution A.
Weighing 43.62 g of nickel nitrate and 17.66 g of ammonium molybdate, respectively dissolving, sequentially adding into a three-neck flask, stirring and heating to enable the mixture to become clear, slowly adding ammonia water when the temperature reaches 93 ℃, enabling the solution to become turbid firstly, stopping dropwise adding when the ammonia water is continuously dropwise added to become clear, and then reacting the solution at 93 ℃ for 10 hours to obtain a green unsupported catalyst precursor suspension B.
And (3) putting 60mL (dry basis is 4 g) of A solution into a beaker, then mixing 284mL (dry basis is 16.0 g) of B with the A solution to obtain a mixture C, stirring the mixture C for 6 hours, then putting the mixture C into a crystallization kettle, crystallizing the mixture C at 160 ℃ for 12 hours under a stirring state, taking out the mixture C, and drying the product at 100 ℃ for 12 hours to obtain modified unsupported NiMo catalyst precursor powder. The precursor powder is formed by tabletting and is roasted for 4 hours at 350 ℃ to obtain the non-supported NiMo catalyst which is marked as Cat-3.
Example 4
This example illustrates a method for evaluating catalyst activity.
At 3 wt% CS2Petroleum ether solution as presulfurizing reagent and liquid hourly space velocity of 6h-1The catalyst was presulfided for 8 hours at a hydrogen to oil ratio of 300:1, a pressure of 3Mpa, and a temperature of 330 ℃. The reaction stage comprises DBT hydrodesulfurization and naphthalene hydrogenation, and the reaction conditions are as follows: (1) 1 wt% DBT/petroleum ether solution is used as raw material, and the liquid hourly space velocity is 10h-1The hydrogen-oil ratio is 300:1, the pressure is 3Mpa, the temperature is 280 ℃, and the dosage of the catalyst is 5 mL. (2) Using 8 wt% naphthalene/petroleum ether solution as raw material, liquid hourly space velocity of 4h-1Hydrogen-oil ratio of 300:1, pressure of 4.0Mpa, temperature of 360 deg.C, catalystThe dosage is 5 mL.
FIG. 1 shows the pyridine infrared (Py-IR) spectrum of ZSM-5 molecular sieve based non-supported hydrogenation catalyst prepared by the present invention. It is clear from this that the unsupported catalysts prepared using the process of the invention, L and B acids, are significantly enhanced. FIG. 2 shows NH of ZSM-5 molecular sieve based non-supported hydrogenation catalyst prepared by the invention3-TPD map. It is clear from this that the total acid content of the unsupported catalysts prepared using the process of the invention is significantly enhanced.
Table 1 gives the results of the DBT and naphthalene hydrogenation reactions on different catalysts. It can be seen that the hydrogenation activity of the unsupported catalyst is slightly increased after the unsupported catalyst is modified by the ZSM-5 type molecular sieve nanocluster, and particularly the cracking activity of the unsupported catalyst is obviously improved.
TABLE 1 DBT and naphthalene hydrogenation results on different catalysts
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (3)
1. A method for synthesizing a ZSM-5 molecular sieve based unsupported hydrogenation catalyst by a eutectic method is characterized in that the catalyst is prepared by the following steps:
(1) firstly, synthesizing a precursor of a ZSM-5 molecular sieve in an alkali metal ion-free system: taking stoichiometric tetrapropylammonium hydroxide in a beaker according to a certain proportion, marking the tetrapropylammonium hydroxide as TPAOH, then adding a proper amount of aluminum isopropoxide, slowly adding tetraethyl orthosilicate and deionized water after stirring and clarifying, continuously stirring for a certain time to clarify the mixture again to obtain a ZSM-5 molecular sieve precursor stock solution, and crystallizing the precursor stock solution at a proper temperature for a certain time to obtain a ZSM-5 molecular sieve nanocluster solution A;
(2) adding ammonium molybdate and nickel nitrate into a three-neck flask containing deionized water according to the molar ratio of nickel to molybdenum of 1-2: 1, stirring and heating to clarify the mixture, starting to slowly dropwise add ammonia water when the temperature reaches 90-100 ℃, continuing dropwise adding ammonia water when precipitation occurs until the solution becomes clear again, stopping dropwise adding, stirring and reacting the solution at the constant temperature of 90-100 ℃ for 2-20 hours to obtain a green suspension B;
(3) adding the solution A into the solution B in a certain proportion, and stirring and mixing to obtain slurry C;
(4) and (2) putting the slurry C into a crystallization kettle, crystallizing at 90-180 ℃ for 10-24 hours under a stirring state, taking out, filtering, washing, drying the product at 60-100 ℃ for 10-24 hours to obtain catalyst precursor powder, performing tabletting molding or extrusion molding on the precursor powder by adopting a conventional molding method, roasting at 300-550 ℃ for 3-5 hours to obtain a ZSM-5 molecular sieve based non-supported NiMo catalyst, and performing presulfurization treatment on the obtained ZSM-5 molecular sieve based non-supported NiMo catalyst in a presulfurization reagent before catalytic reaction.
