CN113042025B - Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof - Google Patents
Non-metal porous carbon material catalyst prepared by taking saccharides as raw materials and preparation method and application thereof Download PDFInfo
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- CN113042025B CN113042025B CN202110359609.8A CN202110359609A CN113042025B CN 113042025 B CN113042025 B CN 113042025B CN 202110359609 A CN202110359609 A CN 202110359609A CN 113042025 B CN113042025 B CN 113042025B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 39
- 239000002994 raw material Substances 0.000 title claims abstract description 34
- 150000001720 carbohydrates Chemical class 0.000 title claims abstract description 19
- 229910052755 nonmetal Inorganic materials 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title description 5
- 150000002843 nonmetals Chemical class 0.000 title description 2
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- 239000001294 propane Substances 0.000 claims abstract description 53
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 28
- 239000003513 alkali Substances 0.000 claims abstract description 17
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 16
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 14
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- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/56—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/18—Carbon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a non-metal porous carbon material catalyst which is directly used for catalyzing propane dehydrogenation to prepare propylene without loading any metal. Firstly, the invention adopts cheap saccharides as carbon sources, and then changes the roasting temperature and the alkali treatment strength to prepare the high-performance propane dehydrogenation non-metallic porous carbon material catalyst, and has the advantages of cheap and easily-obtained raw materials, no metal pollution, no toxicity and simple and easy manufacturing process. And secondly, the porous structure of the catalyst improves the mass transfer and heat transfer efficiency and increases the contact area of propane and active groups, and the catalyst has the advantages of high catalytic activity and high catalytic stability when applied to the propane dehydrogenation catalytic reaction.
Description
Technical Field
The invention relates to a non-metal porous carbon material catalyst and a method for preparing the catalyst by using saccharides as raw materials, and belongs to the field of preparation of low-carbon alkane dehydrogenation catalysts.
Background
Cr-series catalysts and Pt-series catalysts are two most commonly used catalysts for industrially catalyzing the reaction of preparing propylene by propane dehydrogenation. The dehydrogenation of propane to propylene is a reaction with increased molecular number and strong heat absorption, and the reaction conditions of high temperature and low pressure are favorable for the dehydrogenation of propane to propylene. At present, the serious environmental pollution problem of the traditional Cr series catalyst is gradually eliminated. The Pt-based catalyst is expensive although it causes little environmental pollution, and is liable to irreversible aggregation of metal particles at high reaction temperature to greatly reduce the activity of propane dehydrogenation, and this disadvantage is usually improved by adding some metal promoters. The most commonly used supports in industry are alumina and molecular sieves, but the strong acidity of the supports can lead to deep cracking of propane to generate byproducts, further carbon deposit is generated to cover active centers, and the activity of the catalyst is reduced.
In recent years, carbon materials such as carbon black, activated carbon, carbon nanotubes, nanodiamonds, and ordered mesoporous carbons have been increasingly used as a novel carrier or catalyst for propane dehydrogenation. The carbon materials change the electron density and the geometric structure of the loaded active metal due to the unique physicochemical properties, so that the catalytic performance of the carbon materials is greatly improved, and the surfaces of the carbon materials contain a large amount of active groups, so that the carbon materials can be directly used as catalysts for propane dehydrogenation reactions, such as Liu et al (L, Liu, Q.F. Deng, B.Agula, X.ZHao, T.Z. Ren, Z.Y. Yuan, Ordered mesoporous carbon catalyst for dehydrogenation of propane to propylene, Chem Commun (Camb), 47 (2011) 8334 hydrothermal 8336), resorcinol, F127 triblock polymer and formaldehyde aqueous solution are used as raw materials to synthesize phenolic resin by adopting a low-temperature roasting method, and then an Ordered mesoporous carbon containing a large amount of active groups is synthesized by high-temperature roasting, and the Ordered mesoporous carbon is successfully applied to the propane dehydrogenation catalytic reactions. However, the carbon material catalyst obtained by the method has high cost of raw materials, the raw materials and reagents used in the preparation process have certain pollution and toxicity, and the preparation process is complex.
