CN1278773C - Catalyst for reducing petrol olefinic content and its preparing method - Google Patents
Catalyst for reducing petrol olefinic content and its preparing method Download PDFInfo
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- CN1278773C CN1278773C CN 200410101802 CN200410101802A CN1278773C CN 1278773 C CN1278773 C CN 1278773C CN 200410101802 CN200410101802 CN 200410101802 CN 200410101802 A CN200410101802 A CN 200410101802A CN 1278773 C CN1278773 C CN 1278773C
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Abstract
The present invention relates to a catalyst for reducing the content of olefine in gasoline and maintaining the octane value, which comprises active components of a molecular sieve, amorphous Si-Al oxide and kaolin, wherein the active components comprise 0.5 to 10 % (accounting for the weight percentage of the catalyst) of rare earth-ZSM5/MCM22 cocrystallization molecular sieve and 15 to 40% of rare earth Y molecular sieve. After a compound molecular sieve is uniformly mixed with aluminum oxide and the kaolin, the catalyst is prepared by the steps of spray forming, dryness and steam treatment. The catalyst has the characteristics for obviously reducing the content of olefine in gasoline and maintaining the octane value of gasoline without falling.
Description
Technical field
The present invention relates to a kind of gasoline modified technology, particularly relate to a kind of catalyst that content of olefin in gasoline is protected octane number that reduces.
The invention still further relates to above-mentioned Preparation of catalysts method.
Background technology
With improving constantly of worldwide gasoline and diesel oil standard, people are more and more stricter to the motor petrol quality requirement, the gasoline standard of China's main cities execution in 2003: sulfur content is not more than 0.08%, olefin(e) centent is not more than 35%, benzene content is not more than 2.5%, arene content is not more than 40%, 2005 year further reduces in the gasoline olefin(e) centent less than 20%.External gasoline mainly is catalytic reforming gasoline, arene content height in the gasoline, and olefin(e) centent is low, and octane number is mainly by the aromatic hydrocarbons contribution, and its research direction is to reduce benzene and aromatic hydrocarbon content; China's gasoline mainly is catalytically cracked gasoline, and benzene and aromatic hydrocarbon content are low, olefin(e) centent very high (reaching 50～55%), octane number is mainly contributed by alkene, thereby main direction of studying is when reducing olefin(e) centent, guarantees that gasoline has qualified octane number.
U.S. Pat P5,865,988 have introduced a kind of low-quality gasoline upgrading technology of Mobil company exploitation.This process using two step method: at first raw gasoline is passed through CoMo/Al
2O
3Beds is removed the sulfide hydrogenation, makes part alkene saturated simultaneously; Second step will generate previously product by containing the bed of ZSM-5 catalyst, with the octane number that recovers in hydrogenation process, to lose.Adopt this technology can reduce sulfur content and olefin(e) centent in the oil product greatly, increased arene content simultaneously, and keep octane number not reduce.
Disclose a kind of low-quality gasoline upgrading among the CN1350051A and produced the composite catalyst of clean gasoline.This catalyst has comprised a kind of ZSM-5 molecular sieve with small crystal grains, rare earth and transition metal oxide, under very high hydrogen-oil ratio condition, be used for catalytically cracked gasoline, catalytic cracking gasoline, pyrolysis gasoline, during the upgrading of low-quality gasoline such as coker gasoline, can reduce its alkene, benzene and sulfur content, satisfy the requirement of standard GB 17930-1999, keep octane number not reduce simultaneously.
Disclosed a kind of catalytic cracking catalyst that is rich in isoparaffin gasoline that is used to produce among the CN1354223, be by 0～70 heavy % clay that is benchmark with the catalyst weight, the zeolite of 5～90 heavy % inorganic oxides and 1～50 heavy % is formed, zeolite wherein is for being that the silica alumina ratio of 25～75 heavy % of benchmark is 5～15 with zeolite weight, with Re
2O
3The content of rare earth of meter is that the high-silicon Y-Zeolite of 8～20 heavy % and the silica alumina ratio of 25～75 heavy % are 16～50, with Re
2O
3The content of rare earth of meter is the mixture of the high-silicon Y-Zeolite of 2～7 heavy %.Use this catalyst can obviously improve the content of isoparaffin in the gasoline.