2. The method for synthesizing ZSM-5 molecular sieve based unsupported hydrogenation catalyst according to claim 1, wherein the molar ratio of the materials in the synthesis solution A is SiO for tetraethyl orthosilicate2Calculated as Al, aluminum isopropoxide2O3The meter specifically comprises the following steps: 1.0SiO2:0.003～0.005Al2O3:0.45～0.5TPAOH:30～40H2O。
3. The use of a ZSM-5 molecular sieve based unsupported hydrogenation catalyst prepared according to the method of claim 1 in the hydrorefining, hydrocracking, or hydrocracking reactions of petroleum fractions, aromatics.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103122256A (en) * | 2013-01-29 | 2013-05-29 | 沈阳三聚凯特催化剂有限公司 | Application of W-Mo-Ni catalyst in hydrogenation of mixture of crude benzene and absorber oil |
| WO2014158843A1 (en) * | 2013-03-14 | 2014-10-02 | Exxonmobil Research And Engineering Company | Methods for producing basestocks from renewable sources using dewaxing catalyst |
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| CN100348311C (en) * | 2004-11-26 | 2007-11-14 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst containing molecular sieve |
| CN100548487C (en) * | 2006-06-16 | 2009-10-14 | 中国石油化工股份有限公司 | A kind of aromatized eutectic superfine zeolite grain catalyst and its production and application |
| CN101380589B (en) * | 2007-09-04 | 2011-07-20 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN101939102B (en) * | 2008-02-08 | 2013-06-26 | 吉坤日矿日石能源株式会社 | Hydroisomerization catalyst, process for producing the same, method of dewaxing hydrocarbon oil, and process for producing lube base oi |
| CN101255356B (en) * | 2008-04-17 | 2012-07-18 | 中国石油天然气集团公司 | Unsupported catalyst and preparation method thereof |
| CN101837299B (en) * | 2009-03-18 | 2012-08-08 | 中国石油天然气股份有限公司 | Catalyst for catalytic gasoline hydrogenation modification and preparation method thereof |
| CN104941695B (en) * | 2015-06-08 | 2019-01-11 | 清华大学 | A kind of nano-ZSM-5 molecular sieve catalyst and preparation, application method |
| CN106925338B (en) * | 2015-12-30 | 2020-01-07 | 中国石油天然气股份有限公司 | Sulfur-carrying type hydrodesulfurization modification catalyst and preparation method thereof |
| CN106215973A (en) * | 2016-08-12 | 2016-12-14 | 清华大学 | A kind of modified ZSM-5 5 molecular sieve catalyst method of preparation and use |
| CN108786903B (en) * | 2017-05-02 | 2020-09-11 | 中国石油化工股份有限公司 | Olefin disproportionation catalyst and preparation method thereof |
| CN108097294A (en) * | 2017-12-15 | 2018-06-01 | 广东工业大学 | A kind of stratiform ZSM-5 catalyst and preparation method thereof and application |
| CN108273514B (en) * | 2018-01-18 | 2020-12-22 | 中国石油大学(华东) | Preparation method of non-supported hydrogenation catalyst with acidity |
| CN108212204B (en) * | 2018-03-23 | 2021-02-09 | 安徽理工大学 | Catalyst for directly preparing high-carbon olefin from methane by microwave assistance and catalysis process |
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| WO2014158843A1 (en) * | 2013-03-14 | 2014-10-02 | Exxonmobil Research And Engineering Company | Methods for producing basestocks from renewable sources using dewaxing catalyst |
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