Disclosure of Invention
In order to solve the problems, the invention synthesizes the non-metal porous carbon material catalyst which has low price, non-metal, no metal pollution, no toxicity and simple manufacturing process, and is used for catalyzing propane dehydrogenation to produce propylene. The catalyst does not need to load any metal, can be directly applied to catalytic reaction, overcomes the defects that the traditional metal-loaded catalyst is expensive and easy to cause metal pollution, and is easy to sinter at high temperature to cause inactivation, and has high activity and high stability in the reaction of catalyzing the propane dehydrogenation to prepare propylene.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a non-metallic porous carbon material catalyst by taking saccharides as raw materials comprises the following steps:
s1, mixing the saccharide raw materials with water, putting the mixture into a hydrothermal kettle, carrying out hydrothermal carbonization at 120-200 ℃ to obtain a carbonized material, and filtering and washing the carbonized material;
s2, roasting the carbonized material at low temperature of 300-600 ℃;
s3, putting the carbonized material after low-temperature roasting into a strong alkali aqueous solution, stirring to remove amorphous carbon in the carbonized material, roasting at the high temperature of 600-1100 ℃, and washing the carbonized material after high-temperature roasting to be neutral;
and s4, reducing the carbonized material obtained in s3 by using a reducing agent or a hydrogen reducing atmosphere for the carbonized material obtained in s3, and obtaining the non-metal porous carbon material catalyst.
The method comprises the steps of taking saccharides as raw materials, firstly carrying out hydrothermal treatment on the saccharides to obtain a basic carbonized material, then roasting the carbonized material at a relatively low temperature to further carbonize the non-carbonized part, removing amorphous free carbon in the carbonized material by using alkali liquor, simultaneously eroding the porous carbon by using the alkali liquor to generate more pores and active sites on the porous carbon, improving the mass and heat transfer efficiency and increasing the contact area of propane and active groups, and finally shaping the porous carbon by high-temperature roasting and carrying out reduction treatment on the shaped porous carbon to obtain a catalyst finished product. According to the invention, through the two-step roasting and alkali liquor treatment processes, the pore channels of the porous carbon are increased, the catalytic activity is improved, the stability is enhanced, and the porous carbon is not easy to inactivate at high temperature.
Further, the saccharide is selected from one or more of starch, sucrose, fructose, glucose, maltose, cellulose or lactose.
Further, the reducing agent in s4 is selected from one or more of ethylene glycol, C1-C3 carboxylic acid or C1-C3 sodium carboxylate.
Further, the strong alkali aqueous solution is a NaOH solution, a KOH solution or a mixed solution of NaOH and KOH, and the mass of alkali in the strong alkali aqueous solution is 1-10 times of that of the carbonized material after low-temperature roasting in s 2. Preferably, the mass of the strong base is 2-4 times of that of the carbonized material.
Preferably, the temperature of the high-temperature roasting process is 650-750 ℃.
Further, the low-temperature roasting process is carried out under the protective atmosphere of inert gas or nitrogen.
Further, the high-temperature roasting process is carried out under the protective atmosphere of inert gas or nitrogen.
The carbon material is used as the catalyst, and oxygen is required to be isolated in the high-temperature treatment process, so that the roasting is required to be carried out under the protection of inert gas or nitrogen.
As another object of the present invention, the present invention also uses the above catalyst for catalytic dehydrogenation of propane to produce propylene. Preferably, the catalytic reaction is carried out at a temperature of 550 to 750 ℃ and a pressure of 0 to 0.3 MPa.
In summary, the application of the invention has the following advantages:
1. the invention adopts the nonmetal porous carbon material as the catalyst, can achieve higher catalytic activity without carrying out metal loading, avoids the problems of cost rise and metal pollution caused by metal loading, and simultaneously avoids the problem of activity reduction caused by metal loss of the conventional metal-loaded catalyst in the reaction process.