Disclosed a kind of assistant for calalytic cracking that reduces content of olefin in gasoline among the CN1388221A, be made up of the y-type zeolite that contains rare earth, the MFI structural zeolite, clay, aluminium oxide, the phosphorus that contain rare earth, wherein containing the y-type zeolite middle rare earth of rare earth and the ratio of MFI structural zeolite middle rare earth content is 0.05-200: 1.This auxiliary agent be MFI structural zeolite, the clay that will handle with the y-type zeolite that contains rare earth of phosphorus-containing compound solution-treated, with earth solution and mix homogeneous the matrix three that double aluminium binder synthesizes after spray-drying, and then carry out post processing with phosphorus-containing compound solution, filter, drying obtains.This auxiliary agent can reduce 5-9 percentage point with olefin(e) centent in the catalytic cracking production gasoline.
Disclosed a kind of FCC catalyst that reduces content of olefin in gasoline among the CN1317547, form by zeolite type active component, amorphous silicon aluminium oxide and kaolin, wherein active component is to be made up of 0.5-5% (accounting for the percentage by weight of FCC catalyst, down together) ZSM-5,0.5-15% rare earth exchanged Y zeolite, 20-40% phosphorus and the composite modified overstable gamma zeolite of rare earth.Composite molecular screen and aluminium oxide, binding agent, kaolin mix, then through spraying, curing, washing, dry back preparation cost invention FCC catalyst.Compare with conventional catalyst, guaranteeing obviously to reduce the olefin(e) centent of gasoline under the prerequisite that other products distribute and octane number is constant substantially.
Summary of the invention
The purpose of this invention is to provide a kind of obvious reduction content of olefin in gasoline guarantor octane number catalyst that has.
Another object of the present invention provides above-mentioned Preparation of catalysts method.
For achieving the above object, reduction content of olefin in gasoline provided by the invention is protected octane number catalyst composition, and (ratio of each component is removed special instruction, be the percentage by weight that accounts for whole catalyst) as follows: 0.5-10% rare earth-ZSM5/ZSM11 cocrystallization molecular sieve, 0.05-3% phosphorus, the 15-40% rare-earth Y molecular sieve, total molecular sieve content 20-50%, all the other are matrix components.
In the catalyst of the present invention, matrix contains components such as aluminium oxide, kaolin.Aluminium oxide derives from aluminium colloidal sol, the alumina content 20-80% that is weight percentage, the kaolin content 80-20% that is weight percentage.
In the catalyst of the present invention, phosphorus-containing compound solution is selected from a kind of or their aqueous solution of mixture in phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), the ammonium phosphite.
In the catalyst of the present invention, rare-earth Y molecular sieve middle rare earth content accounts for the percentage by weight 0.5-20% of rare-earth Y molecular sieve, and Y molecular sieve comprises among USY, REY and the REHY one or more mixture.
In the catalyst of the present invention, contain rare earth and have ZSM5 and the molecular sieve of ZSM11 cocrystallization structure, wherein having ZSM5 crystal phase structure part is 0.05-20 with the weight ratio with ZSM11 crystal phase structure part, and internal standard method is adopted in the calculating of ZSM5 content.
