CN112371116A - Long-life sulfur-containing catalyst for methylcyclohexane and preparation method thereof - Google Patents

Long-life sulfur-containing catalyst for methylcyclohexane and preparation method thereof Download PDF

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CN112371116A
CN112371116A CN202011355114.XA CN202011355114A CN112371116A CN 112371116 A CN112371116 A CN 112371116A CN 202011355114 A CN202011355114 A CN 202011355114A CN 112371116 A CN112371116 A CN 112371116A
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刘喆
王绍伟
杨光
吕金昆
杨磊
王聪
刘新伟
杨克俭
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China Tianchen Engineering Corp
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

The invention provides a long-life sulfur-containing catalyst for methylcyclohexane, which comprises a main catalyst and a catalyst carrier, wherein the main catalyst is Pt, and the catalyst carrier is sulfur-containing gamma-Al2O3The mass content of the main catalyst Pt is 0.4-1%, preferably 0.8-1% of the total catalyst amount, and the mass content of the S element is 0.1-0.5%, preferably 0.3-0.5% of the total catalyst amount. The long-life sulfur-containing catalyst for methyl cyclohexane and the preparation method thereof have the advantages of simple preparation steps, mild preparation conditions, no need of adding other metal element auxiliaries, low cost and easy industrial production, and the catalyst is applied to a reaction system for methyl cyclohexane dehydrogenation to obtain hydrogen with the purity higher than 99.9 percent and the service life longer than 3000 hoursThen (c) is performed.

