CN112403512B - Platinum-based catalyst loaded by nano titanium-silicon molecular sieve, preparation method and application thereof - Google Patents
Platinum-based catalyst loaded by nano titanium-silicon molecular sieve, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a platinum-based catalyst loaded by a nano titanium-silicon molecular sieve, a preparation method and application thereof, and belongs to the preparation of organic chemical raw materials. The catalyst consists of two phases of a nano titanium-silicon molecular sieve and a platinum metal cluster, wherein strong interaction and tight combination occur between the two phases, 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-2nm. The invention prepares the platinum-based single-metal catalyst loaded by the nano titanium-silicon molecular sieve by an ethylene glycol pre-reduction method. The catalyst prepared by the method can better disperse pt, and has more concentrated and smaller particle size.
Description
Technical Field
The invention belongs to the technical field of preparation of organic chemical raw materials, and particularly relates to a platinum-based catalyst loaded by a nano titanium-silicon molecular sieve, and a preparation method and application thereof.
Background
Butane is an important component of liquefied petroleum gas, and has low cost and wide sources. The liquefied petroleum gas with huge annual output is mainly used as fuel, and belongs to the great waste of energy. Butene is an intermediate product of important chemicals in the chemical industry, is used for producing rubber, plastics and other polymers, and is an important chemical basic raw material next to ethylene and propylene. The market demand for butenes has increased year by year as the downstream market, particularly the yield of synthetic rubber, has increased. Therefore, the butane is changed into olefin by a catalytic dehydrogenation method, and the method has important application value. The current technological processes for preparing butene by butane dehydrogenation mainly comprise direct dehydrogenation and oxidative dehydrogenation. Oxidative dehydrogenation has no thermodynamic limitation due to the presence of oxides in the reaction, but also has a problem that excessive oxidation is liable to occur, so that the product selectivity of the final target products of butene and butadiene is low. Compared with oxidative dehydrogenation, the research of direct dehydrogenation is more extensive, the direct dehydrogenation is limited by thermomechanics, is a strong endothermic reaction and needs to be carried out at a higher temperature, and the conversion rate of butane dehydrogenation to olefin is more than or equal to 50% at the temperature range of 1bar and 550-750 ℃, so the butane dehydrogenation temperature is generally more than 500 ℃. However, high temperatures result in 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 directly dehydrogenating butane, the platinum-based catalyst prepared by the traditional impregnation method is easy to cause the problem of uneven distribution of active components. The catalyst prepared by the glycol pre-reduction method can effectively solve the problem. The catalyst prepared by the method has more centralized size distribution of platinum particles, smaller size and strong interaction with the carrier. This is advantageous for improving the catalytic activity and stability of the catalyst, and effectively reducing the occurrence of side reactions (carbon deposition and hydrogenolysis reactions). Although carbon deposition can be removed by means of catalyst recycling, how to promote stable use of the catalyst has been a focus of attention.
Disclosure of Invention
The invention aims to: a platinum-based catalyst loaded by nano titanium-silicon molecular sieve, its preparing process and application are disclosed.
The technical scheme is as follows: a platinum-based catalyst loaded by a nano titanium-silicon molecular sieve, a preparation method and application thereof comprise the following steps:
the catalyst consists of two phases of a nano titanium-silicon molecular sieve and a platinum metal cluster, wherein strong interaction and tight combination occur between the two phases, 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-2nm.
The invention also provides a preparation method of the platinum-based catalyst loaded by the nano titanium-silicon molecular sieve, which is characterized in that the method is characterized in that firstly the nano titanium-silicon molecular sieve is prepared, and then platinum clusters are loaded on a titanium-silicon molecular sieve carrier in a mode of glycol pre-reduction, so that the platinum-based single-metal catalyst loaded by the nano titanium-silicon molecular sieve can be obtained.
