CN112403512A - Platinum-based catalyst loaded by nano titanium silicalite molecular sieve, preparation method and application thereof - Google Patents
Platinum-based catalyst loaded by nano titanium silicalite molecular sieve, preparation method and application thereof Download PDFInfo
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- CN112403512A CN112403512A CN202011357985.5A CN202011357985A CN112403512A CN 112403512 A CN112403512 A CN 112403512A CN 202011357985 A CN202011357985 A CN 202011357985A CN 112403512 A CN112403512 A CN 112403512A
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Abstract
The invention discloses a platinum-based catalyst loaded by a nano titanium silicalite molecular sieve, a preparation method and application thereof, belonging to the preparation of organic chemical raw materials. The catalyst is composed of two phases of a nano titanium-silicon molecular sieve and a platinum metal cluster, strong interaction occurs between the two phases, the two phases are tightly combined, and platinum is uniformly dispersed on the surface of the titanium-silicon molecular sieve in an atomic cluster form; wherein the content of platinum is 0.5-1.0wt%, and the size of platinum atom cluster is 1nm-2 nm. The invention prepares the platinum-based single metal catalyst loaded by the nano titanium-silicon molecular sieve by an ethylene glycol prereduction method. The catalyst prepared by the method can better disperse pt, and the particle size is more concentrated and smaller.
Description
Technical Field
The invention belongs to the technical field of organic chemical raw material preparation, and particularly relates to a platinum-based catalyst loaded by a nano titanium silicalite molecular sieve, and a preparation method and application thereof.
Background
Butane is an important component of liquefied petroleum gas, and has low price and wide source. The huge liquefied petroleum gas of output is mainly used as fuel to use each year, but belongs to the very big waste to the energy. Butene is an intermediate product of important chemicals in the chemical industry, is used for producing rubber, plastics and other polymers, is an important chemical basic raw material next to ethylene and propylene. With the increase in downstream markets, particularly synthetic rubber production, the market demand for butenes has increased year by year. Therefore, the method for converting butane into olefin through catalytic dehydrogenation has important application value. The current technological process for preparing butylene by butane dehydrogenation mainly comprises direct dehydrogenation and oxidative dehydrogenation. Oxidative dehydrogenation has no thermodynamic limitation because of the existence of oxides in the reaction, but also has the problem that excessive oxidation is easy to occur, so that the final target products of butene and butadiene have low product selectivity. Compared with oxidative dehydrogenation, the research of direct dehydrogenation is more extensive, the direct dehydrogenation is limited by thermodynamics and is a strong endothermic reaction and needs to be carried out at a higher temperature, and the conversion rate of preparing olefin by butane dehydrogenation is more than or equal to 50 percent under the temperature range of 1bar and 550-750 ℃, so the butane dehydrogenation temperature is generally more than 500 ℃. However, high temperatures lead to high energy consumption and cracking and coking, which reduces selectivity. Therefore, it is important to develop a catalyst having high productivity and excellent anti-carbon property at a lower temperature.
In a catalytic reaction system for direct dehydrogenation of butane, the problem of uneven distribution of active components is easy to occur in a platinum-based catalyst prepared by a traditional impregnation method. The problem can be effectively improved by preparing the catalyst by the ethylene glycol pre-reduction method. The catalyst prepared by the method has more concentrated size distribution and smaller size of platinum particles, and has strong interaction with a carrier. The method is beneficial to improving the catalytic activity and stability of the catalyst and effectively reducing the occurrence of side reactions (carbon deposition and hydrogenolysis reaction). Although the carbon deposit can be removed by the method of catalyst cyclic regeneration, how to promote the stable use of the catalyst is always a focus of attention.
Disclosure of Invention
The purpose of the invention is as follows: provides a platinum-based catalyst loaded by a nano titanium silicalite molecular sieve, a preparation method and application thereof, which aim to solve the problems involved in the background technology.