2. The invention adopts the saccharides as the raw materials for preparing the non-metallic porous carbon material, the raw materials are renewable materials, the source is wide, the cost is low, the cost of the catalyst can be greatly reduced, and the use of some toxic chemical raw materials is avoided.
3. The nonmetal porous carbon material catalyst prepared by the invention has strong stability and can keep higher selectivity for a long time under the condition of high temperature.
Drawings
FIG. 1 is a Scanning Electron Micrograph (SEM) of a comparative catalyst F (scale bar: 8 μm);
FIG. 2 is a scanning electron micrograph (SEM, scale bar of 8 μm) of catalyst C of the present invention.
Detailed Description
The method comprises the steps of fully mixing one or more mixtures in different proportions in the sugar with water, putting the mixture into a hydrothermal kettle for hydrothermal treatment, washing and drying a hydrothermal product, and roasting the hydrothermal product at a low temperature in an inert gas atmosphere to obtain an original carbon material; mixing and stirring an original carbon material and a strong alkali aqueous solution, drying, and roasting a dried product at a high temperature in an inert gas atmosphere; and washing the product after high-temperature roasting to be neutral, drying, and finally carrying out reduction treatment to obtain the final catalyst.
The present invention will be described in further detail with reference to the following examples, which are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
Taking 4.0g of anhydrous glucose and 40mL of deionized water, uniformly mixing, transferring to a 80mL polytetrafluoroethylene stainless steel autoclave, carrying out hydrothermal treatment for 12h at 180 ℃, cooling, carrying out suction filtration washing on the product with deionized water for many times until the filtrate is colorless, drying the suction-filtered product at 110 ℃ for 12h, and roasting at 400 ℃ for 2h in a nitrogen atmosphere after drying. Mixing 1.1g of the original carbon material after low-temperature roasting with an aqueous solution containing 1.1g of NaOH, and stirring for 12 hours; drying the stirred product at 110 ℃ for 12h, roasting the product at 700 ℃ for 2h in a nitrogen atmosphere after drying is finished, performing suction filtration and washing on the high-temperature roasted product for multiple times by using deionized water until the product is neutral, drying the washed product at 110 ℃ for 12h, and finally reducing the product at 580 ℃ for 1h to obtain the catalyst A.
Filling 0.2g of A catalyst in a fixed bed micro-reaction device, taking the mixed gas of propane and nitrogen with the volume fraction of 5 percent as reaction raw materials, and keeping the mass space velocity of the propane at 600 ℃, normal pressure and propane of 0.6h-1Reacting under reaction conditions, after continuously introducing reaction raw materials for 5min, carrying out component measurement on the mixed gas at the discharging position, detecting the content of propane and propylene, and calculating the conversion rate of propane and the selectivity of propylene (the same below) by the following method:
noting that the propane content in the product is x (volume fraction) and the propylene content is y (volume fraction), the following are:
propane conversion = (5% -x)/5%, propylene selectivity = y/(5% -x).
The results of this example are reported in table 1.
Example 2
Uniformly mixing 4.0g of anhydrous glucose with 40mL of deionized water, transferring the mixture to a 80mL polytetrafluoroethylene inner stainless steel autoclave, carrying out hydrothermal treatment for 12h at the temperature of 180 ℃, cooling, carrying out suction filtration and washing on the product for multiple times by using the deionized water until the filtrate is colorless, drying the product subjected to suction filtration at the temperature of 110 ℃ for 12h, and roasting the product at the low temperature of 400 ℃ for 2h in the nitrogen atmosphere after drying. Mixing 1.1g of the original carbon material after low-temperature roasting with 2.2g of NaOH-containing aqueous solution, and stirring for 12 hours; drying the stirred product at 110 ℃ for 12h, roasting the dried product at 700 ℃ for 2h under the nitrogen atmosphere, performing suction filtration and washing on the high-temperature roasted product for multiple times by using deionized water until the product is neutral, drying the product at 110 ℃ for 12h, and finally reducing the product for 1h under the 580 ℃ hydrogen atmosphere to obtain the catalyst B.
