CN102935378B - A kind of anti-coking Catalysts and its preparation method and application - Google Patents
A kind of anti-coking Catalysts and its preparation method and application Download PDFInfo
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- CN102935378B CN102935378B CN201210455387.0A CN201210455387A CN102935378B CN 102935378 B CN102935378 B CN 102935378B CN 201210455387 A CN201210455387 A CN 201210455387A CN 102935378 B CN102935378 B CN 102935378B
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Abstract
The invention discloses a kind of anti-coking Catalysts and its preparation method and application, catalyst active ingredient is the molecular sieve of molecular sieve or metallic element modification, adopt atomic layer deposition method at the surface of catalyst active ingredient coating oxide coating, after calcination processing, obtain finished catalyst, described oxide is Al
2o
3, SiO
2, TiO
2in one or more.To solve in the reaction of existing Aldehyde-ammonia Condensation due to catalyst surface coking, cause the problem that catalyst easy in inactivation, life-span are short.
Description
Technical field
The present invention relates to a kind of anti-coking Catalysts and its preparation method and application, particularly relate to the molecular sieve catalyst used in Aldehyde-ammonia Condensation reaction.
Background technology
Catalysqt deactivation is the focal issue that industrial quarters is paid close attention to always, and catalyst surface carbon distribution and metal agglomeration are two main causes of petrochemical industry catalysqt deactivation.The formation of carbon distribution makes that high value carbon source is irreversible has turned to low value carbon source (coke), and when large-scale production, this loss is huge.The catalysqt deactivation caused due to catalyst surface carbon distribution is the subject matter faced during Aldehyde-ammonia Condensation reaction industryization is produced.
The pyridine base-synthesized production technology of Aldehyde-ammonia Condensation is since the industrialization fifties, because its raw material is cheap and easy to get, and synthetic route can be adjusted according to the market demand, produce multiple product, be the heat subject of research, its research direction mainly concentrates on the improvement in catalyst activity and life-span always.Research at present about catalyst activity is a lot, is wherein that the catalyst of carrier shows higher activity and selectivity in Aldehyde-ammonia Condensation reaction with ZSM-5 molecular sieve.Patent CN1506354A is with ammonia, formaldehyde, acetaldehyde for raw material, and adopt ZSM-5 molecular sieve through strong alkali aqueous solution process as catalyst, pyridine base total recovery can reach 74.7%.Patent CN1263741C and CN1565736A carries out modification with mixture that is plumbous and cobalt to ZSM-5 catalyst, and react 4 hours under 450 DEG C of conditions, pyridine yield can reach 55.5%, and the total recovery of pyridine base reaches 81%.Patent CN102430423A is using the mixture of ZSM-5 and Co-ZSM-5 as catalyst, and under 450 DEG C of conditions, the total recovery of formaldehyde, acetaldehyde, ammonia react pyridine base can reach 84%, and the yield of pyridine can reach 60%.The activity and selectivity of these catalyst is all higher, but poor stability, and react after 5-6 hour, the activity of catalyst obviously declines.Due to catalyst carbon deposit inactivation, the extending catalyst life-span has become the subject matter that Aldehyde-ammonia Condensation production pyridine and its derivatives needs to overcome.
Patent CN1631536A is using the mixed and modified ZSM-5 molecular sieve of palladium, cobalt and lead as catalyst, and at 450 DEG C, air speed is 1000h
-1under condition, pyridine yield reaches 70%, and pyridine base total recovery can reach 87%, and the catalyst regeneration time can extend to 48 hours.The ZSM-5 molecular sieve of this hybrid metal modification had both had higher activity, extended again the service life of catalyst simultaneously, but still can not meet the needs of suitability for industrialized production.
Summary of the invention
Technical problem: in order to solve the problem of the easy coking of Aldehyde-ammonia Condensation reacting middle catalyst, the invention provides a kind of anti-coking Catalysts and its preparation method and application, by promoting catalytic performance to catalyst surface coating oxide coating, anti-coking, long service life, active high.
