CN108160089B - Preparation method of dehydrogenation catalyst for reducing material loading and unloading - Google Patents
Preparation method of dehydrogenation catalyst for reducing material loading and unloading Download PDFInfo
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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
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- 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
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- C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals
- C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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- C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
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- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a dehydrogenation catalyst preparation method for reducing material loading and unloading, which comprises the steps of one or more or all preparation steps of carrier impregnation, drying, roasting, post-treatment and reduction treatment in the dehydrogenation catalyst preparation process, wherein the solid materials do not need to be unloaded in the intermediate step until a catalyst finished product is obtained; the preparation container comprises a cylindrical container main body, the front end of the cylindrical container main body is connected with a plurality of liquid material inlets and a plurality of gas material inlets through pipelines, and a distributor is arranged inside the cylindrical container main body; the tail end is provided with a liquid material outlet, a gas material outlet and a solid material inlet and outlet; the outer surface of the container main body is coated with a heating layer and a heat-insulating layer from inside to outside; the container body is provided with an axial rotation shaft and a radial rotation shaft. The method can reduce the loading and unloading of solid materials in the preparation process of the catalyst, reduce the operation cost, improve the stability of the catalyst and the dispersion of active components, has simple preparation method, and is beneficial to industrial scale-up production.
Description
Technical Field
The invention belongs to the field of catalyst preparation, and particularly relates to a preparation method of a dehydrogenation catalyst for reducing material loading and unloading.
Background
In recent years, with the rapid development of the global petrochemical industry, the demand for low-carbon olefins is increasing day by day, and the dehydrogenation of low-carbon alkanes (C3-C4) is an important way for realizing the optimized utilization of natural gas, refinery gas and oil field associated gas resources, and can relieve the contradiction of the short supply and short demand of the low-carbon olefins, particularly propylene. Currently, the world low-carbon alkane dehydrogenation technology comprises: oleflex process by UOP, Catofin process by ABB rum, Star process by Comphyte, FBD-4 process by Snamprogetti/Yarsintz, PDH process by Linde/Pasteur, etc. The existing mature process for preparing low-carbon olefin by dehydrogenating low-carbon alkane is an 'Oleflex' process developed by UOP company in the United states. The process combines a 'Pacol' process of long-chain alkane dehydrogenation and a continuous regeneration process of a platinum reforming catalyst, and the used catalyst is similar to the catalyst of the 'Pacol' process, namely, the supported Pt/gamma-Al2O3A catalyst.
The prior art is directed to catalyst compositions comprising a group VIII noble metal component, a component selected from the group consisting of tin, germanium, indium, gallium, thallium, or mixtures thereof, a group IA or IIA metal component and a halogen component, formed by one or more impregnation steps, and dried and calcined. However, the prior art has no preparation method of the catalyst as follows: active components and all the auxiliary components are impregnated in the reaction tube, the impregnation method is simpler, the loss of the auxiliary elements is reduced, the auxiliary elements are completely impregnated on the catalyst, the impregnation is more uniform, the acidity modulation of the catalyst is facilitated, and the dehydrogenation reaction of the catalyst is facilitated.
CN1265878C discloses a catalystA composition comprising a group VIII noble metal component, an alkali metal and tin, germanium and mixtures thereof, said component being impregnated in steps on an alumina support. The alumina carrier is also characterized by having a larger bulk density of 0.5g/cm3. CN1069226C discloses a preparation method of a Pt-based low-carbon alkane dehydrogenation catalyst, which adopts a step-by-step impregnation mode to load various active components and auxiliaries on the catalyst, and in the preparation process of the catalyst, wet solid materials are required to be taken out for drying and roasting after each step of impregnation.
The existing dehydrogenation catalyst preparation technology generally adopts the modes of impregnation, mixing or coprecipitation and the like, so that active components are uniformly distributed in the catalyst as much as possible. In the alkane dehydrogenation reaction process, the uniform distribution of the active component noble metal is a necessary condition for ensuring the initial conversion rate in the reaction of preparing the olefin by alkane dehydrogenation and is also a key for improving the conversion rate and the selectivity of the dehydrogenation catalyst, the uniform distribution of the alkali metal is a key for adjusting the acidity in the catalyst and is a premise for ensuring the stability of the catalyst, and the uniform distribution of the halogen element is a necessary condition for adjusting the strength of the catalyst, so that a proper impregnation method still needs to be selected to ensure that the active component and the auxiliary agent component are uniformly distributed on a carrier, thereby improving the conversion rate and the selectivity of the dehydrogenation catalyst. However, in the existing preparation method of the Pt-based dehydrogenation catalyst, the solid particles need to be taken out of the equipment and put into the equipment for many times in the preparation process, so that the operation cost of the catalyst preparation process is greatly increased, the catalyst particles are crushed, and higher requirements are put forward on indexes such as carrier strength and the like.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the existing preparation method of the low-carbon alkane dehydrogenation catalyst, and provide the preparation method of the dehydrogenation catalyst with less material loading and unloading.