The technical scheme is as follows: a platinum-based catalyst loaded by a nano titanium silicalite molecular sieve, a preparation method and an application thereof comprise:
the catalyst is composed of two phases of a nano titanium-silicon molecular sieve and a platinum metal cluster, strong interaction occurs between the two phases, the two phases are tightly combined, and platinum is uniformly dispersed on the surface of the titanium-silicon molecular sieve in an atomic cluster form; wherein the content of platinum is 0.5-1.0wt%, and the size of platinum atom cluster is 1nm-2 nm.
The invention also provides a preparation method of the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve, which is characterized in that the method comprises the steps of firstly preparing the nano titanium silicalite molecular sieve, and then loading platinum atom clusters on a titanium silicalite molecular sieve carrier in an ethylene glycol prereduction mode to obtain the platinum-based single metal catalyst loaded by the nano titanium silicalite molecular sieve.
In a further embodiment, the preparation method comprises the following steps:
step 1, preparation of nano titanium silicalite molecular sieve carrier
Preparing a catalyst by a hydrothermal synthesis method through a hydrothermal reaction by using tetraethyl silicate as a silicon source, tetraethyl titanate as a titanium source and tetrapropyl ammonium hydroxide as a template agent; after the hydrothermal reaction is finished, washing, drying and roasting to obtain a nano titanium silicalite molecular sieve; wherein, the proportion of silicon and titanium is adjusted by adjusting the proportion of tetraethyl silicate and tetraethyl titanate;
step 2, ethylene glycol pre-reduction method
Mixing a platinum nitrate aqueous solution and a certain amount of ethylene glycol according to a mass ratio, adding a certain amount of PVP polyvinylpyrrolidone, stirring, uniformly dissolving, adding a certain amount of nano titanium silicalite, heating to a preset temperature in a reflux device, and heating and stirring for a preset time; and after cooling, removing the glycol solvent and the polyvinylpyrrolidone, and roasting to obtain the platinum-based single metal catalyst loaded by the nano titanium silicalite molecular sieve.
In a further embodiment, in step 1, the ratio of Si: the molar ratio of Ti is 10 to 50.
In a further embodiment, in the step 2, the mass ratio of the titanium silicalite molecular sieve to the ethylene glycol is 1: (20-50), the mass of platinum in the platinum nitrate is 0.1-1.0 wt% of that of the nano titanium silicalite molecular sieve, and the mass ratio of the mass of the ethylene glycol to the mass of the PVP polyvinylpyrrolidone is 1 (0.1-0.15).
In a further embodiment, the predetermined temperature is 160-170 ℃, and the heating and stirring time is 16-18 hours.
The invention also provides an application of the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve in n-butane dehydrogenation.
In a further embodiment, in the reaction process of the direct dehydrogenation of the n-butane, the service temperature of the catalyst is 400-550 ℃; the reaction conditions of the catalyst are as follows: the space velocity is 1500-15000 ml/g.h, the molar concentration of n-butane is 10-50%, and the molar ratio of n-butane to hydrogen is 1: 0.5-5.
In a further embodiment, the catalyst is used for the direct dehydrogenation of n-butane to butene, wherein the butenes are 1-butene, cis-2-butene, trans-2-butene, and butadiene.
Has the advantages that: the invention relates to a platinum-based catalyst loaded by a nano titanium-silicon molecular sieve, a preparation method and application thereof. The catalyst prepared by the method can better disperse pt, and the particle size is more concentrated and smaller. Moreover, platinum is uniformly distributed on the surface of the nano titanium silicalite molecular sieve in the form of atomic clusters, and strong interaction force is generated between the platinum and a carrier, so that the stability is better, and the sintering resistance is higher.
The catalyst of the invention has good catalytic activity at 500 ℃, the selectivity of olefin products is stabilized at more than 96%, the initial conversion rate can reach 21%, and the catalyst does not obviously decrease in 10 hours. The catalyst has good stability, no pollution to the environment, environmental protection and high efficiency.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to be illustrative of the invention and are not to be construed as limiting the invention.
