CN102935378A - Anti-coking catalyst and preparation method and applications thereof - Google Patents
Anti-coking catalyst and preparation method and applications thereof Download PDFInfo
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- CN102935378A CN102935378A CN2012104553870A CN201210455387A CN102935378A CN 102935378 A CN102935378 A CN 102935378A CN 2012104553870 A CN2012104553870 A CN 2012104553870A CN 201210455387 A CN201210455387 A CN 201210455387A CN 102935378 A CN102935378 A CN 102935378A
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Abstract
The invention discloses an anti-coking catalyst and a preparation method and applications thereof. Effective components of the catalyst include molecular sieves or metal element modified molecular sieves, oxide coatings are coated on surfaces of the catalyst effective components by using an atomic layer sedimentation method, the coated catalyst effective components are calcined to form catalyst products, and the oxide is one or more of Al2O3, SiO2 and TiO2. According to the anti-coking catalyst and the preparation method and applications thereof, problems that catalysts are easy to be inactive and the service life is short for the coking of catalyst surfaces in prior aldehyde ammonia condensation reaction are solved.
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 that in the Aldehyde-ammonia Condensation reaction, uses.
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 is so that the irreversible low value carbon source (coke) that turned to of high value carbon source, and this loss is huge when large-scale production.The catalysqt deactivation that causes owing to the catalyst surface carbon distribution is a subject matter that faces in the production of Aldehyde-ammonia Condensation reaction industry.
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 can adjust synthetic route 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.At present a lot of about the research of catalyst activity, wherein the catalyst take ZSM-5 molecular sieve as carrier shows higher activity and selectivity in the Aldehyde-ammonia Condensation reaction.Patent CN 1506354A adopts the ZSM-5 molecular sieve of processing through strong alkali aqueous solution as catalyst take ammonia, formaldehyde, acetaldehyde as raw material, and the pyridine base total recovery can reach 74.7%.Patent CN1263741C and CN1565736A carry out modification with the mixture of plumbous and cobalt to the ZSM-5 catalyst, and reaction is 4 hours under 450 ℃ of conditions, and the pyridine yield can reach 55.5%, and the total recovery of pyridine base reaches 81%.As catalyst, under 450 ℃ of conditions, the total recovery of formaldehyde, acetaldehyde, ammonia react pyridine base can reach 84% to patent CN 102430423A with the mixture of ZSM-5 and Co-ZSM-5, and the yield of pyridine can reach 60%.The activity and selectivity of these catalyst is all higher, but poor stability reacted after 5-6 hour, and the active of catalyst obviously descends.Because the catalyst carbon deposit inactivation, the extending catalyst life-span has become Aldehyde-ammonia Condensation and has produced the subject matter that pyridine and its derivatives need to overcome.
As catalyst, at 450 ℃, air speed is 1000h to patent CN 1631536A with palladium, cobalt and plumbous mixed and modified ZSM-5 molecular sieve
-1Under the condition, the pyridine yield reaches 70%, and the 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, had prolonged again the service life of catalyst simultaneously, but still can not satisfy 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 being applied oxide coating, catalyst surface promotes catalytic performance, 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 to apply oxide coating on the surface of catalyst active ingredient, obtain the catalyst finished product after calcination processing, 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 be 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 the Y zeolite arbitrarily.
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, the yttrium any one or multiple.
The method for preparing described anti-coking catalyst adopts atomic layer deposition method to apply oxide coating on the surface of catalyst active ingredient, obtains the catalyst finished product after calcination processing.
Described calcination processing temperature is 300-900 ℃, calcination time 2-10 hour.
The application of described anti-coking catalyst in the Aldehyde-ammonia Condensation reaction.
Beneficial effect: technique for atomic layer deposition (ALD) distinctively extremely strongly can carry out at catalyst surface coating, the processing of particular oxides film from the restraining growth characteristic with it, can make film thickness precisely controlled by the method, obtain surface uniform, smooth film.The present invention adopts the ALD method that raw catalyst is carried out Al
2O
3, SiO
2, TiO
2In the coating of one or more sulls, then adopt calcination processing, generated new duct at catalyst surface, can either make catalytic active center exposed, guarantee efficiently carrying out of reaction, can effectively reduce catalyst coking, the service life of extending catalyst again, catalyst extends to more than 55 hours the longest reaching about 80h service life.