Description

Long-life sulfur-containing catalyst for methylcyclohexane and preparation method thereof
Technical Field
The invention belongs to the field of chemical hydrogen storage, and particularly relates to a longevity life sulfur-containing catalyst for methyl cyclohexane dehydrogenation and a preparation method thereof.
Background
Hydrogen energy is a secondary energy source with many advantages: the hydrogen has various sources and wide application, can be used for power generation, heat supply and traffic, and does not produce pollution in the using process; the energy density of hydrogen is large, the heat value is 3 times of gasoline, and the storage and transportation of hydrogen energy become a hot spot of global research. The liquid organic hydrogen storage material has the advantages of high hydrogen storage capacity, stable performance, high safety, capability of being stored and transported at normal temperature and normal pressure as gasoline in principle, and direct utilization of the existing gasoline transportation mode and the gas station framework. However, the dehydrogenation temperature is high, side reactions are generated in the dehydrogenation process, so that the purity of hydrogen is not high, and the catalyst is quickly deactivated at high temperature and has short service life. Therefore, the development of long-life, high-selectivity, high-conversion dehydrogenation catalysts has become a key point in this technology.
The common dehydrogenation catalyst is a supported catalyst, the active components comprise metals such as Pt, Rh, Ni, Cu, Pd and the like, and the carriers mainly comprise alumina, activated carbon, layered double hydroxide, silicon dioxide, hydrotalcite and the like.
Patent CN1201715 discloses a preparation method of a Pt-Sn-K/Al2O3 catalyst.
Patent CN101066532 discloses a gamma-Al 2O3 pellet carrier with a double-pore structure, which is used for a dehydrogenation catalyst of straight-chain alkane and has good dehydrogenation performance.
Patent CN106622228A discloses a dehydrogenation catalyst of naphthenic hydrocarbon, which uses hydrotalcite as carrier and Pt as active component, and has high conversion rate but short life, which is only 10 hours.
Patent CN105037066B discloses a Pt/C dehydrogenation catalyst for dehydrogenation of methylcyclohexane, which has high dehydrogenation efficiency but short life.
In summary, the main problems of the existing dehydrogenation catalysts are that the catalyst is deactivated quickly, the stability is poor, byproducts are easy to generate, and the purity of hydrogen is low, the service life is short, and the like.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention provides a long-life sulfur-containing catalyst for methylcyclohexane and a preparation method thereof.
One purpose of the invention is to provide a long-life sulfur-containing catalyst for methylcyclohexane, which comprises a main catalyst and a catalyst carrier, wherein the main catalyst is Pt, and the catalyst carrier is sulfur-containing gamma-Al2O3
Preferably, the mass content of the S element is 0.1-0.5%, preferably 0.3-0.5%, of the total catalyst amount.
Preferably, the mass content of the main catalyst Pt is 0.8-1%, preferably 0.4-1% of the total catalyst amount.
In order to achieve the above object, another object of the present invention is to provide a method for preparing a long-life sulfur-containing catalyst for methylcyclohexane, comprising the following steps:
(1) sulfur-containing gamma-Al2O3Preparation of modified support
Mixing gamma-Al2O3Adding sulfur-containing ammonium salt and deionized water, and mixing uniformly2O3The mass ratio of S element to the ammonium sulfate is 1:0.001-0.005, then the mixture is stood for 12 hours at room temperature, the mixture is dried for 1-3 hours in the air atmosphere at the temperature of 100-120 ℃ after being filtered, and the dried mixture is roasted for 4 hours in the air atmosphere at the temperature of 450-550 ℃ after being dried, thus obtaining the sulfur-containing gamma-Al2O3The modified support of (1);
(2) preparation of Pt impregnation liquid
Dissolving a metal Pt compound in deionized water to obtain a Pt impregnation solution, and adjusting the pH value to 8-11, wherein the mass fraction of the Pt compound-containing solution is 10%;
(3) preparation of sulfur-containing catalyst
The sulfur-containing gamma-Al prepared in the step 12O3Change (1) toAnd (3) adding the sex carrier into the Pt impregnation liquid obtained in the step (2), aging at room temperature for 12-24 hours, drying at 100-120 ℃ in the air atmosphere for 12 hours, crushing, tabletting and molding, and roasting at 300-600 ℃ in the air atmosphere for 4 hours to obtain the sulfur-containing catalyst.
Preferably, the sulfur-containing ammonium salt in step (1) is one of ammonium sulfate, ammonium bisulfate, ammonium sulfite and ammonium bisulfite, and preferably ammonium sulfate or ammonium bisulfate.
Preferably, the metal Pt compound in step (2) is one of chloroplatinic acid, platinum chloride, platinum acetylacetonate, dinitroso diammine platinum and platinum tetraammine dichloride, and chloroplatinic acid and platinum chloride are preferred.
Preferably, the pH in step (2) is in the range of 9 to 10.
Preferably, the pH adjusting solution in the step (2) is at least one of 1, 4-diazabicyclo [2.2.2] octane or an ethanol aqueous solution of 4-dimethylaminopyridine; wherein the mass ratio of the water to the ethanol is 4:6-6: 4.
Preferably, the aging time of the step (3) is 18 to 24 hours.
Preferably, the calcination temperature in the step (3) is 400-500 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the long-life sulfur-containing catalyst for methylcyclohexane and the preparation method thereof have the advantages of simple preparation steps, mild preparation conditions, no need of adding other metal element auxiliaries, low cost and easiness in industrial production.
(2) According to the long-life sulfur-containing catalyst for methylcyclohexane and the preparation method thereof, the sulfur content of the catalyst is low, and the sulfur can form a certain chemical bond action with Pt, so that the Pt is dispersed on the carrier more uniformly, and the surface of the catalyst is less prone to carbon deposition and inactivation.
(3) The dehydrogenation catalyst with small crystal grains and uniform dispersion, which is prepared by the catalyst, can reduce dehydrogenation temperature, improve the activity of the catalyst and simultaneously keep longer catalyst life, wherein the catalyst life can reach more than 3000 hours.
(4) According to the long-life sulfur-containing catalyst for methylcyclohexane and the preparation method thereof, the catalyst is adjusted in pH by using the ethanol aqueous solution of 1, 4-diazabicyclo [2.2.2] octane or 4-dimethylaminopyridine in the preparation process, so that the growth of Pt crystal grains can be further limited, and Pt nano particles with small and uniform crystal grains are obtained.
(5) The catalyst is used for the dehydrogenation reaction of the methylcyclohexane, a fixed bed reactor is adopted for reaction, the reaction is continuous, products and the catalyst do not need to be separated, and the purity of the obtained hydrogen is high.
Detailed Description
