CN106607105B - Activation method of platinum-containing low-carbon alkane dehydrogenation catalyst - Google Patents
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Abstract
2 2The invention relates to an activation method of a low-carbon alkane dehydrogenation catalyst, which mainly solves the problem that the conversion rate selectivity of the existing low-carbon alkane dehydrogenation catalyst containing platinum is low.
Description
Technical Field
The invention relates to an activation method of a platinum-containing low-carbon alkane dehydrogenation catalyst.
Background
With the development of chemical industry, low-carbon olefin has wide application and value as an important raw material for producing plastics, synthetic rubber, medicines, gasoline additives, ion exchange resins, detergents, spices and various chemical intermediates. Propylene/isobutene mainly comes from co-production or by-products in steam cracking and refinery fluid catalytic cracking processes, and the traditional production process is difficult to meet the rapid increase of market demand along with the increasing demand of low-carbon olefins. In order to meet the great demand on the low-carbon olefin, the development of the process for preparing the low-carbon olefin from the low-additional-value carbon alkane has important significance for fully utilizing the low-carbon alkane to open up a new olefin source.
The catalyst disclosed in the Chinese patent (CN200710025372.X) is prepared by dipping a platinum-tin component on an alumina-modified mesoporous molecular sieve serving as a carrier, wherein the propane conversion rate is only 17 percent and the propylene selectivity is 93 percent, the catalyst disclosed in the U.S. patent (US4438288) uses platinum-tin metals loaded on gamma-Al 2 O 3, SiO 2 and MgO, and alkali metals or alkaline earth metals are added into the carrier, and the catalyst has the defects of low activity and selectivity and 39-44 percent of isobutane conversion rate.
The catalyst adopts an impregnation method to load PtSn on a carrier, and is easy to deposit carbon and deactivate in the high-temperature use process, poor in stability and short in service life. The invention adopts the activation treatment to the catalyst, controls the water/chlorine balance in the chlorine supplementing process and effectively improves the redispersion of the active component Pt, thereby improving the catalytic activity. On the other hand, research also finds that mixing hydrogen with trace hydrogen sulfide in the catalyst reduction process and simultaneously carrying out sulfidation treatment on the catalyst can effectively inhibit the cracking performance of the catalyst, thereby being beneficial to reducing the occurrence of side reaction, promoting dehydrogenation activity and maintaining long-term stability, simultaneously enhancing the hydrogen adsorption capacity of the catalyst at high temperature and inhibiting the formation of carbon deposit under the high-temperature reaction condition, and the research result is consistent with the sulfidation treatment effect in the Pt-containing catalyst for alkane dehydrogenation disclosed in Linluo et al (Chinese patent CN 87101513).
Disclosure of Invention
The invention mainly solves the problem that the prior platinum-containing low-carbon alkane dehydrogenation catalyst has low conversion rate and low selectivity, and provides a novel activation method for the platinum-containing low-carbon alkane dehydrogenation catalyst.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the activation method of the platinum-containing low-carbon alkane dehydrogenation catalyst comprises the following steps:
a) Treating for 0.5-10 hours in stages at 100-800 ℃ in air atmosphere;
b) Treating the catalyst for 1-10 hours by using -1 airflow with the volume ratio of oxygen to water vapor of 0.01-0.1 and the volume space velocity of water vapor of 400-4000 hours at 400-600 ℃ to promote the redispersion of the active metal component Pt and the halogen element Cl;
c) The catalyst active metal component was reduced under a trace hydrogen sulfide/H 2 reducing atmosphere.
In the above catalyst activation method, the activation process is carried out in a reactor comprising a fixed bed, a fluidized bed or a moving bed.
The catalyst activation method comprises the step of treating in air atmosphere in stages at 200-400 ℃ and 500-700 ℃ for 0.5-10 hours respectively.
Preferably, the treatment is carried out in stages under the air atmosphere, and the treatment is carried out for 1 to 2 hours at the temperature of between 250 and 350 ℃.
Preferably, the treatment is carried out in stages under the air atmosphere, and the treatment is carried out for 4 to 8 hours at the temperature of 550 to 650 ℃.
Preferably, the volume ratio of oxygen to water vapor is 0.01-0.06.
Preferably, the volume space velocity of the water vapor is 600-2400 hours -1.
Preferably, the catalyst is treated with oxygen/water vapor at 450-600 ℃ for 2-6 hours.