In order to achieve the purpose, the invention adopts the following technical scheme: preparing the main active substance and other component substances into impregnation liquid, filling the carrier into a catalyst preparation container, sending the impregnation liquid into the preparation container, and directly roasting in the preparation container to obtain the catalyst finished product. If stepwise impregnation is required, the impregnation is carried out stepwise as required, and during these operations the solid particles may be in the preparation vessel at all times. The specific technical scheme is as follows:
a method of preparing a dehydrogenation catalyst that reduces material handling, comprising:
the first step is as follows: loading the carrier into a catalyst preparation container;
the second step is that: preparing a steeping fluid;
the third step: conveying the impregnation liquid to a catalyst preparation container, uniformly loading the active components to a carrier by adopting an impregnation mode, and then drying; preferably, the preparation vessel is purged with a drying gas to accelerate the removal of impregnation
Drying the resulting gas in a vessel;
the fourth step: roasting the catalyst precursor obtained in the third step, preferably introducing gas, and accelerating the removal of gas generated by roasting in the preparation container;
the fifth step: adopting multiple times of dipping according to requirements, and repeating the second step to the fourth step;
and a sixth step: post-treating the catalyst precursor in an oxygen-containing atmosphere;
the seventh step: reducing the catalyst precursor in an atmosphere containing reducing substances to obtain a catalyst finished product;
wherein, all preparation steps of carrier impregnation, drying, roasting, post-treatment and reduction treatment are carried out in one preparation container, and solid materials do not need to be discharged in the middle step until a catalyst finished product is obtained;
the preparation container comprises a cylindrical container main body, the front end of the container main body is connected with a plurality of liquid material inlets and a plurality of gas material inlets through pipelines, and a distributor is arranged in the container main body, so that gas and liquid uniformly pass through a catalyst bed layer after passing through the distributor; the tail end of the container main body is provided with a liquid material outlet, a gas material outlet and a solid material inlet and outlet; the outer surface of the container main body is coated with a heating layer and a heat-insulating layer from inside to outside; the inner wall of the container main body is made of corrosion-resistant and high-temperature-resistant steel, alloy or ceramic;
axial rotating shafts are arranged on two axial sides of the container main body so as to realize the axial rotation of the cylindrical container main body; the middle parts of the two sides of the container are provided with radial rotating shafts perpendicular to the axis direction so as to realize that the container body rotates up and down to facilitate loading and unloading of materials, and the radial rotating shafts are fixed on the fixed support.
The catalyst preparation process can be used for preparing Pt dehydrogenation catalysts. The catalyst is made of Al2O3The catalyst is used as a carrier, platinum is used as a main active component or a first component, a second component is one of tin, germanium and lead and a mixture thereof, an alkali metal is used as a promoter component and is used as a third component, and halogen is used as a fourth component. The weight percentage of each component of the obtained catalyst is (calculated by simple substance), the content of platinum is 0.01-10%, preferably 0.2-0.5%; the content of the second component is 0.01-10%, preferably 0.01-5%; the content of alkali metal is 0.1-20%, preferably 1-10%; the halogen content is 0.1-5%, preferably 1.1-1.6%;
the platinum of the catalyst active component is mainly from a platinum-containing solution, including chloroplatinic acid and the like. The auxiliary component is selected from chlorides of tin, germanium and lead. The alkali metal additives include potassium and sodium sulfates, nitrates, carbonates, phosphates, bicarbonates, and the additives also include alkaline earth metal compounds, including calcium and magnesium nitrates. The halogen component is one or more of fluorine and chlorine, including dichloroethane, tetrachloroethylene, tetrafluoroethylene, and tetrafluoroethane. Acids used to prepare the dehydrogenation catalyst include hydrochloric acid, nitric acid, acetic acid, and aqueous solutions thereof.