In a further embodiment, the preparation method comprises the steps of:
step 1, preparation of nano titanium silicon molecular sieve carrier
Using a hydrothermal synthesis method, using tetraethyl silicate as a silicon source, using tetraethyl titanate as a titanium source, using tetrapropylammonium hydroxide as a template agent, and preparing a catalyst through a hydrothermal reaction; after the hydrothermal reaction is finished, washing, drying and roasting to obtain the nano titanium-silicon molecular sieve; wherein the proportion of silicon to titanium is adjusted by adjusting the proportion of tetraethyl silicate and tetraethyl titanate;
step 2, glycol prereduction method
Mixing a platinum nitrate aqueous solution with a certain amount of glycol according to a mass ratio, adding a certain amount of PVP polyvinylpyrrolidone, stirring to dissolve uniformly, adding a certain amount of nano titanium silicon molecular sieve, heating to a preset temperature in a reflux device, and heating and stirring for a preset hour; and cooling, removing the glycol solvent and polyvinylpyrrolidone, and roasting to obtain the platinum-based single-metal catalyst loaded by the nano titanium silicon molecular sieve.
In a further embodiment, in the step 1, si in the titanium silicalite molecular sieve: the Ti molar ratio is in the range of 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 the mass of the nano titanium silicon molecular sieve, and the mass ratio of ethylene glycol to PVP polyvinylpyrrolidone is 1 (0.1-0.15).
In a further embodiment, the predetermined temperature is 160 to 170 ℃ and the heating and stirring time is 16 to 18 hours.
The invention also provides application of the platinum-based catalyst loaded by the nano titanium-silicon molecular sieve in dehydrogenation of n-butane.
In a further embodiment, the catalyst is used at a temperature of 400-550 ℃ during the reaction of direct dehydrogenation of n-butane; the reaction conditions of the catalyst are: the airspeed 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 produce butenes, wherein the butenes are 1-butene, cis-2-butene, trans-2-butene and butadiene.
The beneficial effects are 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 has more concentrated and smaller particle size. In addition, platinum is uniformly distributed on the surface of the nano titanium silicon molecular sieve in the form of atomic clusters, and a strong interaction force is generated between the platinum and the carrier, so that the platinum has better stability and sintering resistance.
The catalyst has good catalytic activity at 500 ℃, the selectivity of olefin products is stabilized to be more than 96%, the initial conversion rate can reach 21%, and no obvious drop exists in 10 hours. The catalyst has good stability, no pollution to the environment, and environmental protection and high efficiency.
Description of the embodiments
The invention is further illustrated below in conjunction with examples, examples of which are intended to illustrate the invention and are not to be construed as limiting the invention.
Examples 1 to 5
The catalyst preparation process in examples 1 to 5 is as follows:
step 1, preparation of nano titanium silicon molecular sieve carrier
The catalyst is prepared by hydrothermal reaction by using a hydrothermal synthesis method, wherein tetraethyl silicate is used as a silicon source, tetraethyl titanate is used as a titanium source, tetrapropylammonium hydroxide is used as a template agent. The ratio of silicon to titanium is adjusted by adjusting the ratio of tetraethyl silicate to tetraethyl titanate, ti: the Si ratio was 1:50. The hydrothermal reaction temperature was controlled at 160℃and the temperature was maintained for 4 hours. And after the hydrothermal reaction is finished, washing, drying, and roasting for 4 hours at 550 ℃ to obtain the nano titanium-silicon molecular sieve.
Step 2, glycol prereduction method
Placing an aqueous 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, stirring to dissolve uniformly, adding a certain amount of nano titanium silicon molecular sieve, heating to 160 ℃ in a reflux device, and heating and stirring for 18 hours; and cooling, removing the glycol solvent and polyvinylpyrrolidone, and roasting to obtain the platinum-based single-metal catalyst loaded by the nano titanium silicon molecular sieve. Wherein, the mass ratio of the glycol to PVP polyvinylpyrrolidone is 1:0.05, 1:0.10, 1:0.12, 1:0.15, 1:0.5, si in the titanium silicalite molecular sieve: the molar ratio of Ti is 49:1, the mass ratio of the titanium silicon molecular sieve to the ethylene glycol is 1:50; the mass of platinum in the platinum nitrate is 1.0wt percent of the mass of the nano titanium silicon molecular sieve.