Preferably, the catalyst is treated with trace hydrogen sulfide/H 2 at 450-650 ℃ for 0.5-5 hours.
The treatment according to the present invention is mainly a baking treatment.
The platinum-containing low-carbon alkane dehydrogenation catalyst comprises the following components, as is well known in the art, platinum serving as an active component, auxiliaries including but not limited to Sn, Li, Na, K, Ca, Mg, Ba, Zn, Cd, La, Ce, Pr, Eu, Sm or Tm, carriers including but not limited to SiO 2, TiO 2, Al 2 O 3, TiO 2/SiO 2 composite material, TiO 2/Al 2 O 3 composite material or zinc/magnesium aluminate, in the embodiment, two supported Pt-containing low-carbon alkane dehydrogenation catalyst precursors A and B are mainly used, the active component of the catalyst precursor A is Pt-Sn, the carrier is gamma-Al 2 O 3, the weight percentage of the catalyst components is Pt 0.4%, Sn 0.8%, the balance is gamma-Al 2 O 3, the catalyst precursor A is impregnated in equal volume and is dried for later use, the active component of the deactivated catalyst B is Pt-Sn-Mg, the carrier is zinc/magnesium aluminate, the weight percentage of the catalyst components is Pt 0.8%, Sn 0.8%, the balance is zinc chlorate, and the balance is dried for later use.
The invention adopts staged treatment to prevent the sintering of the active components of the catalyst caused by temperature runaway. The level of chlorine content of a fresh catalyst is controlled by treating the catalyst with oxygen/water vapor, the high dispersibility of Pt is improved, and the aggregation of Pt is prevented, so that the catalytic activity is improved, and meanwhile, the catalyst is subjected to vulcanization treatment, so that the performances of cracking and the like of the catalyst can be effectively inhibited, the occurrence of side reactions is reduced, the dehydrogenation activity is promoted, the long-term stability is maintained, the adsorption capacity of the catalyst on hydrogen at high temperature is enhanced, the formation of carbon deposit under the high-temperature reaction condition is inhibited, and the dehydrogenation activity is promoted and the long-term stability is maintained. The catalyst activated by the activation method provided by the invention is used for dehydrogenation reaction of low-carbon alkane, and has high conversion rate and selectivity and good stability; after 100 times of activation, the catalyst has stable performance and obtains better technical effect.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
5.0 g of catalyst precursor A was activated in a continuous flow quartz tube reactor, the catalyst precursor A was treated at 250 ℃ for 1 hour in an air atmosphere and then at 550 ℃ for 6 hours, further treated with a gas stream containing 5 mol% O 2 at 600 ℃ for 4 hours using water vapor as a carrier gas, and finally treated with a gas stream containing 3ppm H 2 S H 2 at 600 ℃ for 2 hours to obtain activated catalyst C.
[ example 2 ]
5.0 g of the catalyst precursor A was activated in a continuous flow quartz tube reactor, and the catalyst precursor A was treated at 250 ℃ for 2 hours in an air atmosphere and then at 600 ℃ for 4 hours, and further treated with a gas stream containing 5 mol% of O 2 at 600 ℃ for 4 hours using water vapor as a carrier gas, and finally treated with a gas stream of H 2 containing 3ppm of H 2 S at 600 ℃ for 2 hours to obtain an activated catalyst D.
[ example 3 ]
5.0 g of catalyst precursor A was activated on a micro catalytic reactor in a continuous flow quartz tube reactor, the catalyst precursor A was treated at 250 ℃ for 1 hour in an air atmosphere and then at 550 ℃ for 8 hours, further treated with a gas stream containing 5 mol% O 2 at 600 ℃ for 4 hours using water vapor as a carrier gas, and finally treated with a gas stream containing 3ppm H 2 S H 2 at 600 ℃ for 2 hours to obtain an activated catalyst E.
[ example 4 ]
5.0 g of catalyst precursor B was activated in a continuous flow quartz tube reactor, the catalyst precursor B was treated at 350 ℃ for 1 hour in an air atmosphere and then at 550 ℃ for 8 hours, then treated with a gas stream containing 1 mol% O 2 at 500 ℃ for 4 hours using water vapor as a carrier gas, and finally treated with a gas stream containing 3ppm H 2 S H 2 at 600 ℃ for 2 hours to obtain an activated catalyst F.