Filling 0.2gB catalyst in a fixed bed micro-reaction device by volume fraction5 percent of propane and nitrogen mixed gas is used as reaction raw material, the temperature is 600 ℃, the normal pressure and the propane mass space velocity are 0.6h-1Reacting under the reaction condition, after continuously introducing the reaction raw materials for 5min, carrying out component measurement on the mixed gas at the discharging position, detecting the content of propane and propylene in the mixed gas, and calculating the conversion rate of the propane and the selectivity of the propylene. The results of this example are reported in table 1.
Example 3
Uniformly mixing 4.0g of anhydrous glucose with 40mL of deionized water, transferring the mixture to a 80mL polytetrafluoroethylene inner stainless steel autoclave, carrying out hydrothermal treatment for 12h at the temperature of 180 ℃, cooling, carrying out suction filtration and washing on the product for multiple times by using the deionized water until the filtrate is colorless, drying the product subjected to suction filtration at the temperature of 110 ℃ for 12h, and roasting the product at the low temperature of 400 ℃ for 2h in the nitrogen atmosphere after drying. Mixing 1.1g of the original carbon material after low-temperature roasting with an aqueous solution containing 3.3g of NaOH, and stirring for 12 hours; drying the stirred product at 110 ℃ for 12h, roasting at 700 ℃ for 2h in a nitrogen atmosphere after drying, performing suction filtration and washing on the high-temperature roasted product for multiple times by using deionized water until the product is neutral, drying at 110 ℃ for 12h, and finally reducing for 1h in a 580 ℃ hydrogen atmosphere to obtain the catalyst C.
Filling 0.2g of C catalyst in a fixed bed micro-reaction device, taking 5 volume percent of propane and nitrogen mixed gas as reaction raw materials, and keeping the mass space velocity of the propane at 600 ℃, normal pressure and 0.6h-1Reacting under the reaction condition, after continuously introducing the reaction raw materials for 5min, carrying out component measurement on the mixed gas at the discharging position, detecting the content of propane and propylene in the mixed gas, and calculating the conversion rate of the propane and the selectivity of the propylene. The results of this example are reported in table 1.
Example 4
Uniformly mixing 4.0g of anhydrous glucose with 40mL of deionized water, transferring the mixture to a 80mL polytetrafluoroethylene inner stainless steel autoclave, carrying out hydrothermal treatment for 12h at the temperature of 180 ℃, cooling, carrying out suction filtration and washing on the product for multiple times by using the deionized water until the filtrate is colorless, drying the product subjected to suction filtration at the temperature of 110 ℃ for 12h, and roasting the product at the low temperature of 400 ℃ for 2h in the nitrogen atmosphere after drying. Mixing 1.1g of the original carbon material after low-temperature roasting with 2.2g of NaOH-containing aqueous solution, and stirring for 12 hours; drying the stirred product at 110 ℃ for 12h, roasting at 600 ℃ for 2h under the nitrogen atmosphere after drying, performing suction filtration and washing on the high-temperature roasted product for multiple times by using deionized water until the product is neutral, drying at 110 ℃ for 12h, and finally reducing for 1h under the 580 ℃ hydrogen atmosphere to obtain the catalyst D.
Filling 0.2g of D catalyst in a fixed bed micro-reaction device, taking the mixed gas of propane and nitrogen with the volume fraction of 5 percent as a reaction raw material, and keeping the mass space velocity of the propane at 600 ℃, normal pressure and 0.6h-1Reacting under the reaction condition, after continuously introducing the reaction raw materials for 5min, carrying out component measurement on the mixed gas at the discharging position, detecting the content of propane and propylene in the mixed gas, and calculating the conversion rate of the propane and the selectivity of the propylene. The results of this example are reported in table 1.