Examples 1 to 5
The preparation of the catalysts in examples 1 to 5 was as follows:
step 1, preparation of nano titanium silicalite molecular sieve carrier
The preparation method comprises the steps of using a hydrothermal synthesis method, using tetraethyl silicate as a silicon source, using tetraethyl titanate as a titanium source, and using tetrapropyl ammonium hydroxide as a template agent to prepare the catalyst through a hydrothermal reaction. The ratio of silicon to titanium is adjusted by adjusting the ratio of tetraethyl silicate to tetraethyl titanate, Ti: the ratio of Si is 1: 50. The hydrothermal reaction temperature was controlled at 160 ℃ and maintained at this temperature for 4 hours. After the hydrothermal reaction is finished, washing, drying and then roasting for 4 hours at 550 ℃ in air to obtain the nano titanium silicalite molecular sieve.
Step 2, ethylene glycol pre-reduction method
Putting a water solution of platinum nitrate into a flask according to a proportion, adding a certain amount of ethylene glycol, adding a certain amount of PVP polyvinylpyrrolidone, uniformly dissolving under stirring, adding a certain amount of nano titanium silicalite, heating to 160 ℃ in a reflux device, and heating and stirring for 18 hours; and after cooling, removing the glycol solvent and the polyvinylpyrrolidone, and roasting to obtain the platinum-based single metal catalyst loaded by the nano titanium silicalite molecular sieve. Wherein the mass ratio of the ethylene glycol to the PVP polyvinylpyrrolidone is 1: 0.05, 1: 0.10, 1: 0.12, 1: 0.15, 1:0.5, Si in the titanium silicalite: the molar ratio of Ti was 49: 1, the mass ratio of the titanium silicalite molecular sieve to the ethylene glycol is 1: 50; the mass of platinum in the platinum nitrate is 1.0wt% of the mass of the nano titanium silicalite molecular sieve.
The reaction conditions and structural properties (transmission electron microscopy) characterization parameters of the catalysts obtained in examples 1-5 are as follows:
TABLE 1
Table 1 shows statistics of transmission electron micrographs of the catalyst, specifically by counting the abundance of Pt metal clusters at specific positions in the catalyst and the sizes and particle sizes of 200 random Pt metal clusters. From the above table, it can be seen that, as the mass ratio increases, the abundance of Pt metal clusters on the nano titanium silicalite molecular sieve gradually increases, and when the mass ratio of ethylene glycol to PVP polyvinylpyrrolidone is 1: 0.12, the size distribution of the Pt metal clusters shows a better Pt nanoparticle distribution diagram. It was also found that the average size of the Pt metal clusters of each catalyst gradually increased with increasing mass ratio. Under the condition of the mass ratio, the Pt metal clusters are effectively reduced and loaded on the carrier, but as the mass ratio is increased, the Pt nano particles are gradually increased, and even a more obvious agglomeration phenomenon occurs.
Example 6
On the basis of the embodiment 3, before the ethylene glycol is pre-reduced, ammonia water is added to adjust the pH value to 10.5, then a certain amount of nano titanium silicalite molecular sieve is added, the temperature is raised to 160 ℃ in a reflux device, and the mixture is heated and stirred for 18 hours; the rest of the process and parameters were the same as in example 3.
Example 7
On the basis of the embodiment 3, before the ethylene glycol is pre-reduced, the pH is adjusted to 10.5 by adding a sodium hydroxide solution, then a certain amount of nano titanium silicalite molecular sieve is added, the temperature is raised to 160 ℃ in a reflux device, and the mixture is heated and stirred for 18 hours; the rest of the process and parameters were the same as in example 3.
Example 8
On the basis of the embodiment 3, before the ethylene glycol is pre-reduced, the pH value is adjusted to 10.5 by adding an ethylene diamine aqueous solution, then a certain amount of nano titanium silicalite molecular sieve is added, the temperature is raised to 160 ℃ in a reflux device, and the mixture is heated and stirred for 18 hours; the rest of the process and parameters were the same as in example 3.