[ example 5 ]
5.0G of catalyst precursor B was activated in a continuous flow quartz tube reactor, the catalyst precursor B was treated at 300 ℃ for 1 hour in an air atmosphere and then at 550 ℃ for 6 hours, then treated with 2 mol% O 2 in a stream of 2 mol% O 2 at 500 ℃ for 4 hours using water vapor as a carrier gas, and finally treated with 5ppm H 2 S in a stream of H 2 at 600 ℃ for 2 hours to obtain an activated catalyst G.
[ example 6 ]
5.0 g of catalyst precursor B was activated in a continuous flow quartz tube reactor, the catalyst precursor B was treated at 250 ℃ for 2 hours in an air atmosphere and then at 550 ℃ for 4 hours, then treated with a stream of 5 mol% O 2 at 450 ℃ for 4 hours using water vapor as a carrier gas, and finally treated with a stream of H 2 containing 10ppm H 2 S at 600 ℃ for 0.5 hour to obtain activated catalyst H.
[ example 7 ]
Activating 5.0 g of catalyst precursor B on a micro catalytic reactor of a continuous flow quartz tube reactor, treating the catalyst precursor B at 300 ℃ for 1 hour under the atmosphere of air, treating the catalyst precursor B at 550 ℃ for 6 hours, treating the catalyst subjected to chlorine supplementation at 600 ℃ for 4 hours by using a gas flow containing 5 mol% of O 2 by using water vapor as a carrier gas, and finally treating the catalyst at 600 ℃ for 4 hours by using a H 2 gas flow containing 1ppm of H 2 S to obtain an activated catalyst I.
[ example 8 ]
0.07g of chloroplatinic acid, 0.23g of tin tetrachloride and 0.08g of sodium nitrate are dissolved in deionized water, dipped on a gamma-Al 2 O 3 carrier in equal volume, dried to obtain a catalyst precursor, then activated on a micro catalytic reaction device of a continuous flow quartz tube reactor, the catalyst precursor is treated for 1 hour at 250 ℃ under the air atmosphere and then treated for 6 hours at 550 ℃, then treated for 6 hours at 600 ℃ by using steam as a carrier gas and using gas flow containing 2 mol% of O 2, and finally the catalyst is treated for 1 hour at 500 ℃ by using H 2 gas flow containing 5ppm of H 2 S to obtain an activated catalyst J.
[ example 9 ]
0.07g of chloroplatinic acid, 0.23g of stannic chloride and 0.14g of potassium nitrate are dissolved in deionized water, dipped on a gamma-Al 2 O 3 carrier in equal volume, dried to obtain a catalyst precursor, then activated on a micro catalytic reaction device of a continuous flow quartz tube reactor, the catalyst precursor is treated at 250 ℃ for 1 hour under the air atmosphere and then at 550 ℃ for 6 hours, then treated at 600 ℃ for 6 hours by using steam as carrier gas and using gas flow containing 2 mol% of O 2, and finally the catalyst is treated at 500 ℃ for 1 hour by using H 2 gas flow containing 5ppm of H 2 S to obtain an activated catalyst K.
[ example 10 ]
0.07g of chloroplatinic acid, 0.23g of tin tetrachloride, 0.14g of potassium nitrate and 0.21g of zinc nitrate are dissolved in deionized water, dipped on a gamma-Al 2 O 3 carrier in equal volume, dried to obtain a catalyst precursor, then activated on a micro catalytic reaction device of a continuous flow quartz tube reactor, the catalyst precursor A is treated at 250 ℃ for 2 hours under the air atmosphere, then treated at 550 ℃ for 4 hours, treated at 450 ℃ for 4 hours by using steam as a carrier gas and using an air flow containing 5 mol% of O 2, and finally the catalyst is treated at 600 ℃ for 0.5 hour by using an H 2 air flow containing 10ppm of H 2 S to obtain an activated catalyst L.
[ example 11 ]
0.07g of chloroplatinic acid, 0.23g of tin tetrachloride, 0.17g of zinc nitrate and 0.11g of cadmium nitrate are dissolved in deionized water, dipped on a gamma-Al 2 O 3 carrier in equal volume, dried to obtain a catalyst precursor, then activated on a micro catalytic reaction device of a continuous flow quartz tube reactor, the catalyst precursor A is treated for 1 hour at 250 ℃ under the air atmosphere and then treated for 8 hours at 550 ℃, then treated for 4 hours at 600 ℃ by using an air flow containing 5mol percent of O 2 and finally treated for 2 hours at 600 ℃ by using an H 2 air flow containing 3ppm of H 2 S to obtain an activated catalyst M.