Technical scheme: a kind of anti-coking catalyst, catalyst active ingredient is the molecular sieve of molecular sieve or metallic element modification, adopt atomic layer deposition method at the surface of catalyst active ingredient coating oxide coating, after calcination processing, obtain finished catalyst, described oxide is Al
2o
3, SiO
2, TiO
2in one or more.
Described oxide coating thickness 2-30nm.
Described oxide coating thickness is 5-20nm.
Described molecular sieve is any in ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ZSM-58, MCM-22, MCM-36, MCM-41, MCM-49, MCM-56, β zeolite, X zeolite or Y zeolite.
Described metallic element be in magnesium, calcium, lanthanum, titanium, zirconium, molybdenum, vanadium, manganese, chromium, iron, cobalt, nickel, copper, zinc, palladium, platinum, niobium, thallium, lead, bismuth, tin, antimony, tungsten, indium, hafnium, germanium, cadmium, yttrium any one or multiple.
The method of the anti-coking catalyst described in preparation, adopts atomic layer deposition method at the surface of catalyst active ingredient coating oxide coating, after calcination processing, obtains finished catalyst.
Described calcination processing temperature is 300-900 DEG C, calcination time 2-10 hour.
The application of described anti-coking catalyst in Aldehyde-ammonia Condensation reaction.
Beneficial effect: technique for atomic layer deposition (ALD) is with its distinctive extremely strong coating, process can carrying out particular oxides film from restraining growth characteristic at catalyst surface, film thickness can be made precisely controlled by the method, obtain surface uniform, smooth film.The present invention adopts ALD method to carry out Al to raw catalyst
2o
3, SiO
2, TiO
2in the coating of one or more sulls, then calcination processing is adopted, new duct is generated at catalyst surface, catalytic active center can either be made exposed, ensure efficiently carrying out of reaction, can effectively reduce catalyst coking again, the service life of extending catalyst, catalyst extends to more than 55 hours service life, the longlyest reaches about 80h.
Detailed description of the invention
Below will the present invention is further illustrated by embodiment:
The molecular sieve used in the present invention is commercially available, the molecular sieve of metallic element modification used adopts document Jiang Jie, Mao Dongsen, Yang Weimin etc. (2003). " different preparation method is on the impact of Aldehyde-ammonia Condensation catalyst P b-H-ZSM-5 performance ", petrochemical technology is prepared with the method recorded in application 21 (4): 246-248.Atomic layer deposition method bibliography Elam used, J.W., A.Zinovev, etal. (2006). " AtomiclayerdepositionofpalladiumfilmsonAl2O3surfaces. " ThinSolidFilms515 (4): the method recorded in 1664-1673..
Embodiment 1: prepare cobalt, lead, palladium modified ZSM-5 catalyst
1) add water 5 grams of cobalt nitrates and 10 grams of plumbi nitras 125ml wiring solution-forming, by 0.017 gram of palladium bichloride 1.25ml aqua regia dissolution, join in mixed solution, 50 grams, HZSM-5 type molecular sieve is immersed in mixed liquor, stir 20 hours at 90-100 DEG C, being cooled to room temperature, then filtering, is 6-7 by deionized water rinsing to pH value.Then at 110 DEG C dry 8 hours, 550 DEG C of roastings 4 hours, were placed in air and naturally cool to room temperature, obtain cobalt, lead, palladium modified ZSM-5 catalyst.
Embodiment 2:
Preparation has Al
2o
3the cobalt of film coating, lead, palladium modified ZSM-5 catalyst:
1) identical with embodiment 1 step 1).
2) by step 1) pressed powder that obtains is placed in the flow chamber of ALD reaction, under 200 DEG C of conditions, the mode replaced with pulse in flow chamber is by trimethyl aluminium and water, period purges with high pure nitrogen, each step is respectively 10s, and its single cycle reaction time is (10s-10s-10s-10s).After 150 circular responses, take out sample, at 600 DEG C, roasting 3 hours, obtains having Al
2o
3the cobalt of film, lead, palladium modified ZSM-5 catalyst.Al
2o
3the about 15nm of thickness of film.