The reaction conditions and structural properties (transmission electron microscopy) characterization parameters of the catalysts obtained in examples 6-8 are as follows:
as can be seen from the above table: by adding the aqueous solution of alkali liquor, the abundance ratio of the Pt metal cluster can be effectively improved, and the average size of Pt can be reduced, but because inorganic alkali introduces new metal impurities in the synthesis process, Pt atoms can be agglomerated, and the size of the Pt metal cluster is enlarged.
Firstly, compared with a hydrogen calcination reduction method, silicon dioxide cannot be reduced, and the acting force between the Pt metal cluster and the nano titanium silicalite molecular sieve is influenced to a certain extent, so that the stability of the catalyst is reduced. And the pre-reduction by the glycol has little influence on the structure of the carrier and even has positive synergistic effect.
Specifically, the reduction of platinum nitrate to platinum in ethylene glycol solution generally involves two steps, in a first reaction, combining with hydroxide ions in a solvent to form platinum hydroxide; in the second reaction, the platinum is reduced to metal platinum under the action of ethylene glycol. Wherein, as water belongs to an oxidant, when water molecules are contained in a reaction system, the normal reduction process of the glycol can be interfered. And when the reaction solution reaches the preset temperature, the water is considered to be completely removed, then a condensation circulating system of the reflux device is started, and the refluxed polyol is collected. The polyhydric alcohol can not only dissolve the platinum nitrate, but also serve as a reducing agent for reducing the platinum nitrate in the reaction. In the initial state, as the organic alkali is in the aqueous solvent and can provide more hydroxide ions, the platinum nitrate and the organic alkali liquor produce a large amount of platinum hydroxide, and then the platinum hydroxide is reduced into metal platinum under the reduction action of the ethylene glycol along with the complete evaporation of water, so that the interference action of water molecules is avoided.
Application example 1
Based on the catalyst of example 3, a catalytic performance test of the catalyst was carried out using a fixed-bed microreactor, quartz wool being placed in a quartz reactor, 50mg of the catalyst being weighed in the middle of the reactor and being in a constant-temperature zone in the fixed bed. The catalyst was reduced at 500 ℃ with a 40% hydrogen mixture for 1 hour using argon as the balance gas before testing and then cooled using an argon purge. In the direct dehydrogenation reaction process of the n-butane, the use temperature of the catalyst is 550 ℃; the reaction conditions of the catalyst are as follows: the space velocity was 15000 ml/g.h, the molar concentration of n-butane was 5%, the molar ratio of n-butane to hydrogen was 1:0.5, and the aeration was carried out for 1 hour.
And (3) continuing the reaction according to the catalyst dosage, the operation condition and the catalyst dosage until the reaction time is 10 hours, and keeping the rest conditions unchanged.
Application example 2
Based on the catalyst of example 8, the reaction was continued until the reaction time was 1 and 10 hours, with the remaining conditions being maintained, in accordance with the amount of catalyst and the operating conditions and the amount of catalyst of application example 1.
Comparative example
Preparation of the catalyst: the same nano titanium silicalite molecular sieve is used for preparing the platinum-based single metal catalyst by a traditional impregnation method. And (3) testing the catalytic performance: the amount of catalyst and operating conditions and amount of catalyst according to example 2 were varied to 10 hours, the remaining conditions were maintained and the conversion and product selectivity are shown in the table.
During which the composition of the reaction products, 1-butene, cis, trans-2-butene and butadiene were analyzed on-line using gas chromatography. The results of conversion and product selectivity are given in table 3 below.
Table 3:
from table 3, it can be seen that the catalysts obtained in examples 3 and 8 have high activity and good stability during use, and have excellent activity and stability when the reaction time reaches 10 hours.
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.