The method that the present invention prepares above-mentioned catalyst is as follows:
With 0.5-10% rare earth-ZSM5/ZSM11 cocrystallization molecular sieve, 0.05-3% phosphorus, the 15-40% rare-earth Y molecular sieve, the 20-80% aluminium oxide, 80-20% kaolin mixes back (solid/water in the mixture=0.3-0.5, weight by weight) spray shaping, drying, steam treatment makes catalyst of the present invention.Wherein spray condition is inlet temperature 250-450 ℃, exhaust temperature 50-350 ℃, and atomisation pressure 0.2-1.0MPa, baking temperature 400-600 ℃, time 2-4 hour, the steam treatment condition was that 100% water vapour was handled 4-20 hour down in 700-800 ℃.
Its middle rare earth-ZSM5/ZSM11 cocrystallization molecular sieve can be synthetic by the described method of Chinese patent CN1137022A.Synthesis of molecular sieve raw material proportioning:
XNa
2O.YRE
2O
3.Al
2O
3.ZSiO
2
X=0.1～1.0 wherein, Y=0.01～1.0, Z=20～300 (mol ratio).
With salt, waterglass and the deionized water of a certain amount of reaction raw materials aluminium source, inorganic acid, rare earth element, under constantly stirring, add in the stainless steel cauldron in sequence when synthetic, synthetic under certain temperature and crystallization time condition.
The reduction content of olefin in gasoline of the present invention's preparation is protected in the octane number catalyst, and the effect of Rare Earth Y is the hydrogen migration ability that adds powerful catalyst, but often causes the octane number decline (seeing comparative example 1 and embodiment 8) of gasoline.The effect of catalyst middle rare earth-ZSM5/ZSM11 cocrystallization molecular sieve is cracking ability, aromatisation and the isomerization ability that increases gasoline olefin, and compensation causes the loss of octane number owing to the minimizing of gasoline olefin.Rare earth-ZSM5/ZSM11 cocrystallization molecular sieve is different from the mechanical impurity of rare earth, ZSM5 and ZSM11.This cocrystallization molecular sieve is rare earth to be mounted in the cocrystallization ZSM5/ZSM11 framework of molecular sieve to form in synthetic cocrystallization ZSM5/ZSM11 molecular sieve (mechanical impurity that is different from ZSM and ZSM11).This zeolite molecular sieve has good acid water heat endurance and anti-contaminating impurity ability (seeing Chinese patent CN1137022A).This has great industrial Practical significance for the catalytic process that relates to hydrothermal treatment consists (as the regeneration of catalyst).
The specific embodiment
Below in conjunction with preferable comparative example and embodiment the present invention is further elaborated.
Comparative example 1
With a certain amount of phosphoric acid, rare earth REHY molecular sieve (content of rare earth accounts for 4.5 heavy % of rare earth REHY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mixes back (solid/water in the mixture=0.4, weight by weight) spray shaping, drying, steam treatment makes catalyst A.Wherein spray condition is 300 ℃ of inlet temperatures, 250 ℃ of exhaust temperatures, and atomisation pressure 0.2MPa, 500 ℃ of baking temperatures, the steam treatment condition is 700 ℃ of 100% water vapour 6 hours.The catalyst A that makes, wherein the weight content of P and rare-earth Y molecular sieve is respectively 0.5% and 42%.
Embodiment 1
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of a certain amount of rare earth-70 molecular sieve (content of rare earth accounts for 1.2 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of rare earth-70 molecular sieve), phosphoric acid, rare earth REHY molecular sieve (content of rare earth accounts for 4.5 heavy % of rare earth REHY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mix (solid/water in the mixture=0.4, back, weight by weight) spray shaping, drying, steam treatment makes catalyst B.Wherein spray condition is 300 ℃ of inlet temperatures, 250 ℃ of exhaust temperatures, and atomisation pressure 0.2MPa, 500 ℃ of 2 hours times of baking temperature, the steam treatment condition is 700 ℃ of 100% water vapour 6 hours.Make catalyst B, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of its middle rare earth-70 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 7%, 0.5% and 35%.