The specific embodiment
The below will the present invention is further illustrated by embodiment:
Employed molecular sieve is commercially available among the present invention, the molecular sieve of used metallic element modification adopts document Jiang Jie, Mao Dongsen, Yang Weimin etc. (2003). " different preparation methods are on the impact of Aldehyde-ammonia Condensation catalyst P b-H-ZSM-5 performance ", petrochemical technology and application 21 (4): the method preparation of putting down in writing among the 246-248.Used atomic layer deposition method list of references Elam, J.W., A.Zinovev, et al. (2006). " Atomic layer deposition ofpalladium films on Al2O3 surfaces. " Thin Solid Films 515 (4): the method for putting down in writing among the 1664-1673..
Embodiment 1: preparation cobalt, lead, palladium modified ZSM-5 catalyst
1) 5 gram cobalt nitrates and 10 gram plumbi nitras are added water 125ml wiring solution-forming, with 0.017 gram palladium bichloride 1.25ml aqua regia dissolution, join in the mixed solution, HZSM-5 type molecular sieve 50 grams are immersed in the mixed liquor, 90-100 ℃ of lower the stirring 20 hours, being cooled to room temperature, then filtering, is 6-7 with deionized water rinsing to pH value.Then 110 ℃ lower dry 8 hours, 550 ℃ of roastings 4 hours place air to naturally cool to room temperature, obtain cobalt, lead, palladium modified ZSM-5 catalyst.
Embodiment 2:
Be prepared with Al
2O
3The cobalt of film coating, lead, palladium modified ZSM-5 catalyst:
1) identical with embodiment 1 step 1).
2) with step 1) pressed powder that obtains places the flow chamber of ALD reaction, under 200 ℃ of conditions, the mode that replaces with pulse in flow chamber is by trimethyl aluminium and water, purge with high pure nitrogen during this time, each step is respectively 10s, and its single cycle reaction time is (10s-10s-10s-10s).Take out later on sample through 150 circular responses, in 600 ℃ of lower roastings 3 hours, obtain having Al
2O
3The cobalt of film, lead, palladium modified ZSM-5 catalyst.Al
2O
3The about 15nm of the thickness of film.
Embodiment 3:
Preparation process is identical with embodiment 2 with method, just with embodiment 2 steps 2) in the circular response number reduce to 100, in 600 ℃ of lower roastings 3 hours, the Al of resulting 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 with embodiment 2 steps 2) in the circular response number reduce to 80, in 600 ℃ of lower roastings 3 hours, the Al of prepared cobalt, lead, palladium modified ZSM-5 catalyst
2O
3The about 8nm of film thickness.
Embodiment 5:
Be prepared with SiO
2The cobalt of film coating, lead, palladium modified ZSM-5 catalyst
1) identical with embodiment 1 step 1).
2) with step 1) pressed powder that obtains places the flow chamber of ALD reaction, under 240 ℃ of conditions, the mode that replaces with pulse in flow chamber is by tetrachloro silicane and water, purge with high pure nitrogen during this time, each step is respectively 60s, and its single cycle reaction time is (60s-60s-60s-60s).Take out later on sample through 100 circular responses, in 700 ℃ of roastings 6 hours, obtain having SiO
2The cobalt of film, lead, palladium modified ZSM-5 obtain catalyst, SiO
2The about 8nm of film thickness.
Embodiment 6:
Be prepared with TiO
2The cobalt of film coating, lead, palladium modified ZSM-5 catalyst
1) identical with embodiment 1 step 1).
2) with step 1) pressed powder that obtains places the flow chamber of ALD reaction, under 110 ℃ of conditions, the mode that replaces with pulse in flow chamber is by isopropyl titanate and water, purge with high pure nitrogen during this time, each step is respectively 10s, and its single cycle reaction time is (10s-10s-10s-10s).Take out later on sample through 45 circular responses, in 500 ℃ of roastings 8 hours, obtain having TiO
2The cobalt of film, lead, palladium modified ZSM-5 obtain catalyst, TiO
2The about 8nm of film thickness.
Embodiment 7:
Be prepared with Al
2O
3And TiO
2The cobalt of film coating, lead, palladium modified ZSM-5 catalyst
1) identical with embodiment 1 step 1).