Example 5
Taking 4.0g of anhydrous glucose and 40mL of deionized water, uniformly mixing, transferring to a 80mL polytetrafluoroethylene stainless steel autoclave, carrying out hydrothermal treatment for 12h at 180 ℃, cooling, carrying out suction filtration washing on the product with deionized water for many times until the filtrate is colorless, drying the suction-filtered product at 110 ℃ for 12h, and roasting at 400 ℃ for 2h in a nitrogen atmosphere after drying. Mixing 1.1g of the original carbon material after low-temperature roasting with 2.2g of NaOH-containing aqueous solution, and stirring for 12 hours; drying the stirred product at 110 ℃ for 12h, roasting at 800 ℃ for 2h in a nitrogen atmosphere after drying, performing suction filtration and washing on the high-temperature roasted product for multiple times by using deionized water until the product is neutral, drying at 110 ℃ for 12h, and finally reducing for 1h in a 580 ℃ hydrogen atmosphere to obtain the catalyst E.
Filling 0.2g of E catalyst in a fixed bed micro-reaction device, taking the mixed gas of propane and nitrogen with the volume fraction of 5 percent as a reaction raw material, and keeping the mass space velocity of the propane at 600 ℃, normal pressure and 0.6h-1Reacting under the reaction condition, continuously introducing reaction raw materials for 5min, then carrying out component determination on the mixed gas at the discharge position, detecting the content of propane and propylene, and calculating the conversion rate of propane and the selectivity of propylene. The results of this example are reported in table 1.
Comparative example
Uniformly mixing 4.0g of anhydrous glucose with 40mL of deionized water, transferring the mixture to a 80mL polytetrafluoroethylene inner stainless steel autoclave, carrying out hydrothermal treatment for 12h at the temperature of 180 ℃, cooling, carrying out suction filtration and washing on the product for multiple times by using the deionized water until the filtrate is colorless, drying the product subjected to suction filtration at the temperature of 110 ℃ for 12h, and roasting the product at the low temperature of 400 ℃ for 2h in the nitrogen atmosphere after drying. Mixing 1.1g of the original carbon material after low-temperature roasting with a NaOH-free aqueous solution, and stirring for 12 hours; drying the stirred product at 110 ℃ for 12h, roasting at 700 ℃ for 2h in a nitrogen atmosphere after drying, performing suction filtration and washing on the high-temperature roasted product for multiple times by using deionized water until the product is neutral, drying at 110 ℃ for 12h, and finally reducing for 1h in a 580 ℃ hydrogen atmosphere to obtain the catalyst F.
Filling 0.2g of F catalyst in a fixed bed micro-reaction device, taking the mixed gas of propane and nitrogen with the volume fraction of 5 percent as reaction raw materials, and keeping the mass space velocity of the propane at 600 ℃, normal pressure and 0.6h-1Reacting under the reaction condition, after continuously introducing the reaction raw materials for 5min, carrying out component measurement on the mixed gas at the discharging position, detecting the content of propane and propylene in the mixed gas, and calculating the conversion rate of the propane and the selectivity of the propylene. The results of this comparative example are reported in table 1.
TABLE 1
When the reaction is performed for 5min, since the activity of the catalyst is not substantially reduced due to the progress of the reaction, the activity at this time can be regarded as the initial activity of the catalyst, and it can be seen from table 1 that the propane conversion rates of examples 1 to 5 are improved in different ranges compared to the comparative examples, and the propane selectivity is not uniformly increased or decreased, which indicates that the treatment of the carbon material with the strong base solution can improve the adsorption and treatment capacity of the carbon material to propane, and the effect of improving the propylene selectivity can be achieved by selecting an appropriate ratio of the strong base solution in terms of selectivity, as in example 3. Comparing the scanning electron micrographs (fig. 1 and 2) of the comparative catalyst F and the catalyst C of the present invention, it can be seen that the catalyst C after the strong alkali treatment has a honeycomb-shaped porous structure, whereas the comparative catalyst F does not have such a structure, indicating that the strong alkali treatment can remove unstable impurity carbon on the original carbon material and can produce a large number of cell channels; the honeycomb porous structure can increase the contact area of propane and active groups, and can quickly desorb the product propylene to prevent the selectivity reduction of the target product propylene caused by further deep cracking.