Compared with the prior art, the invention has the following advantages:
in the whole catalyst preparation process, solid particles in all the operation steps can be discharged from the preparation container without loading the carrier into the preparation container until obtaining a catalyst finished product, so that the catalyst preparation process is simplified, and the operation cost is saved; in addition, the supported Pt catalyst prepared by the preparation method has the advantage of high dispersion of Pt component (the particle size range of Pt metal is between 0.5 and 5 nm), and the supported Pt catalyst has good stability in high-temperature reaction at the temperature of 600 ℃ or above, solves the problem of high-temperature stability of noble metal catalysts which cannot be well solved at present, and has good large-scale production and industrial application prospects.
Drawings
FIG. 1 is a schematic diagram of a preparation vessel used in a process for preparing a dehydrogenation catalyst having reduced material loading and unloading according to the present invention.
In the figure, 1 is a preparation container main body, 2 is a distributor, 3 is a rotating shaft, 4 is a gas material inlet, 5 is a liquid material inlet, 6 is a gas material outlet, 7 is a fixed support, and 8 is a liquid/solid material outlet.
Detailed Description
The invention is further illustrated by the following specific examples:
example 1
50 g of aluminum oxide carrier is weighed and put into a preparation container, 0.39 g of H is weighed2PtCl66H2Dissolving the solution into 50mL of deionized water to prepare an impregnation solution a, adding the impregnation solution a into a preparation container filled with the carrier for volume impregnation, drying the solid material for 2h at 120 ℃ without taking out the solid material after the impregnation is finished for 12h, and roasting the solid material for 4h at 510 ℃;
0.032 g of SnCl is weighed2.2H2Dissolving the raw materials by using 15mL of 35% diluted hydrochloric acid, adding 25mL of deionized water to dilute the raw materials into an impregnation solution b, adding the impregnation solution b into a preparation container filled with the active component platinum after impregnation for isovolumetric impregnation, after the impregnation is completed for 8 hours, taking out the solid materials, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
weighing 0.21 g of potassium chloride, dissolving the potassium chloride by using 40mL of deionized water to prepare a potassium chloride impregnation liquid c, adding the impregnation liquid c into a preparation container filled with platinum tin after impregnation for isovolumetric impregnation, not taking out solid materials after the impregnation is finished for 8 hours, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
adding 40 mu L of dichloroethane liquid into a preparation container filled with impregnated platinum, tin and potassium, treating the halogen element for 1h, drying the solid material in the preparation container at 120 ℃ for 5h without taking out the solid material, and roasting the solid material at 510 ℃ for 9 h;
then at 480 ℃, introducing 20% of air and 80% of nitrogen into the preparation container filled with the impregnated active components for treatment for 2 hours, and then introducing a mixed gas of 12% of hydrogen and 88% of nitrogen for catalyst reduction for 4 hours to prepare a finished catalyst product a 1;
the mass content of the active component of the catalyst a1 is Pt: 0.35 percent; sn: 0.12 percent; k: 1.0%, Cl: 1.1 percent.
Example 2
50 g of alumina carrier is weighed and put into a preparation container, 0.31 g of H is weighed2PtCl66H2Dissolving the solution into 50mL of deionized water to prepare an impregnation solution a, adding the impregnation solution a into a preparation container filled with the carrier for volume impregnation, drying the solid material for 2h at 120 ℃ without taking out the solid material after the impregnation is finished for 12h, and roasting the solid material for 4h at 510 ℃;
0.032 g of SnCl is weighed2.2H2Dissolving the raw materials by using 15mL of 35% diluted hydrochloric acid, adding 25mL of deionized water to dilute the raw materials into an impregnation solution b, adding the impregnation solution b into a preparation container filled with the active component platinum after impregnation for isovolumetric impregnation, after the impregnation is completed for 8 hours, taking out the solid materials, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
weighing 0.2 g of potassium chloride, dissolving the potassium chloride by using 40mL of deionized water to prepare a potassium chloride impregnation liquid c, adding the impregnation liquid c into a preparation container filled with platinum tin after impregnation for isovolumetric impregnation, not taking out solid materials after the impregnation is finished for 8 hours, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
adding 40 mu L of dichloroethane liquid into a preparation container filled with impregnated platinum, tin and potassium, treating the halogen element for 1h, drying the solid material in the preparation container at 120 ℃ for 5h without taking out the solid material, and roasting the solid material at 510 ℃ for 9 h;
then at 480 ℃, introducing 20% of air and 80% of nitrogen into the preparation container filled with the impregnated active components for treatment for 2 hours, and then introducing a mixed gas of 12% of hydrogen and 88% of nitrogen for catalyst reduction for 4 hours to prepare a finished catalyst product a 2;
the mass content of the active component of the catalyst a2 is Pt: 0.21 percent; sn: 0.12 percent; k: 1.0%, Cl: 1.1 percent.
