CN114260007A - Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof - Google Patents
Catalyst for preparing propylene by high mechanical strength propane dehydrogenation and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst material with high mechanical strength for preparing propylene by propane catalytic dehydrogenation and a preparation method thereof, wherein the catalyst material is xCr2O3V (support + A) wherein x is Cr2O3Carrying capacity: x is 5-25%; the carrier is yMaOb·zAl2O3A is SiC or SiO with 50-200 meshes2、Al2O3h-BN, SiN or carbo-silicon-boronAnd the carrier: the mass ratio of A is 1-9: 1. The carrier material and the catalyst are used in the reaction process of preparing propylene by propane catalytic dehydrogenation, the mechanical strength of the carrier material and the catalyst is greatly improved on the basis of keeping higher propane dehydrogenation activity and selectivity, and the service life of the catalyst is hopefully prolonged and the stability of the catalyst is improved in industrial application.
Description
Technical Field
The invention aims at a propane catalytic dehydrogenation process, relates to a high-side pressure strength carrier, a loaded catalyst material and a preparation method thereof, and belongs to the field of materials or chemical engineering.
Background
Propylene is an important petrochemical basic raw material second only to ethylene, and is widely used for producing polypropylene, butanol and octanol, acrylonitrile, propylene oxide, epichlorohydrin, acetone, acrylic acid and the like. At present, propylene mainly comes from ethylene co-production and catalytic cracking, in recent years, the development speed of propylene in China gradually exceeds that of ethylene, in 2017, the annual average growth rate of the equivalent demand of propylene in China reaches 7.6 percent, and the growth rate of the production capacity of propylene is exceeded. In view of equivalent demand, the contradiction between supply and demand of propylene is increasingly prominent, so that the production process prospect of PDH (PDH) propylene from which propylene is derived is very wide in recent years.
In the fixed bed process of the CATofin propane dehydrogenation, the height of a catalyst bed layer in a fixed bed reactor is about 2 m. In addition, the propane dehydrogenation process involves high-temperature and negative-pressure reaction conditions and frequent switching of reaction, steam treatment, and air regeneration, which all place very high demands on the mechanical strength of the catalyst. The mechanical strength of the catalyst is insufficient, so that the catalyst is easy to be pulverized in the reaction process, and the pulverization not only affects the propane dehydrogenation performance of the catalyst, but also has obvious influence on the mass transfer and heat transfer performance of the catalyst in the reaction process, so that the product propylene is easy to generate deep dehydrogenation reaction to generate carbon deposition. Therefore, in order to reduce the pulverization rate of the catalyst under the industrial working condition propane dehydrogenation reaction condition, the invention develops the carrier and the catalyst material for preparing the propylene by propane dehydrogenation with extremely high side pressure strength.
Disclosure of Invention
The invention provides a reaction carrier and a supported catalyst material for preparing propylene by catalytic dehydrogenation of propane with extremely high side pressure strength and a preparation method thereof.
A preparation method of a carrier material of a high mechanical (high side pressure) strength catalyst applied to a reaction process for preparing propylene by propane catalytic dehydrogenation comprises the following steps:
(1) preparation of metal-doped aluminum oxide salt yM by precipitationaOb·zAl2O3The carrier material is characterized by comprising the following components, wherein M is one or more of Ba, Mg, La, Mn, Zr, K, Na, Ca, Zn, Ce, Bi, Fe, Nb and Sb, a is 1-3, b is 1-4, y is 0-1, and z is 1-8;
(2) roasting the carrier material obtained in the step (1) for 2-10 hours at 500-1000 ℃;
(3) mechanically mixing the carrier obtained in the step (2) with a material A, wherein A is SiC or SiO with the mesh number of 50-2002、Al2O3h-BN, SiN or carbon silicon boron, and the carrier: the mass ratio of A is 1-9: 1;
(4) molding the (carrier + A) obtained in the step (3), wherein the shape of the (carrier + A) is one of columnar, spherical and flaky, and is preferably columnar;
(5) and (4) roasting the (carrier + A) material formed in the step (4) for 3-10 hours at 500-1000 ℃ in an air atmosphere.
The invention also provides a carrier of the high-side pressure strength catalyst, which is prepared by the method and applied to the reaction process for preparing propylene by catalytic dehydrogenation of propane.
The invention also aims to provide a preparation method of the high-side pressure strength catalyst applied to the reaction process for preparing propylene by propane catalytic dehydrogenation, which comprises the following steps:
(1) the formed (carrier + A) material is used as a carrier of the catalyst, and an impregnation method is adopted to prepare xCr2O3V (carrier + A) material carrying catalyst, x is Cr2O3The loading capacity is 5-25%;
(2) the xCr prepared in the step (1)2O3And (V) roasting the (carrier + A) material loaded catalyst for 3-10 hours at 500-900 ℃.