2) with step 1) pressed powder that obtains places the flow chamber of ALD reaction, under 200 ℃ of conditions, adopt embodiment 2 steps 2) in method do 5 circular responses, adopt afterwards embodiment 6 steps 2) in method do 5 circular responses, these 10 circular responses are designated as 1 systemic circulation reaction.Through taking out sample after 5 systemic circulation reactions, in 550 ℃ of roastings 6 hours, obtain having Al
2O
3And TiO
2The cobalt of film, lead, palladium modified ZSM-5 catalyst, film thickness is 9nm approximately.
Embodiment 8:
The catalytic activity examination.
Prepare pyridine with Aldehyde-ammonia Condensation and react comparing embodiment 1-7.Reaction condition is as follows: the mol ratio of acetaldehyde, formaldehyde and ammonia is 2:1:4 in the charging, 450 ℃ of reaction temperatures, and reaction gas air speed GHSV is 1000h
-1, reactor is the stainless steel tube of internal diameter 8mm, product is analyzed with gas-chromatography.Use through Al respectively
2O
3The catalyst (embodiment 2-4) that applies, through SiO
2The catalyst (embodiment 5) that applies, through TiO
2The catalyst (embodiment 6) that applies, through Al
2O
3And TiO
2The catalyst (embodiment 7) that applies and the catalyst (embodiment 1) of not oxidised thing thin film coated, the catalyst activity test result is as shown in table 1.
Table 1 embodiment 1-7 Aldehyde-ammonia Condensation catalytic performance relatively
From table 1 data as can be known, on the catalyst that makes in embodiment 2-7, the regeneration period of catalyst is not waited from 55 hours by 79 hours, 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 that adopts the present invention to make can significantly improve the regeneration period of catalyst, the service life of extending catalyst.
Embodiment 9: be prepared with TiO
2The plumbous modified ZSM-5 catalyst of film coating
1) 15 gram plumbi nitras are added water 125ml wiring solution-forming, HZSM-5 type molecular sieve 50 grams are immersed in the lead nitrate solution, 90-100 ℃ of lower the stirring 20 hours is cooled to room temperature, then filter, and be 6-7 with deionized water rinsing to pH value.Then 110 ℃ lower dry 8 hours, 550 ℃ of roastings 4 hours place air to naturally cool to room temperature, obtain plumbous modified ZSM-5 catalyst.
2) pressed powder that step 1) is obtained places the flow chamber of ALD reaction, according to embodiment 6 steps 2) described method takes out sample after doing 53 circular responses, in 500 ℃ of roastings 8 hours, obtained TiO
2The plumbous modified ZSM-5 catalyst of film coating, TiO
2The about 9nm of film thickness.
Embodiment 10: be prepared with Al
2O
3The iron modified ZSM-5 catalyst of film coating
1) 18 gram ferric nitrates are added water 125ml wiring solution-forming, HZSM-5 type molecular sieve 50 grams are immersed in the iron nitrate solution, 90-100 ℃ of lower the stirring 20 hours is cooled to room temperature, then filter, and be 6-7 with deionized water rinsing to pH value.Then 110 ℃ lower dry 8 hours, 550 ℃ of roastings 4 hours place air to naturally cool to room temperature, obtain the iron modified ZSM-5 catalyst.
2) pressed powder that step 1) is obtained places the flow chamber of ALD reaction, according to embodiment 2 steps 2) described method takes out sample after doing 120 circular responses, in 800 ℃ 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:
Be prepared with Al
2O
3And TiO
2The lanthanum modification beta-zeolite catalyst of film coating
1) 4 gram lanthanum nitrates is added water 50ml wiring solution-forming, 50 gram beta-zeolites are immersed in the lanthanum nitrate hexahydrate, 80 ℃ lower stir after 24 hours in 120 ℃ lower dry 12 hours, 550 ℃ of roastings 4 hours, place air to naturally cool to room temperature, obtain the beta-zeolite catalyst of lanthanum modification.
2) with step 1) pressed powder that obtains places the flow chamber of ALD reaction, adopts embodiment 7 steps 2) in method take out samples after doing 4 systemic circulations reactions, in 550 ℃ of roastings 7 hours, obtain having Al
2O
3And TiO
2The beta-zeolite catalyst of the lanthanum modification of laminated film, the about 7nm of film thickness.