The reaction conditions and structural properties (transmission electron microscopy) of the catalysts obtained in examples 1 to 5 are characterized by the following table 1:
TABLE 1
Table 1 is a graph of a transmission electron microscope of a catalyst, specifically by counting the abundance of Pt metal clusters at specific positions in the catalyst and the size and particle size of 200 Pt metal clusters at random. As can be seen from the above table, with the increase of mass ratio, the abundance of Pt metal clusters on the nano titanium silicalite molecular sieve is gradually increased, and the mass ratio of ethylene glycol to PVP polyvinylpyrrolidone is 1:0.12, the size distribution of the Pt metal clusters presents a more excellent distribution pattern of Pt nanoparticles. It was also found that as the mass ratio increased, the average size of Pt metal clusters of each catalyst also gradually increased. Under the condition of the mass ratio, pt metal clusters are effectively reduced and loaded on the carrier, but Pt nano particles become larger gradually and even more obvious agglomeration phenomenon occurs along with the larger mass ratio.
Examples
On the basis of the example 3, before glycol pre-reduction, ammonia water is added to adjust the pH value to 10.5, then a certain amount of nano titanium silicon molecular sieve is added, and 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 are the same as in example 3.
Examples
On the basis of the example 3, before glycol pre-reduction, the pH is adjusted to 10.5 by adding sodium hydroxide solution, then a certain amount of nano titanium silicon molecular sieve is added, and 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 are the same as in example 3.
Examples
On the basis of the example 3, before the glycol is prereduced, the pH is adjusted to 10.5 by adding an ethylenediamine water solution, then a certain amount of nano titanium silicon molecular sieve is added, and 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 are the same as in example 3.
The reaction conditions and structural properties (transmission electron microscopy) of the catalysts obtained in examples 6 to 8 are characterized by the following table 2:
as can be seen from the table above: by adding the aqueous solution of the alkali liquor, the abundance of Pt metal clusters can be effectively improved, and the average size of Pt can be reduced, but because new metal impurities can be introduced in the synthesis process of the inorganic alkali, pt atoms can be agglomerated, and the size of the Pt metal clusters is enlarged.
Firstly, compared with the hydrogen calcination reduction method, the silicon dioxide is not reduced, so that acting force between Pt metal clusters and the nano titanium silicalite molecular sieve can be influenced to a certain extent, and the stability of the catalyst is reduced. And the glycol pre-reduction is adopted, so that the influence on the structure of the carrier is small, and even the positive synergistic effect is achieved.
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, it is reduced to metallic platinum by the action of ethylene glycol. Wherein, because water belongs to an oxidant, when the reaction system contains water molecules, the normal reduction process of ethylene glycol can be interfered. When the reaction solution reaches the preset temperature, the water is considered to be completely removed, then a condensation circulation system of the reflux device is started, and the polyol after reflux is collected. The polyol can not only play a role in dissolving the platinum nitrate, but also play a role in serving as a reducing agent for reducing the platinum nitrate in the reaction. In the initial state, because the organic alkali is in the water solvent, more hydroxide ions can be provided, and 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 along with complete evaporation of water under the reduction effect of glycol, so that the interference effect of water molecules is avoided.
Application example 1
Based on the catalyst of example 3, the catalytic performance test of the catalyst was performed using a fixed bed microreactor, in which quartz wool was placed, 50mg of the catalyst was weighed and placed in the middle of the reactor, and in a constant temperature zone in the fixed bed. The catalyst was reduced with argon as an equilibrium gas for 1 hour at 500 ℃ with a 40% hydrogen mixture before testing, and then cooled using an argon purge. In the process of direct dehydrogenation of n-butane, the use temperature of the catalyst is 550 ℃; the reaction conditions of the catalyst are: the space velocity was 15000ml/g.h, the molar concentration of n-butane was 5%, the molar ratio of n-butane to hydrogen was 1:0.5, and the mixture was aerated for 1 hour.