Embodiment 2
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/50 of a certain amount of rare earth-50 molecular sieve (content of rare earth accounts for 5.2 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/50 of rare earth-50 molecular sieve), ammonium dihydrogen phosphate (ADP), rare earth REY molecular sieve (content of rare earth accounts for 10 heavy % of rare earth REY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mix (solid/water in the mixture=0.5, back, weight by weight) spray shaping, drying, steam treatment makes catalyst C.Wherein spray condition is 450 ℃ of inlet temperatures, 50 ℃ of exhaust temperatures, and atomisation pressure 1.0MPa, 600 ℃ of baking temperatures, 4 hours time, the steam treatment condition is 700 ℃ of 100% water vapour 20 hours.Make catalyst C, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/50 of its middle rare earth-50 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 0.5%, 2.5% and 40%.
Embodiment 3
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/90 of a certain amount of rare earth-10 molecular sieve (content of rare earth accounts for 3.2 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/90 of rare earth-10 molecular sieve), ammonium hydrogen phosphate, rare earth REHY and REY molecular sieve (REHY/REY=50/50 (weight by weight), content of rare earth accounts for 18 heavy % of rare earth REHY and REY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mixes (solid/water in the mixture=0.3, back, weight by weight) spray shaping, dry, steam treatment makes catalyst D.Wherein spray condition is 250 ℃ of inlet temperatures, 350 ℃ of exhaust temperatures, and atomisation pressure 0.8MPa, 400 ℃ of baking temperatures, 3 hours time, the steam treatment condition is 800 ℃ of 100% water vapour 4 hours.Make catalyst D, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/90 of its middle rare earth-10 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 10%, 1.0% and 15%.
Embodiment 4
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/10 of a certain amount of rare earth-90 molecular sieve (content of rare earth accounts for 0.8 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/10 of rare earth-90 molecular sieve), phosphoric acid, rare earth USY molecular sieve (content of rare earth accounts for 2 heavy % of rare earth USY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mix (solid/water in the mixture=0.3, back, weight by weight) spray shaping, drying, steam treatment makes catalyst E.Wherein spray condition is 320 ℃ of inlet temperatures, 200 ℃ of exhaust temperatures, and atomisation pressure 0.5MPa, 550 ℃ of baking temperatures, 4 hours time, the steam treatment condition is 700 ℃ of 100% water vapour 5 hours.Make catalyst E, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/10 of its middle rare earth-90 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 5%, 0.1% and 25%.
Embodiment 5
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of a certain amount of rare earth-70 molecular sieve (content of rare earth accounts for 3.0 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of rare earth-70 molecular sieve), phosphoric acid, rare earth REHY molecular sieve (content of rare earth accounts for 4.5 heavy % of rare earth REHY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mix (solid/water in the mixture=0.3, back, weight by weight) spray shaping, drying, steam treatment makes catalyst F.Wherein spray condition is 300 ℃ of inlet temperatures, 250 ℃ of exhaust temperatures, and atomisation pressure 0.2MPa, 500 ℃ of baking temperatures, the steam treatment condition is 700 ℃ of 100% water vapour 16 hours.Make catalyst F, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of its middle rare earth-70 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 7%, 1.0% and 20%.
Embodiment 6
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of a certain amount of rare earth-70 molecular sieve (content of rare earth accounts for 4.1 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of rare earth-70 molecular sieve), phosphoric acid, rare earth REHY molecular sieve (content of rare earth accounts for 4.5 heavy % of rare earth REHY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mix (solid/water in the mixture=0.3, back, weight by weight) spray shaping, drying, steam treatment makes catalyst G.Wherein spray condition is 300 ℃ of inlet temperatures, 250 ℃ of exhaust temperatures, and atomisation pressure 0.2MPa, 500 ℃ of baking temperatures, the steam treatment condition is 700 ℃ of 100% water vapour 6 hours.Make catalyst G, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of its middle rare earth-70 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 7%, 1.0% and 27%.