Embodiment 3:
Preparation process is identical with embodiment 2 with method, just by embodiment 2 step 2) in circular response number reduce to 100, roasting 3 hours at 600 DEG C, obtain the Al of cobalt, lead, palladium modified ZSM-5 catalyst
2o
3the about 10nm of film thickness.
Embodiment 4:
Preparation process is identical with embodiment 2 with method, just by embodiment 2 step 2) in circular response number reduce to 80, roasting 3 hours at 600 DEG C, the Al of prepared cobalt, lead, palladium modified ZSM-5 catalyst
2o
3the about 8nm of film thickness.
Embodiment 5:
Preparation has SiO
2the cobalt of film coating, lead, palladium modified ZSM-5 catalyst
1) identical with embodiment 1 step 1).
2) by step 1) pressed powder that obtains is placed in the flow chamber of ALD reaction, under 240 DEG C of conditions, the mode replaced with pulse in flow chamber is by tetrachloro silicane and water, period purges with high pure nitrogen, each step is respectively 60s, and its single cycle reaction time is (60s-60s-60s-60s).After 100 circular responses, take out sample, in 700 DEG C of roastings 6 hours, obtain that there is SiO
2the cobalt of film, lead, palladium modified ZSM-5 obtain catalyst, SiO
2the about 8nm of film thickness.
Embodiment 6:
Preparation has TiO
2the cobalt of film coating, lead, palladium modified ZSM-5 catalyst
1) identical with embodiment 1 step 1).
2) by step 1) pressed powder that obtains is placed in the flow chamber of ALD reaction, under 110 DEG C of conditions, the mode replaced with pulse in flow chamber is by isopropyl titanate and water, period purges with high pure nitrogen, each step is respectively 10s, and its single cycle reaction time is (10s-10s-10s-10s).After 45 circular responses, take out sample, in 500 DEG C of roastings 8 hours, obtain that there is TiO
2the cobalt of film, lead, palladium modified ZSM-5 obtain catalyst, TiO
2the about 8nm of film thickness.
Embodiment 7:
Preparation has Al
2o
3and TiO
2the cobalt of film coating, lead, palladium modified ZSM-5 catalyst
1) identical with embodiment 1 step 1).
2) by step 1) pressed powder that obtains is placed in the flow chamber of ALD reaction, under 200 DEG C of conditions, adopt embodiment 2 step 2) in method do 5 circular responses, adopt embodiment 6 step 2 afterwards) in method do 5 circular responses, these 10 circular responses are designated as 1 systemic circulation reaction.After 5 systemic circulation reactions, take out sample, in 550 DEG C of roastings 6 hours, obtain that there is Al
2o
3and TiO
2the cobalt of film, lead, palladium modified ZSM-5 catalyst, film thickness is about 9nm.
Embodiment 8:
Catalytic activity is checked and rated.
Prepare pyridine reaction with Aldehyde-ammonia Condensation and carry out comparing embodiment 1-7.Reaction condition is as follows: in charging, the mol ratio of acetaldehyde, formaldehyde and ammonia is 2:1:4, reaction temperature 450 DEG C, and reaction gas air speed GHSV is 1000h
-1, reactor is the stainless steel tube of internal diameter 8mm, and product gas-chromatography is analyzed.Use respectively through Al
2o
3coating catalyst (embodiment 2-4), through SiO
2coating catalyst (embodiment 5), through TiO
2coating catalyst (embodiment 6), through Al
2o
3and TiO
2the catalyst (embodiment 7) of coating and the catalyst (embodiment 1) of not oxidised thing thin film coated, catalyst activity test result is as shown in table 1.