The catalyst C obtained in example 3 was subjected to a long-term reactivity test as follows:
filling 0.2g of C catalyst in a fixed bed micro-reaction device, taking mixed gas of propane and nitrogen with volume fraction of 5% as reaction raw materials, reacting under the reaction conditions of 600 ℃, normal pressure and propane mass space velocity of 0.6h < -1 >, measuring components of the mixed gas at a discharge position every 30min, detecting the content of propane and propylene, and calculating the conversion rate of propane and the selectivity of propylene. The reaction was continued for a total of 10h and the test results are reported in table 2.
TABLE 2
As can be seen from Table 2, the catalyst prepared by the invention can maintain higher reaction activity under long-term reaction conditions, and generates fewer byproducts in the reaction process. The catalytic activity of the catalyst is gradually reduced due to the carbon deposition problem in the reaction process, but the catalyst prepared by the invention has low cost, is environment-friendly and simple to prepare, and can be replaced when the reaction activity is low without generating great influence on the production cost.
Claims (9)
1. A method for preparing a non-metal porous carbon material catalyst by taking saccharides as raw materials is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing the saccharide raw materials with water, putting the mixture into a hydrothermal kettle, carrying out hydrothermal carbonization at 120-200 ℃ to obtain a carbonized material, and filtering and washing the carbonized material;
s2, roasting the carbonized material at a low temperature of 300-600 ℃;
s3, putting the carbonized material after low-temperature roasting into a strong alkali aqueous solution, stirring to remove amorphous carbon in the carbonized material, roasting at the high temperature of 600-1100 ℃, and washing the carbonized material after high-temperature roasting to be neutral;
s4, reducing the carbonized material obtained in s3 by using a reducing agent or hydrogen reducing atmosphere to obtain a nonmetal porous carbon material catalyst;
the strong alkali aqueous solution is NaOH solution, KOH solution or a mixed solution of NaOH and KOH, and the mass of alkali in the strong alkali aqueous solution is 1-10 times of that of the carbonized material subjected to low-temperature roasting in s 2.
2. The method for preparing a non-metallic porous carbon material catalyst using a saccharide as a raw material according to claim 1, wherein: the saccharide is selected from one or more of starch, sucrose, fructose, glucose, maltose, cellulose or lactose.
3. The method for preparing a non-metallic porous carbon material catalyst using a saccharide as a raw material according to claim 1, wherein: the reducing agent in s4 is selected from one or more of ethylene glycol, C1-C3 carboxylic acid or C1-C3 sodium carboxylate.
4. The method for preparing a non-metallic porous carbon material catalyst using a saccharide as a raw material according to claim 1, wherein: in the strong alkali water solution, the mass of the strong alkali is 2-4 times of that of the carbonized material after low-temperature roasting in s 2.
5. The method for preparing a non-metallic porous carbon material catalyst using a saccharide as a raw material according to claim 1, wherein: the temperature of the high-temperature roasting process is 650-750 ℃.
6. The method for preparing a non-metallic porous carbon material catalyst using a saccharide as a raw material according to claim 1, wherein: the low-temperature roasting process is carried out under the protective atmosphere of inert gas or nitrogen.
7. The method for preparing a non-metallic porous carbon material catalyst using a saccharide as a raw material according to claim 1, wherein: the high-temperature roasting process is carried out under the protective atmosphere of inert gas or nitrogen.
8. A non-metallic porous carbon material catalyst is characterized in that: prepared by the method of any one of claims 1 to 7.
9. The use of the non-metallic porous carbon material catalyst according to claim 8 for catalyzing the dehydrogenation of propane to propylene.
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