Embodiment 12:
Be prepared with SiO
2Film coating molybdenum modified MC M-22 catalyst
1) 5 gram ammonium heptamolybdates is added water 50ml wiring solution-forming, 50 gram MCM-12 are immersed in the ammonium molybdate solution, place under the room temperature after 24 hours in 120 ℃ lower dry 12 hours, 500 ℃ of roastings 4 hours, place air to naturally cool to room temperature, obtain the MCM-22 catalyst of molybdenum modification.
2) with step 1) pressed powder that obtains places the flow chamber of ALD reaction, adopts embodiment 5 steps 2) in method take out sample after doing 80 circular responses, in 500 ℃ of roastings 3 hours, obtain having SiO
2The molybdenum modified MC M-22 catalyst of film, the about 6.5nm of film thickness.
Embodiment 13:
Be prepared with Al
2O
3Film coating ZSM-5 catalyst
Unmodified HZSM-5 powder is placed the flow chamber of ALD reaction, adopts embodiment 2 steps 2) in method take out sample after doing 100 circular responses, in 700 ℃ of lower roastings 5 hours, obtain having Al
2O
3The ZSM-5 catalyst of film.
Claims (8)
1. anti-coking catalyst, catalyst active ingredient is the molecular sieve of molecular sieve or metallic element modification, it is characterized in that, adopts atomic layer deposition method to apply oxide coating on the surface of catalyst active ingredient, obtain the catalyst finished product after calcination processing, described oxide is Al
2O
3, SiO
2, TiO
2In one or more.
2. by anti-coking catalyst claimed in claim 1, it is characterized in that described oxide coating thickness 2-30nm.
3. by claim 1 or 2 described anti-coking catalyst, it is characterized in that, described oxide coating thickness is 5-20nm.
4. by anti-coking catalyst claimed in claim 1, it is characterized in that, described molecular sieve be 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 the Y zeolite arbitrarily.
5. by claim 1 or 4 described anti-coking catalyst, it is characterized in that, 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, the yttrium any one or multiple.
6. prepare the method for the arbitrary described anti-coking catalyst of claim 1 ~ 5, it is characterized in that, adopt atomic layer deposition method to apply oxide coating on the surface of catalyst active ingredient, after calcination processing, obtain the catalyst finished product.
7. by the method for preparing the anti-coking catalyst claimed in claim 6, it is characterized in that, described calcination processing temperature is 300-900 ℃, calcination time 2-10 hour.
8. the application of the arbitrary described anti-coking catalyst of claim 1 ~ 5 in the Aldehyde-ammonia Condensation reaction.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014364A (en) * | 2014-06-19 | 2014-09-03 | 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 |
| CN107754814A (en) * | 2017-11-06 | 2018-03-06 | 江南大学 | A kind of ferrum-based catalyst of high stability and its application in fischer-tropsch reaction |
| CN107855123A (en) * | 2017-11-23 | 2018-03-30 | 中国科学技术大学 | A kind of Pd/SiO2@Al2O3Nanocrystalline material and preparation method thereof, application |
| CN109225128A (en) * | 2018-11-28 | 2019-01-18 | 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 |
| CN113058597A (en) * | 2021-03-18 | 2021-07-02 | 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 |
| WO2022080850A1 (en) | 2020-10-15 | 2022-04-21 | 한화솔루션 주식회사 | Method for producing metal catalyst having composite film deposited thereon by means of ald process, and metal catalyst according thereto |
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| CN104014364A (en) * | 2014-06-19 | 2014-09-03 | 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 |
| CN107754814A (en) * | 2017-11-06 | 2018-03-06 | 江南大学 | A kind of ferrum-based catalyst of high stability and its application in fischer-tropsch reaction |
| CN107855123A (en) * | 2017-11-23 | 2018-03-30 | 中国科学技术大学 | A kind of Pd/SiO2@Al2O3Nanocrystalline material and preparation method thereof, application |
| 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 |
| CN109225128A (en) * | 2018-11-28 | 2019-01-18 | 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 |
| WO2022080850A1 (en) | 2020-10-15 | 2022-04-21 | 한화솔루션 주식회사 | Method for producing metal catalyst having composite film deposited thereon by means of ald process, and metal catalyst according thereto |
| 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 |
| CN113058597A (en) * | 2021-03-18 | 2021-07-02 | 北京工业大学 | Regeneration method of supported platinum-based three-way catalyst |
| 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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