Embodiment 7
With the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of a certain amount of rare earth-70 molecular sieve (content of rare earth accounts for 2.2 heavy % of the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of rare earth-70 molecular sieve), phosphoric acid, rare earth REHY molecular sieve (content of rare earth accounts for 4.5 heavy % of rare earth REHY molecular sieve), aluminium colloidal sol (aluminium oxide accounts for aluminium colloidal sol 23.0 heavy %), kaolin, deionized water mix (solid/water in the mixture=0.3, back, weight by weight) spray shaping, drying, steam treatment makes catalyst H.Wherein spray condition is 300 ℃ of inlet temperatures, 250 ℃ of exhaust temperatures, and atomisation pressure 0.2MPa, 500 ℃ of baking temperatures, the steam treatment condition is 800 ℃ of 100% water vapour 4 hours.Make catalyst H, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/30 of its middle rare earth-70 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 7%, 0.05% and 35%.
Embodiment and comparative example 8
Present embodiment and comparative example explanation catalyst is protected application aspect the octane number falling gasoline olefin.Dress 80g catalyst in fixed fluidized bed reaction tube is at N
2Be warmed up to 500 ℃ of activation under the atmosphere, then at N
2Atmosphere drops to reaction temperature, reacts under the condition shown in table 1 and 2, and raw material is a catalytically cracked gasoline, and concrete one-tenth is grouped into and sees Table 1, and reacted product is through cooler cooling carrying out gas-liquid separation.The online Shimadzu-8A chromatography of gas.Product liquid is formed with Varian 3800 chromatographic system analysis, adopts the PONA capillary column, hydrogen flame detector.Analysis result normalization obtains dry gas, and liquefied gas and product liquid are formed.The chromatogram software that the octane number of gasoline adopts Beijing naphthology research institute to provide calculates.
By the result of table 1 and table 2 as seen, adopt REHY (catalyst A) alkene in the gasoline can be lowered merely, but the octane number of gasoline descend.Catalyst B provided by the invention, C, D, E, F, G and H have obvious reduction content of olefin in gasoline, improve the performance of octane number.
The evaluation result of table 1 catalyst
| Catalyst | Raw material | A | B | C | D | E |
| RON | 88.8 | 86.2 | 93.4 | 93.0 | 93.0 | 92.9 |
| MON | 80.4 | 80.2 | 88.4 | 88.3 | 88.2 | 88.1 |
| 1, product distribution (wt%) | ||||||
| Dry gas | 0 | 0.44 | 0.75 | 0.76 | 0.73 | 0.76 |
| Liquefied gas | 1.75 | 15.11 | 15.77 | 16.77 | 16.47 | 16.57 |
| Liquid | 98.15 | 84.46 | 83.46 | 82.47 | 82.78 | 82.64 |
| 2, liquid is formed (wt%) | ||||||
| N-alkane | 5.35 | 6.88 | 6.75 | 6.77 | 6.73 | 6.67 |
| Isoparaffin | 28.20 | 56.41 | 51.98 | 54.75 | 54.14 | 53.12 |
| Cycloalkane | 6.80 | 6.43 | 4.63 | 4.86 | 4.81 | 4.73 |
| Alkene | 40.68 | 7.10 | 4.50 | 4.70 | 4.66 | 4.45 |
| Aromatic hydrocarbons | 18.86 | 23.17 | 32.13 | 28.92 | 29.65 | 31.00 |
Reaction condition: 450 ℃, 2h
-1, 15 minutes
The evaluation result of table 2 catalyst
| Catalyst | F | G | H |
| RON | 93.1 | 93.2 | 93.1 |
| MON | 87.7 | 87.1 | 87.3 |
| 1, product distribution (wt%) | |||
| Dry gas | 0.42 | 0.44 | 0.44 |
| Liquefied gas | 15.07 | 14.61 | 17.22 |
| Liquid | 84.51 | 84.96 | 82.34 |
| 2, liquid is formed (wt%) | |||
| N-alkane | 7.26 | 6.59 | 6.66 |
| Isoparaffin | 57.77 | 52.99 | 54.90 |
| Cycloalkane | 3.89 | 5.13 | 4.38 |
| Alkene | 4.56 | 5.74 | 3.82 |
| Aromatic hydrocarbons | 26.52 | 29.57 | 30.23 |
Reaction condition: 450 ℃, 2h
-1, 15 minutes
The foregoing description is the part preferred embodiment, is not the present invention is limited.In fact can realize the present invention so long as meet the condition that summary of the invention partly sets forth, therefore, protection domain of the present invention is as the criterion with the claim of application.