The invention also aims to provide a high-side pressure strength catalyst prepared by the method and applied to a reaction process for preparing propylene by propane catalytic dehydrogenation, wherein the catalyst material is xCr2O3And (carrier + A), carrying out a mechanical strength test on the catalyst, wherein the length of the test material is 4-7 cm.
The invention also aims to provide the application of the high-mechanical-strength supported catalyst in the reaction of preparing propylene by propane dehydrogenation, wherein the reaction conditions are as follows: the reaction pressure is 40-60 kPa, the reaction temperature is 560-620 ℃, and the propane reaction space velocity is 300-400 ml/g-1·h-1. The catalyst activity and selectivity were tested, as well as the dusting rate of the catalyst over time.
Has the advantages that:
the supported catalyst with high mechanical strength provided by the invention is used for the reaction of preparing propylene by directly dehydrogenating propane, the mechanical strength of the supported catalyst is greatly improved on the basis of keeping higher propane conversion rate and propylene selectivity, the pulverization rate under the reaction condition of industrial working conditions is greatly reduced, mass transfer and heat transfer in the reaction process are facilitated, the service life of the supported catalyst is greatly prolonged, the stability of the catalyst is improved, and the economic benefit is improved.
The carrier and the loaded catalyst material provided by the invention are simple in preparation method, low in cost and good in repeatability.
Drawings
FIG. 1 propane dehydrogenation stability test of catalysts in example 8 and comparative example 1 (red: example 8 sample; black: comparative example 1 sample).
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
Preparation of BaO.6Al by precipitation method2O3A carrier according to formula Ba: weighing barium nitrate and aluminum nitrate according to the Al atomic ratio, dissolving the barium nitrate and the aluminum nitrate in deionized water, stirring for 25min, dropwise adding excessive ammonia carbonate solution to generate milky precipitate, continuously stirring for 120min, filtering, washing, and drying the filtered solid material in an oven at 100 ℃ overnight. Roasting the dried powder in a muffle furnace at 700 ℃ for 3 hours to obtain BaO.6Al2O3And (3) a carrier.
Example 2
According to BaO.6Al in example 12O3Carrier and 100 mesh SiO2Mechanically mixing the two materials at a weight ratio of 9: 1, and extruding with a plodder to obtain columnar (BaO.6Al)2O3+SiO2) The material, which was calcined in a muffle furnace at 800 ℃ for 3 hours, had the mechanical strength test results shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+SiO2) (9: 1) loading catalyst, weighing a certain amount of chromium nitrate according to the content of active species in the chemical formula, dissolving the chromium nitrate in deionized water, stirring for 25min, and adding the chromium nitrate into the (BaO.6Al) which is formed into a column shape2O3+SiO2) In the material, the obtained supported catalyst is dried in an oven at 100 ℃ overnight and then roasted in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 3
According to BaO.6Al in example 12O3The carrier and the 100-mesh SiC are mechanically mixed according to the weight ratio of 9: 1, and the column is prepared by adopting a way of extrusion molding of a strip extruding machineForm (BaO.6Al)2O3+ SiC) material, which was fired at 800 ℃ for 3 hours in a muffle furnace, and the results of the mechanical strength tests are shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+ SiC) (9: 1) supported catalyst, weighing a certain amount of chromium nitrate according to the content of active species in the chemical formula, dissolving the chromium nitrate in deionized water, stirring for 25min, and adding the chromium nitrate into the (BaO.6Al) which is formed into a column shape2O3+ SiC) material, the obtained supported catalyst was dried in an oven at 100 ℃ overnight and then calcined in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 4
According to BaO.6Al in example 12O3Carrier and 100 mesh Al2O3Mechanically mixing the two materials at a weight ratio of 9: 1, and extruding with a plodder to obtain columnar (BaO.6Al)2O3+Al2O3) The material, which was calcined in a muffle furnace at 800 ℃ for 3 hours, had the mechanical strength test results shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+Al2O3) (9: 1) loading catalyst, weighing a certain amount of chromium nitrate according to the content of active species in the chemical formula, dissolving the chromium nitrate in deionized water, stirring for 25min, and adding the chromium nitrate into the (BaO.6Al) which is formed into a column shape2O3+Al2O3) In the material, the obtained supported catalyst is dried in an oven at 100 ℃ overnight and then roasted in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 5