Comparative example 1
5.0 g of the catalyst precursor A was activated on a micro catalytic reactor apparatus of a continuous flow quartz tube reactor and treated at 550 ℃ for 8 hours to obtain an activated catalyst N.
Comparative example 2
5.0 g of the catalyst precursor A was activated in a micro catalytic reactor of a continuous flow quartz tube reactor, treated at 250 ℃ for 1 hour and then at 550 ℃ for 8 hours to obtain an activated catalyst O.
Comparative example 3
5.0 g of catalyst precursor A was activated in a continuous flow quartz tube reactor, treated at 250 ℃ for 1 hour and then at 550 ℃ for 8 hours, treated with steam as a carrier gas at 600 ℃ for 4 hours using a gas stream containing 5 mol% O 2, and finally treated with a gas stream containing 3ppm H 2 S H 2 at 600 ℃ for 2 hours to obtain an activated catalyst P.
Comparative example 4
5.0 g of catalyst precursor A was activated in a micro catalytic reactor of a continuous flow quartz tube reactor, treated at 250 ℃ for 1 hour and then at 550 ℃ for 8 hours, and further treated with steam as a carrier gas at 600 ℃ for 4 hours using a gas stream containing 5 mol% O 2 to obtain an activated catalyst Q.
Comparative example 5
5.0 g of the catalyst precursor A was activated in a micro catalytic reactor of a continuous flow quartz tube reactor, treated at 250 ℃ for 1 hour and then at 550 ℃ for 8 hours, and then the catalyst was treated with an H 2 gas stream containing 3ppm of H 2 S at 600 ℃ for 2 hours to obtain an activated catalyst R.
comparative example 6
5.0 g of catalyst precursor B was activated in a micro catalytic reactor of a continuous flow quartz tube reactor, treated at 250 ℃ for 1 hour, then at 550 ℃ for 8 hours, and then treated with steam as a carrier gas at 600 ℃ for 4 hours using a gas stream containing 5 mol% O 2 to obtain activated catalyst S.
[ example 12 ]
Evaluation of reaction Performance of activated catalyst
the catalyst C, D, E, F, G, H, I, J, K, L, M activated by the activation method provided by the invention and a catalyst which is not activated by a patent method are subjected to catalytic reaction performance evaluation on a micro catalytic reaction device of a continuous flow quartz tube reactor under the same conditions, wherein the reaction conditions comprise normal pressure, 550 ℃, C n H 2n+2/H 2 (vol/vol), alkane WHSV is 4.6H -1, an Agilent 7890 gas chromatograph (HP-AL/S capillary column, 50m multiplied by 0.53mm multiplied by 15 mu m; FID detector) is adopted for product analysis, alkane and alkene contents in a dehydrogenation product are analyzed on line, and the conversion rate, selectivity and yield of the reaction are calculated, and low-carbon alkane takes propane and isobutane as examples, and the results are shown in tables 1 and 2.
TABLE 1
the reaction conditions are that the temperature is 550 ℃, the Propane/H 2 is 5/2(vol/vol), the space velocity (WHSV) of the alkane is 4.6H -1, and the reaction pressure is normal pressure
TABLE 2
| Catalyst and process for preparing same | Reaction time | Conversion rate% | Selectivity% |
| C | 1 | 55.6 | 94.8 |
| 50 | 50.4 | 95.4 | |
| D | 1 | 53.4 | 94.9 |
| 50 | 48.6 | 94.8 | |
| E | 1 | 54.7 | 94.6 |
| 50 | 49.7 | 95.1 |
| F | 1 | 55.3 | 95.1 |
| 50 | 51.2 | 95.7 | |
| G | 1 | 54.2 | 94.3 |
| 50 | 48.1 | 95.4 | |
| H | 1 | 53.7 | 96.1 |
| 50 | 48.3 | 96.3 | |
| I | 1 | 54.6 | 94.8 |
| 50 | 49.6 | 95.1 | |
| J | 1 | 57.3 | 95.1 |
| 50 | 53.4 | 95.2 | |
| K | 1 | 53.4 | 96.2 |
| 50 | 48.2 | 95.4 | |
| L | 1 | 55.2 | 94.9 |
| 50 | 51.3 | 94.8 | |
| M | 1 | 54.1 | 95.0 |
| 50 | 49.8 | 95.5 | |
| Comparative example 2N | 1 | 49.6 | 93.7 |
| 50 | 44.8 | 93.2 | |
| Comparative example 3O | 1 | 48.7 | 94.0 |
| 50 | 43.5 | 94.3 | |
| (comparative example 4) P | 1 | 49.7 | 94.5 |
| 50 | 42.3 | 93.9 |
The reaction conditions are that the temperature is 550 ℃, the i-Butane/H 2 is 5/2(vol/vol), the alkane space velocity (WHSV) is 4.6H -1, and the reaction pressure is normal pressure.