For a better understanding of the present invention, the following detailed description is given in conjunction with specific examples. The following examples illustrate details of the process for the purpose of describing the invention in detail and are not intended to unduly limit the invention.
Example 1
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (S content: 0.3%) were added to deionized water to prepare a solution having a mass fraction of 60%, and the mixture was mixed uniformly. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.212g of chloroplatinic acid (Pt loading is 0.8%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere 4And h, preparing the catalyst. The catalyst evaluation temperature was 340 ℃.
Example 2
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Baking the mixture for 4 hours at 500 ℃ in an air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Example 3
(1) 10g of gamma-Al2O3And 0.041g of ammonium sulfate (the S content is 0.1%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. Catalytic converterThe agent evaluation temperature was 340 ℃.
Example 4
(1) 10g of gamma-Al2O3And 0.206g of ammonium sulfate (the S content is 0.5%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Example 5
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt loading is 1%) in a certain amount of water, preparing a 10% mass fraction chloroplatinic acid aqueous solution, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining the catalyst for 4 hours at 300 ℃ in an air atmosphere to obtain the catalyst. The catalyst evaluation temperature was 340 deg.C。
Example 6
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Roasting for 4 hours at 500 ℃ in an air atmosphere to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Example 7
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 280 ℃.
Example 8
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 350 ℃.
Comparative example 1
(1) 10g of gamma-Al2O3And 0.413g of ammonium sulfate (S content: 1%) were added to a predetermined amount of deionized water to prepare a solution having a mass fraction of 60%, and the mixture was mixed uniformly. After aging at room temperature for 12 hours, the resultant was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in an air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt load is 1%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Comparative example 2
(1) 10g of gamma-Al2O3Adding into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and uniformly mixing. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt loading is 1%) in a certain amount of water, preparing a 10% mass fraction chloroplatinic acid aqueous solution, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Comparative example 3
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt loading is 1%) and 0.095g of stannous chloride dihydrate (Sn loading is 0.5%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Comparative example 4
(1) 10g of gamma-Al2O3And 0.124g of ammonium sulfate (the S content is 0.3%) are added into a certain amount of deionized water to prepare a solution with the mass fraction of 60%, and the solution is uniformly mixed. After aging at room temperature for 12 hours, the mixture was dried at 120 ℃ for 2 hours in an air atmosphere. Roasting for 4 hours at 500 ℃ in the air atmosphere to obtain a modified carrier;
(2) dissolving 0.264g of chloroplatinic acid (Pt loading amount is 1%) and 0.13g of potassium nitrate (K loading amount is 0.5%) in a certain amount of water to prepare a chloroplatinic acid aqueous solution with the mass fraction of 10%, adjusting the pH value of the chloroplatinic acid aqueous solution to 10 by using an ethanol solution of 1, 4-diazabicyclo [2.2.2] octane, wherein the mass ratio of ethanol to 1, 4-diazabicyclo [2.2.2] octane is 1: 1;
(3) the obtained modified gamma-Al2O3Adding the carrier into the chloroplatinic acid aqueous solution, uniformly mixing, and aging at room temperature for 12 hours. The product was dried at 120 ℃ for 12 hours in an air atmosphere, pulverized, and molded by tableting. Calcining at 400 deg.C in air atmosphere for 4 hr to obtain the catalyst. The catalyst evaluation temperature was 340 ℃.
Evaluation of the effects:
the evaluation method comprises the following steps: the catalyst of examples 1-8 and comparative examples 1-4 is adopted to catalyze the dehydrogenation reaction of the methylcyclohexane on a fixed bed reactor, the dosage of the catalyst is that the mass space velocity of the methylcyclohexane is 2h-1The catalyst loading is 1g, the reaction pressure is normal pressure, the reaction temperature is 280-350 ℃, the hydrogen flow is 5mL/min, and the reaction parameters are adjusted according to the actual reaction condition. The catalyst was continuously evaluated for 180 days under the above reaction conditions.
The catalyst evaluation criteria were: it was characterized by chromatographic detection and tested for conversion and selectivity.
TABLE 1 evaluation results of catalysts
Figure BDA0002802408500000111
As can be seen from Table 1, the calcination temperature of the catalyst is the best at 400 ℃, the too low calcination temperature can lead the grain growth of Pt to be incomplete, and the too high calcination temperature can lead the Pt to agglomerate.
The catalyst evaluation temperature is 340 ℃, the lower temperature can lead to the lower conversion rate of the methylcyclohexane, and the higher temperature can lead to the easy occurrence of carbon deposition on the catalyst, thereby leading to the reduction of the service life.
When the Pt content is 1%, the methyl cyclohexane conversion rate is high, the catalytic active component is insufficient due to the reduction of the Pt content, and the production cost of the catalyst is increased due to the increase of the Pt content.
When the S content is 0.3%, the service life of the catalyst is longest, the effect of the S content is not obvious when the S content is too low, the interaction between Pt and S is insufficient, and the catalyst is poisoned when the S content is too high, so that the adverse effect is played. Meanwhile, the K element and the Sn element are added in the comparative example, the conversion rate and the service life of the methylcyclohexane are reduced after the addition, and the addition of the S element has no practical significance because other metal elements can destroy the combination of Pt and S and occupy the Pt site.
The working principle of the invention is as follows:
in the process of loading Pt, the sulfur-containing alumina carrier can form a certain chemical bond effect with Pt, so that Pt is more uniformly dispersed on the carrier, the acidity of the alumina carrier is reduced, and the surface of the catalyst is not easy to deposit carbon and deactivate. The grain size distribution of the Pt with smaller crystal grains is between 1 and 3 nm, and the dehydrogenation catalyst with uniform dispersion can reduce dehydrogenation temperature, improve the activity of the catalyst and keep longer catalyst life. The method adopts 1, 4-diazabicyclo [2.2.2] octane or 4-dimethylamino pyridine ethanol water solution as pH adjusting solution, so that Pt can grow slowly and uniformly in solution with high viscosity, and Pt can form a metal-organic complex with 1, 4-diazabicyclo [2.2.2] octane or 4-dimethylamino pyridine, thereby further limiting the growth of Pt grains and obtaining Pt nanoparticles with small and uniform grains.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (10)