Table 1 embodiment 1-7 Aldehyde-ammonia Condensation catalytic performance compares
From table 1 data, on catalyst obtained in embodiment 2-7, regeneration period of catalyst from 55 hours to 79 hours not etc., and adopts the catalyst of not oxidised thing thin film coated in embodiment 1, and the regeneration period of catalyst is 48 hours.Show that the catalyst adopting the present invention to obtain can significantly improve the regeneration period of catalyst, the service life of extending catalyst.
Embodiment 9: preparation has TiO
2the plumbous modified ZSM-5 catalyst of film coating
1) add water 15 grams of plumbi nitras 125ml wiring solution-forming, is immersed in lead nitrate solution by 50 grams, HZSM-5 type molecular sieve, and stir 20 hours at 90-100 DEG C, being cooled to room temperature, then filtering, is 6-7 by deionized water rinsing to pH value.Then at 110 DEG C dry 8 hours, 550 DEG C of roastings 4 hours, were placed in air and naturally cool to room temperature, obtain plumbous modified ZSM-5 catalyst.
2) pressed powder that step 1) obtains is placed in ALD reaction flow chamber, according to embodiment 6 step 2) described in method do 53 circular responses after take out sample, in 500 DEG C of roastings 8 hours, obtained TiO
2the plumbous modified ZSM-5 catalyst of film coating, TiO
2the about 9nm of film thickness.
Embodiment 10: preparation has Al
2o
3the iron modified ZSM-5 catalyst of film coating
1) add water 18 grams of ferric nitrates 125ml wiring solution-forming, is immersed in iron nitrate solution by 50 grams, HZSM-5 type molecular sieve, and stir 20 hours at 90-100 DEG C, being cooled to room temperature, then filtering, is 6-7 by deionized water rinsing to pH value.Then at 110 DEG C dry 8 hours, 550 DEG C of roastings 4 hours, were placed in air and naturally cool to room temperature, obtain iron modified ZSM-5 catalyst.
2) pressed powder that step 1) obtains is placed in ALD reaction flow chamber, according to embodiment 2 step 2) described in method do 120 circular responses after take out sample, in 800 DEG C of roastings 2 hours, obtained Al
2o
3the iron modified ZSM-5 catalyst of film coating, Al
2o
3the about 12nm of film thickness.
Embodiment 11:
Preparation has Al
2o
3and TiO
2the lanthanum modification beta-zeolite catalyst of film coating
1) add water 4 grams of lanthanum nitrates 50ml wiring solution-forming, 50 grams of beta-zeolites are immersed in lanthanum nitrate hexahydrate, stir at 80 DEG C after 24 hours at 120 DEG C dry 12 hours, 550 DEG C of roastings 4 hours, be placed in air and naturally cool to room temperature, obtain the beta-zeolite catalyst of lanthanum modification.
2) by step 1) pressed powder that obtains is placed in the flow chamber of ALD reaction, adopts embodiment 7 step 2) in method do 4 systemic circulations reactions after take out sample, in 550 DEG C of roastings 7 hours, obtain that there is Al
2o
3and TiO
2the beta-zeolite catalyst of the lanthanum modification of laminated film, the about 7nm of film thickness.
Embodiment 12:
Preparation has SiO
2film coating molybdenum modified MC M-22 catalyst
1) add water 5 grams of ammonium heptamolybdates 50ml wiring solution-forming, be immersed in ammonium molybdate solution by 50 grams of MCM-12, ambient temperatare to be put after 24 hours at 120 DEG C dry 12 hours, 500 DEG C of roastings 4 hours, be placed in air and naturally cool to room temperature, obtain the MCM-22 catalyst of molybdenum modification.
2) by step 1) pressed powder that obtains is placed in the flow chamber of ALD reaction, adopts embodiment 5 step 2) in method do 80 circular responses after take out sample, in 500 DEG C of roastings 3 hours, obtain that there is SiO
2the molybdenum modified MC M-22 catalyst of film, the about 6.5nm of film thickness.