Claims (5)
1. one kind is reduced the catalyst that content of olefin in gasoline is protected octane number, its component is to account for whole catalyst weight percentage: 0.5-10% rare earth-ZSM5/ZSM11 cocrystallization molecular sieve, 15-40% rare-earth Y molecular sieve, total molecular sieve content 20-50%, 0.05-3% phosphorus, all the other are matrix components; Wherein:
Rare-earth Y molecular sieve middle rare earth content accounts for the 0.5-20% of rare-earth Y molecular sieve percentage by weight;
The 20-80% aluminium oxide that contains percentage by weight in the matrix components, 80-20% kaolin.
2. the catalyst of claim 1 is characterized in that, having ZSM5 crystal phase structure part in rare earth-ZSM5/ZSM11 cocrystallization molecular sieve is 0.05-20 with the weight ratio with ZSM11 crystal phase structure part.
3. method for preparing the described catalyst of claim 1, rare earth-ZSM5/ZSM11 cocrystallization molecular sieve, phosphorus, rare-earth Y molecular sieve, aluminium oxide, kaolin and water are mixed, solid/water is by weight=0.3-0.5 in the mixed solution, spray shaping, dry, steam treatment gets catalyst;
Wherein: spray condition is inlet temperature 250-450 ℃, exhaust temperature 50-350 ℃, and atomisation pressure 0.2-1.0MPa, baking temperature 400-600 ℃, time 2-4 hour, the steam treatment condition was that 100% water vapour was handled 4-20 hour down in 700-800 ℃.
4. the method for claim 3 is characterized in that, aluminium oxide derives from aluminium colloidal sol.
5. the method for claim 3 is characterized in that, phosphorus derives from one or more mixture aqueous solutions of phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium hydrogen phosphate, ammonium dihydrogen phosphate (ADP), ammonium phosphite.
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|---|---|---|---|
| CN 200410101802 CN1278773C (en) | 2004-12-23 | 2004-12-23 | Catalyst for reducing petrol olefinic content and its preparing method |
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|---|---|---|---|
| CN 200410101802 CN1278773C (en) | 2004-12-23 | 2004-12-23 | Catalyst for reducing petrol olefinic content and its preparing method |
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| CN1278773C true CN1278773C (en) | 2006-10-11 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448947C (en) * | 2005-12-21 | 2009-01-07 | 中国石油化工股份有限公司 | Method of lowering olefine content in gasoline |
| CN101020844B (en) * | 2006-02-15 | 2012-03-28 | 中国科学院大连化学物理研究所 | Catalyst for reducing olefin content in mixed material of liquified gas and gasoline |
| CN101559380B (en) * | 2009-06-03 | 2011-02-02 | 中国科学院大连化学物理研究所 | Catalyst used for producing BTX aromatics and clean gasoline by using catalytic gasoline and preparation |
| CN102794195B (en) * | 2012-08-28 | 2014-08-27 | 丁泳 | Catalyst suitable for enhancing gasoline octane number of fuel and lowering olefin content and application thereof |
| CN104492479B (en) * | 2014-12-10 | 2017-01-11 | 中国科学院大连化学物理研究所 | Catalyst for preparing pyridine from 3-methylpyridine and preparation method of catalyst |
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