1. A long-life sulfur-containing catalyst for methylcyclohexane, characterized in that: the sulfur-containing catalyst comprises a main catalyst and a catalyst carrier, wherein the main catalyst is Pt, and the catalyst carrier is sulfur-containing gamma-Al2O3
2. The long life sulfur-containing catalyst for methylcyclohexane according to claim 1, wherein: the mass content of the main catalyst Pt is 0.4-1%, preferably 0.8-1% of the total catalyst amount.
3. The long life sulfur-containing catalyst for methylcyclohexane according to claim 1, wherein: the mass content of the S element is 0.1-0.5%, preferably 0.3-0.5% of the total catalyst amount.
4. A preparation method of a long-life sulfur-containing catalyst for methylcyclohexane is characterized by comprising the following steps: the preparation method comprises the following preparation steps:
(1) sulfur-containing gamma-Al2O3Preparation of modified support
Mixing gamma-Al2O3Adding ammonium sulfate and deionized water, mixing uniformly, gamma-Al2O3And S element in the sulfur ammonium salt in a mass ratio of 1:0.001-0.005, standing at room temperature for 12 hours, filtering, drying at 100-120 ℃ in an air atmosphere for 1-3 hours, drying, and roasting at 450-550 ℃ in an air atmosphere for 4 hours to obtain the sulfur-containing gamma-Al2O3The modified support of (1);
(2) preparation of Pt impregnation liquid
Dissolving a metal Pt compound in deionized water to obtain a Pt impregnation solution, and adjusting the pH value to 8-11, wherein the mass fraction of the Pt compound-containing solution is 10%;
(3) preparation of sulfur-containing catalyst
The sulfur-containing gamma-Al prepared in the step (1)2O3Adding the modified carrier into the Pt impregnation liquid obtained in the step (2), aging at room temperature for 12-24 hours, and drying at 100-120 ℃ in an air atmosphereCrushing, tabletting and forming, and roasting at 300-600 ℃ air atmosphere for 4 hours to obtain the sulfur-containing catalyst.
5. The method for producing a sulfur-containing catalyst according to claim 4, characterized in that: the ammonium sulfate salt in the step (1) is one of ammonium sulfate, ammonium bisulfate, ammonium sulfite and ammonium bisulfite, and preferably ammonium sulfate or ammonium bisulfate.
6. The method for producing a sulfur-containing catalyst according to claim 4, characterized in that: the metal Pt compound in the step (2) is one of chloroplatinic acid, platinum chloride, platinum acetylacetonate, dinitroso diammine platinum and dichlorotetrammine platinum, and the chloroplatinic acid or the platinum chloride is preferred.
7. The method for producing a sulfur-containing catalyst according to claim 4, characterized in that: the pH range in the step (2) is 9-10.
8. The method for producing a sulfur-containing catalyst according to claim 4, characterized in that: the pH adjusting solution in the step (2) is at least one of 1, 4-diazabicyclo [2.2.2] octane or an ethanol water solution of 4-dimethylaminopyridine; wherein the mass ratio of the water to the ethanol is 4:6-6: 4.
9. The method for producing a sulfur-containing catalyst according to claim 4, characterized in that: the aging time in the step (3) is 18-24 hours.
10. The method for producing a sulfur-containing catalyst according to claim 4, characterized in that: the roasting temperature in the step (3) is 400-500 ℃.
CN202011355114.XA 2020-11-26 2020-11-26 Long-life sulfur-containing catalyst for methylcyclohexane and preparation method thereof Pending CN112371116A (en)

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Application publication date: 20210219