Example 3
50 g of alumina carrier is weighed and put into a preparation container, 0.31 g of H is weighed2PtCl66H2Dissolving the solution into 50mL of deionized water to prepare an impregnation solution a, adding the impregnation solution a into a preparation container filled with the carrier for volume impregnation, drying the solid material for 2h at 120 ℃ without taking out the solid material after the impregnation is finished for 12h, and roasting the solid material for 4h at 510 ℃;
0.72 g SnCl was weighed2.2H2Dissolving the raw materials by using 15mL of 35% diluted hydrochloric acid, adding 25mL of deionized water to dilute the raw materials into an impregnation solution b, adding the impregnation solution b into a preparation container filled with the active component platinum after impregnation for isovolumetric impregnation, after the impregnation is completed for 8 hours, taking out the solid materials, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
weighing 0.2 g of potassium chloride, dissolving the potassium chloride by using 40mL of deionized water to prepare a potassium chloride impregnation liquid c, adding the impregnation liquid c into a preparation container filled with platinum tin after impregnation for isovolumetric impregnation, not taking out solid materials after the impregnation is finished for 8 hours, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
adding 40 mu L of dichloroethane liquid into a preparation container filled with impregnated platinum, tin and potassium, treating the halogen element for 1h, drying the solid material in the preparation container at 120 ℃ for 5h without taking out the solid material, and roasting the solid material at 510 ℃ for 9 h;
then at 480 ℃, introducing 20% of air and 80% of nitrogen into the preparation container filled with the impregnated active components for treatment for 2 hours, and then introducing a mixed gas of 12% of hydrogen and 88% of nitrogen for catalyst reduction for 4 hours to prepare a finished catalyst product a 3;
the mass content of the active component of the catalyst a3 is Pt: 0.21 percent; sn: 4.2 percent; k: 1.0%, Cl: 1.1 percent.
Example 4
50 g of alumina carrier is weighed and put into a preparation container, 0.31 g of H is weighed2PtCl66H2Dissolving the solution into 50mL of deionized water to prepare an impregnation solution a, adding the impregnation solution a into a preparation container filled with the carrier for volume impregnation, drying the solid material for 2h at 120 ℃ without taking out the solid material after the impregnation is finished for 12h, and roasting the solid material for 4h at 510 ℃;
0.032 g of SnCl is weighed2.2H2Dissolving the raw materials by using 15mL of 35% diluted hydrochloric acid, adding 25mL of deionized water to dilute the raw materials into an impregnation solution b, adding the impregnation solution b into a preparation container filled with the active component platinum after impregnation for isovolumetric impregnation, after the impregnation is completed for 8 hours, taking out the solid materials, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
weighing 0.4 g of potassium chloride, dissolving the potassium chloride by using 40mL of deionized water to prepare a potassium chloride impregnation liquid c, adding the impregnation liquid c into a preparation container filled with platinum tin after impregnation for isovolumetric impregnation, not taking out solid materials after the impregnation is finished for 8 hours, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
adding 40 mu L of dichloroethane liquid into a preparation container filled with impregnated platinum, tin and potassium, treating the halogen element for 1h, drying the solid material in the preparation container at 120 ℃ for 5h without taking out the solid material, and roasting the solid material at 510 ℃ for 9 h;
then at 480 ℃, introducing 20% of air and 80% of nitrogen into the preparation container filled with the impregnated active components for treatment for 2 hours, and then introducing a mixed gas of 12% of hydrogen and 88% of nitrogen for catalyst reduction for 4 hours to prepare a finished catalyst product a 4;
the mass content of the active component of the catalyst a4 is Pt: 0.21 percent; sn: 0.12 percent; k: 2.0%, Cl: 1.1 percent.