The reaction was continued according to the above catalyst amount and operating conditions and catalyst amount until the reaction time was 10 hours, with the remaining conditions maintained.
Application example 2
Based on the catalyst of example 8, the reaction was continued according to the catalyst amount and the operating conditions and catalyst amount of application example 1 until the reaction time was 1, 10 hours, with the remaining conditions remaining unchanged.
Comparative example
Preparation of the catalyst: the platinum-based single-metal catalyst is prepared by using the same nano titanium-silicon molecular sieve through a traditional impregnation method. Catalytic performance test: the catalyst amount and the operating conditions and catalyst amount of example 2 were changed to 10 hours, and the remaining conditions were maintained, and the conversion and the product selectivity were shown in the table.
During which the composition of the reaction product was analyzed on line using gas chromatography, the butenes being 1-butene, cis, trans-2-butene and butadiene. The results of conversion and product selectivity are shown in Table 3 below.
Table 3:
from Table 3, it can be seen that the catalysts obtained in example 3 and example 8 had higher activity and good stability in use, and still had excellent activity and stability when the reaction time reached 10 hours.
In addition, the specific features described in the above embodiments may be combined in any suitable manner without contradiction. The various possible combinations of the invention are not described in detail in order to avoid unnecessary repetition.
Claims (3)
1. The application of a platinum-based catalyst based on nano titanium silicon molecular sieve loading in n-butane dehydrogenation is characterized in that the platinum-based catalyst loaded by the nano titanium silicon molecular sieve consists of two phases of nano titanium silicon molecular sieve and platinum metal clusters, strong interaction and tight combination occur between the two phases, 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 clusters is 1nm-2nm; the preparation method of the platinum-based catalyst loaded by the nano titanium-silicon molecular sieve comprises the following steps:
step 1, preparation of nano titanium silicon molecular sieve carrier
Using a hydrothermal synthesis method, using tetraethyl silicate as a silicon source, using tetraethyl titanate as a titanium source, using tetrapropylammonium hydroxide as a template agent, and preparing a catalyst through a hydrothermal reaction; after the hydrothermal reaction is finished, washing, drying and roasting to obtain the nano titanium-silicon molecular sieve; wherein the proportion of silicon to titanium is adjusted by adjusting the proportion of tetraethyl silicate and tetraethyl titanate; si in the nano titanium silicon molecular sieve: the molar ratio of Ti is 10-50;
step 2, glycol prereduction method
Mixing a platinum nitrate aqueous solution with a certain amount of glycol according to a mass ratio, adding a certain amount of PVP polyvinylpyrrolidone, stirring to dissolve uniformly, adding a certain amount of nano titanium silicon molecular sieve, heating to a preset temperature in a reflux device, and heating and stirring for a preset hour; after cooling, removing the glycol solvent and polyvinylpyrrolidone, and roasting to obtain the platinum-based single-metal catalyst loaded by the nano titanium silicon molecular sieve; wherein the preset temperature is 160-170 ℃, the heating and stirring time is 16-18 hours, and after the reaction solution reaches the preset temperature, a condensation circulation system of the reflux device is started; the mass ratio of the glycol to PVP polyvinylpyrrolidone is 1 (0.1-0.12).
2. The application of the platinum-based catalyst based on nano titanium silicalite molecular sieve loading in n-butane dehydrogenation according to claim 1, wherein in the step 2, the mass ratio of the nano titanium silicalite molecular sieve to the ethylene glycol is 1: (20-50), the mass of platinum in the aqueous solution of platinum nitrate is 0.1-1.0 wt% of the mass of the nano titanium silicon molecular sieve.
3. The use of a platinum-based catalyst based on nano titanium silicalite molecular sieve according to claim 1, wherein in step 2, the pH is adjusted to 10-11 by adding an aqueous solution of an organic base before the pre-reduction of ethylene glycol.
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