Embodiment 13:
Preparation has Al
2o
3film coating ZSM-5 catalyst
Unmodified HZSM-5 powder is placed in the flow chamber of ALD reaction, adopts embodiment 2 step 2) in method do 100 circular responses after take out sample, at 700 DEG C, roasting 5 hours, obtains having Al
2o
3the ZSM-5 catalyst of film.
Claims (5)
1. the application of anti-coking catalyst in Aldehyde-ammonia Condensation reaction, catalyst active ingredient is the molecular sieve of molecular sieve or metallic element modification, it is characterized in that, adopt atomic layer deposition method at the surface of catalyst active ingredient coating oxide coating, after calcination processing, obtain finished catalyst, described oxide is Al
2o
3, described molecular sieve is any one in ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-57, ZSM-58, MCM-22, MCM-36, MCM-41, MCM-49, MCM-56, β zeolite, X zeolite or Y zeolite; Described metallic element be in magnesium, calcium, lanthanum, titanium, zirconium, molybdenum, vanadium, manganese, chromium, iron, cobalt, nickel, copper, zinc, palladium, platinum, niobium, thallium, lead, bismuth, tin, antimony, tungsten, indium, hafnium, germanium, cadmium, yttrium any one or multiple; Described atomic layer deposition method is specially: under 200 DEG C of conditions, and the mode replaced with pulse in flow chamber is by trimethyl aluminium and water, and period purges with high pure nitrogen, and each step is respectively 10s, and its single cycle reaction time is 10s-10s-10s-10s.
2., by the application of anti-coking catalyst according to claim 1 in Aldehyde-ammonia Condensation reaction, it is characterized in that, described oxide coating thickness 2-30nm.
3., by the application of the anti-coking catalyst described in claim 1 or 2 in Aldehyde-ammonia Condensation reaction, it is characterized in that, described oxide coating thickness is 5-20nm.
4. by the application of anti-coking catalyst according to claim 3 in Aldehyde-ammonia Condensation reaction, it is characterized in that, adopt atomic layer deposition method at the surface of catalyst active ingredient coating oxide coating, after calcination processing, obtain finished catalyst.
5., by the application of anti-coking catalyst according to claim 4 in Aldehyde-ammonia Condensation reaction, it is characterized in that, described calcination processing temperature is 300-900 DEG C, calcination time 2-10 hour.
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| CN104014364B (en) * | 2014-06-19 | 2017-02-15 | 中国石油大学(北京) | Denitrification copper radical molecular sieve catalyst as well as preparation method and application thereof |
| CN107376918A (en) * | 2017-06-22 | 2017-11-24 | 上海师范大学 | High heat stability alundum (Al2O3)/nickel/alundum (Al2O3) sandwich catalyst and preparation method and application |
| CN107754814B (en) * | 2017-11-06 | 2020-09-04 | 江南大学 | High-stability iron-based catalyst and application thereof in Fischer-Tropsch reaction |
| CN107855123B (en) * | 2017-11-23 | 2020-04-10 | 中国科学技术大学 | Pd/SiO2@Al2O3Nanocrystalline material and preparation method and application thereof |
| CN109225128B (en) * | 2018-11-28 | 2019-08-23 | 哈尔滨工业大学 | A kind of spatial molecular pollutant adsorbent material and preparation method thereof |
| CN110694673A (en) * | 2019-10-22 | 2020-01-17 | 淮阴师范学院 | Aromatization catalyst of waste edible oil and preparation method and application thereof |
| KR20220049970A (en) | 2020-10-15 | 2022-04-22 | 한화솔루션 주식회사 | Method for preparing metal catalyst deposited with layer film by ALD process and metal catalyst thereof |
| CN113058597B (en) * | 2021-03-18 | 2023-10-27 | 北京工业大学 | Regeneration method of supported platinum-based three-way catalyst |
| CN113275033A (en) * | 2021-04-21 | 2021-08-20 | 山东省科学院能源研究所 | Hierarchical pore molecular sieve supported metal catalyst and regulation method and application thereof |
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