Example 5
50 g of aluminum oxide carrier is weighed and put into a preparation container, 0.39 g of H is weighed2PtCl66H2Dissolving the solution into 50mL of deionized water to prepare an impregnation solution a, adding the impregnation solution a into a preparation container filled with the carrier for volume impregnation, drying the solid material for 2h at 120 ℃ without taking out the solid material after the impregnation is finished for 12h, and roasting the solid material for 4h at 510 ℃;
0.032 g of SnCl is weighed2.2H2Dissolving the raw materials by using 15mL of 35% diluted hydrochloric acid, adding 25mL of deionized water to dilute the raw materials into an impregnation solution b, adding the impregnation solution b into a preparation container filled with the active component platinum after impregnation for isovolumetric impregnation, after the impregnation is completed for 8 hours, taking out the solid materials, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
weighing 0.2 g of potassium chloride, dissolving the potassium chloride by using 40mL of deionized water to prepare a potassium chloride impregnation liquid c, adding the impregnation liquid c into a preparation container filled with platinum tin after impregnation for isovolumetric impregnation, not taking out solid materials after the impregnation is finished for 8 hours, drying the solid materials at 120 ℃ for 2 hours, and roasting the solid materials at 510 ℃ for 4 hours;
then adding 20 mu L of dichloroethane liquid into a preparation container filled with the platinum-tin-potassium impregnated in the container, carrying out halogen element treatment for 1h, drying the solid material in the preparation container at 120 ℃ for 5h without taking out the solid material, and roasting the solid material at 510 ℃ for 9 h;
then at 480 ℃, introducing 20% of air and 80% of nitrogen into the preparation container filled with the impregnated active components for treatment for 2 hours, and then introducing a mixed gas of 12% of hydrogen and 88% of nitrogen for catalyst reduction for 4 hours to prepare a finished catalyst product a 5;
the mass content of the active component of the catalyst a4 is Pt: 0.35 percent; sn: 4.2 percent; k: 1.0%, Cl: 0.6 percent.
Comparative example 1
1) 50 g of alumina carrier is weighed and put into a container, 0.59 g of H is weighed2PtCl66H2O, 0.72 g SnCl2.2H2Dissolving the solution into 50mL of diluted hydrochloric acid to prepare an impregnation solution a, adding the impregnation solution a into a container of the carrier for impregnation, taking out the solid material after the impregnation for 12 hours, drying the solid material at 120 ℃ for 2 hours, and roasting the solid material at 510 ℃ for 4 hours;
2) weighing 1.6 g of sodium nitrate, dissolving the sodium nitrate by using 50mL of deionized water to prepare sodium nitrate impregnation liquid b, adding the impregnation liquid b into a container to impregnate the solid material obtained in the step 1), taking out the solid material after impregnation, drying the solid material at 120 ℃ for 2h, and roasting the solid material at 510 ℃ for 4 h;
3) adding 40 mu L of tetrachloroethylene liquid into a container, carrying out halogen element treatment on the solid material obtained in the step 2), treating for 1h, taking out the solid material after the treatment, drying for 2h at 120 ℃, and roasting for 4h at 510 ℃;
4) post-treating the solid material obtained in step 3): treating with 20% of air and 80% of nitrogen for 2h at 480 ℃, and then carrying out catalyst reduction for 4h under the condition of mixed gas of 12% of hydrogen and 88% of nitrogen to prepare a finished catalyst product b 1;
the mass content of the active component of the catalyst b1 is Pt: 0.52 percent; sn: 4.1 percent; na: 2.4%, Cl: 1.1 percent.