According to BaO.6Al in example 12O3The carrier and 100 mesh h-BN are mechanically mixed according to the weight ratio of 9: 1, and the columnar (BaO.6Al) is prepared by adopting a strip extruding machine extrusion forming mode2O3+ h-BN) material, which was fired at 800 ℃ for 3 hours in a muffle furnace, the mechanical strength test results are shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+ h-BN) (9: 1) load catalyst, weighing a certain amount of chromic nitrate according to the content of active species in the chemical formula, dissolving the chromic nitrate in deionized water, stirringStirring for 25min, adding into the columnar (BaO.6Al)2O3+ h-BN) material, the obtained supported catalyst is dried in an oven at 100 ℃ overnight and then roasted in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 6
According to BaO.6Al in example 12O3The carrier and 100 meshes of SiN are mechanically mixed according to the weight ratio of 9: 1, and the mixture is extruded and formed by a bar extruder to prepare a columnar (BaO.6Al) structure2O3+ SiN) material, which was fired at 800 ℃ in a muffle furnace for 3 hours, and the results of the mechanical strength tests are shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+ SiN) (9: 1) supported catalyst, weighing certain amount of chromium nitrate according to the active matter content in the chemical formula, dissolving in deionized water, stirring for 25min, and adding into columnar (BaO.6Al)2O3+ SiN) material, the obtained supported catalyst was baked in a 100 ℃ oven overnight at an interval and then baked in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 7
According to BaO.6Al in example 12O3The carrier and 100 meshes of carbon, silicon and boron are mechanically mixed according to the weight ratio of 9: 1, and the mixture is extruded and formed by a bar extruder to prepare a columnar (BaO.6Al) structure2O3+ CSiB) material, which was fired in a muffle furnace at 800 ℃ for 3 hours and the results of the mechanical strength tests are shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+ CSiB) (9: 1) supported catalyst, weighing a certain amount of chromium nitrate according to the content of active species in the chemical formula, dissolving the chromium nitrate in deionized water, stirring for 25min, and adding the chromium nitrate into the (BaO.6Al) which is formed into a column shape2O3+ CSiB) material, the obtained supported catalyst was oven-dried overnight in a 100 ℃ oven and then calcined in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 8
According to BaO.6Al in example 12O3Carrier and 100 mesh SiO2Mechanically mixing the two at a weight ratio of 1: 1The columnar (BaO.6Al) is prepared by adopting a way of extrusion molding of a bar extruder2O3+SiO2) The material, which was calcined in a muffle furnace at 800 ℃ for 3 hours, had the mechanical strength test results shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+SiO2) (1: 1) loading catalyst, weighing a certain amount of chromium nitrate according to the content of active species in the chemical formula, dissolving the chromium nitrate in deionized water, stirring for 25min, and adding the chromium nitrate into the (BaO.6Al) which is formed into a column shape2O3+SiO2) In the material, the obtained supported catalyst is dried in an oven at 100 ℃ overnight and then roasted in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 9
According to BaO.6Al in example 12O3Carrier and 500 mesh SiO2Mechanically mixing the two materials at a weight ratio of 9: 1, and extruding with a plodder to obtain columnar (BaO.6Al)2O3+SiO2-500 mesh) material, which was fired in a muffle furnace at 800 ℃ for 3 hours and the results of the mechanical strength tests are shown in table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/(BaO·6Al2O3+SiO2-500 mesh) (9: 1) supported catalyst, weighing a certain amount of chromium nitrate according to the content of active species in the chemical formula, dissolving the chromium nitrate in deionized water, stirring for 25min, and adding the chromium nitrate into the (BaO.6Al) which is formed into a column shape2O3+SiO2-500 mesh) was dried in an oven at 100 ℃ overnight and then calcined in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Example 10
The supported catalysts with different mechanical strengths in examples 2-8 were used in the reaction of direct dehydrogenation of propane to propylene. Weighing 10g of formed catalyst, wherein the reaction raw material gas is pure propane, the reaction pressure is 50kPa, the reaction temperature is 570 ℃, and the reaction space velocity is 320 ml/g-1·h-1The reaction results are shown in Table 3. Meanwhile, the powdering ratio of the supported catalyst after 10 days of the reaction is shown in Table 3. The results of the 10-day propane dehydrogenation stability of the catalyst of example 8 are shown in fig. 1.
Comparative example 1
BaO.6Al of example 1 without any A material added2O3The carrier is prepared into a columnar carrier by adopting a way of extrusion molding of a bar extruder. The carrier was calcined in a muffle furnace at 800 ℃ for 3 hours, and the results of the mechanical strength test of the carrier are shown in Table 1. The impregnation method is adopted to prepare 18 wt% Cr2O3/BaO·6Al2O3Loading catalyst, weighing a certain amount of chromic nitrate according to the content of active species in the chemical formula, dissolving in deionized water, stirring for 25min, adding into columnar BaO.6Al2O3In the carrier, the obtained supported catalyst was dried in an oven at 100 ℃ overnight and then calcined in a muffle furnace at 800 ℃ for 3 hours. The mechanical strength results are shown in Table 2.