Claims (10)
1. The platinum-based catalyst loaded by the nano titanium silicalite molecular sieve is characterized in that the catalyst consists of two phases of the nano titanium silicalite molecular sieve and a platinum metal cluster, strong interaction occurs between the two phases, the two phases are tightly combined, and platinum is uniformly dispersed on the surface of the titanium silicalite molecular sieve in an atomic cluster form; wherein the content of platinum is 0.5-1.0wt%, and the size of platinum atom cluster is 1nm-2 nm.
2. The preparation method of the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve according to claim 1 is characterized in that the method comprises the steps of firstly preparing the nano titanium silicalite molecular sieve, and then loading platinum atom clusters on a titanium silicalite molecular sieve carrier in an ethylene glycol pre-reduction mode to obtain the platinum-based single metal catalyst loaded by the nano titanium silicalite molecular sieve.
3. The preparation method of the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve according to claim 2, which is characterized by comprising the following steps:
step 1, preparation of nano titanium silicalite molecular sieve carrier
Preparing a catalyst by a hydrothermal synthesis method through a hydrothermal reaction by using tetraethyl silicate as a silicon source, tetraethyl titanate as a titanium source and tetrapropyl ammonium hydroxide as a template agent; after the hydrothermal reaction is finished, washing, drying and roasting to obtain a nano titanium silicalite molecular sieve; wherein, the proportion of silicon and titanium is adjusted by adjusting the proportion of tetraethyl silicate and tetraethyl titanate;
step 2, ethylene glycol pre-reduction method
Mixing a platinum nitrate aqueous solution and a certain amount of ethylene glycol according to a mass ratio, adding a certain amount of PVP polyvinylpyrrolidone, stirring, uniformly dissolving, adding a certain amount of nano titanium silicalite, heating to a preset temperature in a reflux device, and heating and stirring for a preset time; and after cooling, removing the glycol solvent and the polyvinylpyrrolidone, and roasting to obtain the platinum-based single metal catalyst loaded by the nano titanium silicalite molecular sieve.
4. The platinum-based catalyst loaded by the nano titanium silicalite molecular sieve, the preparation method and the application thereof according to claim 3, wherein in the step 1, the ratio of Si: the molar ratio of Ti is 10-50; in the step 2, the mass ratio of the titanium silicalite molecular sieve to the ethylene glycol is 1: (20-50), the mass of platinum in the platinum nitrate is 0.1-1.0 wt% of that of the nano titanium silicalite molecular sieve, and the mass ratio of the mass of the ethylene glycol to the mass of the PVP polyvinylpyrrolidone is 1 (0.1-0.15).
5. The method for preparing the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve according to claim 3, wherein the predetermined temperature is 160-170 ℃, and the heating and stirring time is 16-18 hours.
6. The method for preparing the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve according to claim 3, wherein a condensation circulation system of the reflux device is started after the reaction solution reaches the predetermined temperature.
7. The method for preparing the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve according to claim 3, wherein in the step 2, the pH is adjusted to 10-11 by adding an aqueous solution of organic alkali.
8. The application of the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve in the dehydrogenation of n-butane.
9. The application of the platinum-based catalyst loaded by the nano titanium silicalite molecular sieve according to claim 8, wherein in the reaction process of the direct dehydrogenation of n-butane, the use temperature of the catalyst is 400-550 ℃; the reaction conditions of the catalyst are as follows: the space velocity is 1500-15000 ml/g.h, the molar concentration of n-butane is 10-50%, and the molar ratio of n-butane to hydrogen is 1: 0.5-5.
10. The use of the platinum-based catalyst supported on nano titanium silicalite molecular sieve according to claim 8, wherein the catalyst is used for preparing butene by direct dehydrogenation of n-butane, wherein the butene is 1-butene, cis-2-butene, trans-2-butene and butadiene.
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| CN115722070A (en) * | 2021-08-25 | 2023-03-03 | 中国科学院城市环境研究所 | Electromagnetic induction heating material, preparation method and application thereof in VOCs purification |
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| CN115722070A (en) * | 2021-08-25 | 2023-03-03 | 中国科学院城市环境研究所 | Electromagnetic induction heating material, preparation method and application thereof in VOCs purification |
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