Claims (9)
1. An activation method of a platinum-containing low-carbon alkane dehydrogenation catalyst is characterized by comprising the following steps: the fresh catalyst sequentially adopts the following steps:
a) Treating for 0.5-10 hours in stages at 100-800 ℃ in air atmosphere;
b) Treating the catalyst for 1-10 hours by using -1 airflow at 400-600 ℃ at the volume ratio of oxygen to water vapor of 0.01-0.1 and the volume space velocity of water vapor of 400-4000 hours;
c) Reducing the active metal component of the catalyst under a trace hydrogen sulfide/H 2 reducing atmosphere;
wherein, the step a) is carried out by stages in the air atmosphere, and the treatment is respectively carried out for 1 to 10 hours at 200 to 400 ℃ and 500 to 700 ℃.
2. The method of claim 1, wherein the activation process is in one of a fixed bed, a fluidized bed, or a moving bed.
3. The method of claim 1, wherein the treatment is performed in stages under an air atmosphere, and the treatment is performed at 250 to 350 ℃ for 1 to 2 hours and 550 to 650 ℃ for 4 to 8 hours.
4. The method for activating the dehydrogenation catalyst containing platinum for lower alkanes according to claim 1, wherein the volume ratio of oxygen to water vapor is 0.01 to 0.06.
5. The activation method of the dehydrogenation catalyst containing platinum and light alkane as claimed in claim 1, wherein the water vapor volume space velocity is 600-2400 hours -1.
6. The method for activating the dehydrogenation catalyst containing platinum for light alkanes according to claim 1, wherein the catalyst is treated with oxygen/steam at 450-600 ℃ for 2-6 hours.
7. The method for activating the platinum-containing light alkane dehydrogenation catalyst according to claim 1, wherein the catalyst is treated with trace hydrogen sulfide/H 2 at 450-650 ℃ for 0.5-5 hours.
8. The method for activating the platinum-containing light alkane dehydrogenation catalyst according to claim 1 or 7, wherein the concentration of H 2 S in trace hydrogen sulfide/H 2 is 1-10 ppm.
9. The method of claim 1, wherein the activation is carried out in the presence of propane, isobutane, pentane or mixtures thereof.
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| CN101125298A (en) * | 2007-07-26 | 2008-02-20 | 南京大学 | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene |
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| CN102380426A (en) * | 2010-09-06 | 2012-03-21 | 中国石油化工股份有限公司 | Activation method of dehydrogenation catalyst |
| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN104107704A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for regenerating platinum-containing low carbon alkane dehydrogenation catalyst |
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| CN101125298A (en) * | 2007-07-26 | 2008-02-20 | 南京大学 | Catalyst propane using aluminium oxide modified mesonore molecular sieve as carrier for dehydrogenation producing propylene |
| CN101884922A (en) * | 2009-05-13 | 2010-11-17 | 中国石油化工股份有限公司 | Method for preparing propylene catalyst by propane dehydrogenation process |
| CN102380426A (en) * | 2010-09-06 | 2012-03-21 | 中国石油化工股份有限公司 | Activation method of dehydrogenation catalyst |
| CN102909011A (en) * | 2011-08-01 | 2013-02-06 | 中国石油化工股份有限公司 | Activation and sulfurization method for dehydrogenation catalyst |
| CN104107704A (en) * | 2013-04-16 | 2014-10-22 | 中国石油化工股份有限公司 | Method for regenerating platinum-containing low carbon alkane dehydrogenation catalyst |
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