Comparative example 2
The supported catalyst of comparative example 1 was used in the reaction for producing propylene by direct dehydrogenation of propane. Weighing 10g of formed catalyst, wherein the reaction raw material gas is pure propane, the reaction pressure is 50kPa, the reaction temperature is 570 ℃, and the reaction space velocity is 320 ml/g-1·h-1The reaction results are shown in Table 3. Meanwhile, the pulverization rates of the supported catalysts after 10 days of reaction are shown in Table 3, and the results of propane dehydrogenation stability are shown in FIG. 1.
Claims (6)
1. A preparation method of a carrier material of a catalyst for preparing propylene by catalytic dehydrogenation of propane with high mechanical strength is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of metal-doped aluminum oxide salt yM by precipitationaOb·zAl2O3CarrierThe material is characterized by comprising the following components, wherein M is one or more of Ba, Mg, La, Mn, Zr, K, Na, Ca, Zn, Ce, Bi, Fe, Nb and Sb, a is 1-3, b is 1-4, y is 0-1, and z is 1-8;
(2) roasting the carrier material obtained in the step (1) for 2-10 hours at 500-1000 ℃;
(3) mechanically mixing the carrier obtained in the step (2) with a material A, wherein the material A is SiC or SiO with the mesh number of 50-2002、Al2O3h-BN, SiN and carbon silicon boron, and the carrier: the mass ratio of the material A is 1-9: 1;
(4) molding the (carrier + A) material obtained in the step (3), wherein the molded (carrier + A) material is columnar, spherical or flaky;
(5) and (4) roasting the (carrier + A) material formed in the step (4) for 3-10 hours at 500-1000 ℃ in an air atmosphere.
2. The carrier material of the high mechanical strength propane catalytic dehydrogenation propylene preparation catalyst prepared by the method of claim 1.
3. A preparation method of a catalyst for preparing propylene by catalytic dehydrogenation of propane with high mechanical strength is characterized by comprising the following steps: the method comprises the following steps:
(1) the xCr is prepared by using the carrier material as the carrier of the catalyst in claim 2 and adopting an impregnation method2O3(carrier + A) loading catalyst, wherein the loading amount x is 5-25%;
(2) the xCr prepared in the step (1)2O3And (c) roasting the (carrier + A) supported catalyst for 3-10 hours at 500-900 ℃.
4. The catalyst for preparing propylene by catalytic dehydrogenation of propane with high mechanical strength, which is prepared by the method of claim 3.
5. Use of the catalyst of claim 4 in the dehydrogenation of propane to propylene.
6. According to claim 5Characterized in that the reaction conditions are as follows: the reaction pressure is 40-60 kPa, the reaction temperature is 560-620 ℃, and the propane reaction space velocity is 300-400 ml/g-1·h-1。
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| CN1074631A (en) * | 1992-01-24 | 1993-07-28 | 北京大学 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
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| CA2849485A1 (en) * | 2011-09-20 | 2014-03-27 | Basf Corporation | Chromia alumina catalysts for alkane dehydrogenation |
| CN110152650A (en) * | 2018-02-11 | 2019-08-23 | 中国科学院大连化学物理研究所 | A kind of preparing propylene by dehydrogenating propane supported catalyst and preparation method thereof |
| CN112517036A (en) * | 2019-09-17 | 2021-03-19 | 中国石油天然气股份有限公司 | Synthetic gas methanation catalyst and preparation method thereof |
| CN113289663A (en) * | 2021-06-22 | 2021-08-24 | 中石化南京化工研究院有限公司 | Preparation method of methanation catalyst for isothermal fixed bed |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1074631A (en) * | 1992-01-24 | 1993-07-28 | 北京大学 | Loading type butadiene catalyst made by butylene oxidation dehydrogen |
| CN101507931A (en) * | 2009-03-24 | 2009-08-19 | 南京工业大学 | Preparation method of whisker reinforced preformed catalyst carrier or catalyst |
| CA2849485A1 (en) * | 2011-09-20 | 2014-03-27 | Basf Corporation | Chromia alumina catalysts for alkane dehydrogenation |
| CN110152650A (en) * | 2018-02-11 | 2019-08-23 | 中国科学院大连化学物理研究所 | A kind of preparing propylene by dehydrogenating propane supported catalyst and preparation method thereof |
| CN112517036A (en) * | 2019-09-17 | 2021-03-19 | 中国石油天然气股份有限公司 | Synthetic gas methanation catalyst and preparation method thereof |
| CN113289663A (en) * | 2021-06-22 | 2021-08-24 | 中石化南京化工研究院有限公司 | Preparation method of methanation catalyst for isothermal fixed bed |
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