Comparative example 2
1) 50 g of aluminum oxide carrier is weighed and put into a container, 0.31 g of H is weighed2PtCl6 6H2Dissolving the O in 50mL of deionized water to prepare an impregnation liquid a, adding the impregnation liquid a into a container filled with a carrier for volume impregnation for 12 hours, taking out the solid material, drying at 120 ℃ for 2 hours, and roasting at 510 ℃ for 4 hours;
2) 0.095 g SnCl was weighed2.2H2Dissolving the O with 15mL of 35% diluted hydrochloric acid, adding 25mL of deionized water to dilute the solution into a steeping solution b, steeping 1) to obtain a solid material, steeping for 8 hours in the same volume, taking out the solid material, drying at 120 ℃ for 2 hours, and roasting at 510 ℃ for 4 hours;
3) weighing 1 g of potassium chloride, dissolving the potassium chloride by using 40mL of deionized water to prepare potassium chloride impregnation liquid c, impregnating the potassium chloride impregnation liquid c in an equal volume manner for 2) to obtain a solid material, taking out the solid material after the completion, drying the solid material at 120 ℃ for 2h, and roasting the solid material at 510 ℃ for 4 h;
4) treating the solid material obtained in step 3) with 40 mu L of dichloroethane liquid, taking out the solid material after the impregnation is finished, drying the solid material at the temperature of 120 ℃ for 5 hours, and roasting the solid material at the temperature of 510 ℃ for 9 hours;
5) post-treating the solid material obtained in the step 4): treating with 20% of air and 80% of nitrogen for 2h at 480 ℃, and then carrying out catalyst reduction for 4h under the condition of mixed gas of 12% of hydrogen and 88% of nitrogen to prepare a finished catalyst product b 2;
the mass content of the active component of the catalyst b2 is Pt: 0.22 percent; sn: 0.54 percent; k: 5.1%, Cl: 1.2 percent. Evaluation of catalyst:
propane dehydrogenation reaction performance test of the catalyst: a10 ml microreaction evaluation device was used. About 5g of catalyst is filled in a stainless steel reactor with the inner diameter of 8 mm, and the performance test of the propane dehydrogenation reaction is carried out, wherein the relevant reaction conditions are as follows:
raw material gas: propane;
pressure: normal pressure;
space velocity: 1000 hours-1；
The reaction temperature is 600 ℃;
the results of the propane dehydrogenation performance of the catalyst a1, which were analyzed for propane conversion and propylene selectivity starting after 20 minutes of reaction time, are shown in the following table.
As can be seen from the following table, the initial activator of the catalyst prepared by the invention is higher than that of the comparative catalyst, the propane conversion rate is slightly reduced after 7 days of reaction, the propylene selectivity is not greatly changed, and the propane conversion rate and the propylene selectivity of the comparative catalyst are greatly reduced.
Claims (4)
1. A preparation method of a dehydrogenation catalyst for reducing material loading and unloading is characterized by comprising the following steps:
the first step is as follows: loading the carrier into a catalyst preparation container;
the second step is that: preparing a steeping fluid;
the third step: conveying the impregnation liquid to a catalyst preparation container, uniformly loading the active components to a carrier by adopting an impregnation mode, and then drying;
the fourth step: roasting the catalyst precursor obtained in the third step,
the fifth step: adopting multiple times of dipping according to requirements, and repeating the second step to the fourth step;
and a sixth step: post-treating the catalyst precursor in an oxygen-containing atmosphere;
the seventh step: reducing the catalyst precursor in an atmosphere containing reducing substances to obtain a catalyst finished product;
wherein, all preparation steps of carrier impregnation, drying, roasting, post-treatment and reduction treatment are carried out in one preparation container, and solid materials do not need to be discharged in the middle step until a catalyst finished product is obtained;
the preparation container comprises a cylindrical container main body, the front end of the container main body is connected with a plurality of liquid material inlets and a plurality of gas material inlets through pipelines, and a distributor is arranged in the container main body, so that gas and liquid uniformly pass through a catalyst bed layer after passing through the distributor; the tail end of the container main body is provided with a liquid material outlet, a gas material outlet and a solid material inlet and outlet; the outer surface of the container main body is coated with a heating layer and a heat-insulating layer from inside to outside; the inner wall of the container main body is made of corrosion-resistant and high-temperature-resistant steel, alloy or ceramic;
axial rotating shafts are arranged on two axial sides of the container main body so as to realize the axial rotation of the cylindrical container main body; the middle parts of the two sides of the container are provided with radial rotating shafts perpendicular to the axis direction so as to realize that the container body rotates up and down to facilitate loading and unloading of materials, and the radial rotating shafts are fixed on the fixed support.
2. The process according to claim 1, wherein in the third step, a drying gas is introduced into the preparation vessel to accelerate the removal of the gas generated by the drying in the impregnation vessel.
3. The method of claim 1, wherein in the fourth step, a gas is introduced into the preparation vessel to accelerate the removal of the gas generated by the firing in the preparation vessel.
4. The preparation method according to claim 1, wherein the carrier is alumina, the active component is one or more of platinum, tin, germanium and lead, and the alkali metal and the halogen are used as promoter components, wherein the catalyst active component accounts for 0.01-10% by weight, the alkali metal accounts for 0.1-20% by weight and the halogen accounts for 0.1-5% by weight of the single substance.
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