CN1331990C - Catalyst for modifying gasoline and preparation thereof - Google Patents
Catalyst for modifying gasoline and preparation thereof Download PDFInfo
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- CN1331990C CN1331990C CNB2004101018051A CN200410101805A CN1331990C CN 1331990 C CN1331990 C CN 1331990C CN B2004101018051 A CNB2004101018051 A CN B2004101018051A CN 200410101805 A CN200410101805 A CN 200410101805A CN 1331990 C CN1331990 C CN 1331990C
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Abstract
The present invention relates to a catalyst for gasoline upgrading, which is composed of an active component of molecular sieves, amorphous silica-alumina oxide and kaolin, wherein the active component is composed of 0.5 to 10% (accounting for the weight percentage of the catalyst) of ZSM5/MCM22 cocrystallization molecular sieves and 15 to 40% of rare earth Y molecular sieves. After a compound molecular sieve is uniformly mixed with aluminum oxide and kaolin, the catalyst is prepared by spray forming, dryness and steam treatment. The catalyst of the present invention has the characteristics of obviously reducing the olefinic content of gasoline and keeping the octane number of the gasoline without falling.
Description
Technical field
The present invention relates to a kind of gasoline modified technology, particularly relate to a kind of gasoline upgrading, reduce the catalyzer that content of olefin in gasoline is protected octane value.
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 spirit specification of quality, the gasoline standard of China's main cities execution in 2003: sulphur content is not more than 0.08%, olefin(e) centent is not more than 35%, benzene content is not more than 2.5%, aromaticity 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, aromaticity content height in the gasoline, and olefin(e) centent is low, and gasoline octane rating 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%), gasoline octane rating is mainly contributed by alkene, thereby main direction of studying is when reducing olefin(e) centent, guarantees that gasoline has qualified octane value.
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 gasline is passed through CoMo/Al
2O
3Beds is removed the sulfide hydrogenation, makes part alkene saturated simultaneously; Second step will generate previously reaction product by containing the bed of ZSM-5 catalyzer, with the octane value that recovers in hydrogenation process, to lose.Adopt this technology can reduce sulphur content and olefin(e) centent in the oil product greatly, increased aromaticity content simultaneously, and keep octane value not reduce.
Disclose a kind of low-quality gasoline upgrading among the CN1350051A and produced the composite catalyst of clean gasoline.This catalyzer 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 sulphur content, satisfy the requirement of standard GB 17930-1999, keep octane value 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 catalyzer 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, aluminum oxide, the phosphorus that contain rare earth, wherein containing the y-type zeolite middle-weight rare earths of rare earth and the ratio of MFI structural zeolite middle-weight rare earths content is 0.05-200: 1.This auxiliary agent is MFI structural zeolite, the clay that will handle with the y-type zeolite that contains rare earth of P contained compound solution-treated, with earth solution and spraying drying after double aluminium binder synthetic matrix three mixes homogeneous, and then carry out aftertreatment with P contained 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 catalyzer that reduces content of olefin in gasoline among the CN1317547, form by zeolite type active ingredient, amorphous silicon aluminium oxide compound and kaolin, wherein active ingredient is to be made up of 0.5-5% (accounting for the weight percent of FCC catalyzer, 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 aluminum oxide, binding agent, kaolin mix, then through spraying, curing, washing, dry back preparation cost invention FCC catalyzer.Compare with conventional catalyst, guaranteeing obviously to reduce the olefin(e) centent of gasoline under the prerequisite that other products distribute and gasoline octane rating is constant substantially.
Summary of the invention
The purpose of this invention is to provide a kind of catalyzer that is used for gasoline upgrading, this catalyzer can obviously reduce content of olefin in gasoline and keep octane value.
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 value catalyzer composition, and (ratio of each component is removed special instruction, be the weight percent that accounts for whole catalyzer) as follows: 0.5-10%ZSM5/MCM22 cocrystallization molecular sieve, 0.05-3% phosphorus, the 15-40% rare-earth Y molecular sieve, the heavy % of total molecular sieve content 20-50, all the other are matrix components.
In the catalyzer of the present invention, matrix contains components such as aluminum oxide, kaolin.Aluminum oxide derives from aluminium colloidal sol, content 20-80%, the heavy % of kaolin content 80-20.
In the catalyzer of the present invention, P contained compound solution is selected from a kind of or their aqueous solution of mixture in phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium hydrogen phosphate, primary ammonium phosphate, the ammonium phosphite.
In the catalyzer of the present invention, rare-earth Y molecular sieve middle-weight rare earths content accounts for the 0.5-20% of rare-earth Y molecular sieve, and Y molecular sieve comprises USY, one or more mixture among REY and the REHY.
In the catalyzer of the present invention, the molecular sieve of ZSM5/ZSM22 cocrystallization structure, wherein ZSM5 accounts for the heavy % of 0.5-99.5 of ZSM5/MCM22 cocrystallization molecular sieve.Marker method is adopted in the calculating of ZSM5 content.
The method that the present invention prepares above-mentioned catalyzer is as follows:
With 0.5-10%ZSM5/MCM22 cocrystallization molecular sieve, 0.05-3% phosphorus, 15-40% rare-earth Y molecular sieve, 20-80% aluminum oxide, 80-20% kaolin mix back (solid/water in the mixture=0.3-0.5, weight by weight) spray shaping, drying, steam-treated makes catalyzer of the present invention.Wherein spray condition is temperature in 250-450 ℃, exhaust temperature 50-350 ℃, spray pressure 0.2-1.0MPa, drying temperature 400-600 ℃, time 2-4 hour, the steam-treated condition be 700-800 ℃ 100% water vapor 4-20 hour.
Concrete synthetic ZSM5/MCM22 cocrystallization molecular sieve can be synthetic by the described method of document [Peng Jianbiao, (master thesis), MCM-22 and iron replace synthetic and research, Dalian Inst of Chemicophysics, Chinese Academy of Sciences, 2002 of MCM-22].The synthesis of molecular sieve proportioning raw materials:
SiO
2: Al
2O
3: Na
2O: HMI: H
2O=1: 0.033: 0.11: 0.35: 45 (mol ratios).
With a certain amount of reaction raw materials sodium metaaluminate, sodium hydroxide, hexamethylene imine, water glass and deionized water, under constantly stirring, add in the stainless steel cauldron in order 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 value catalyzer, and the effect of Rare Earth Y is the hydrogen transference ability that adds powerful catalyst, but often causes the octane value decline (seeing comparative example 1 and embodiment 8) of gasoline.The effect of ZSM5/MCM22 cocrystallization molecular sieve is the cracking ability that increases gasoline olefin in the catalyzer, aromizing and isomerization ability, and compensation causes the loss of gasoline octane rating owing to the minimizing of gasoline olefin.ZSM5/MCM22 cocrystallization molecular sieve is different from the mechanically mixing sample of ZSM5 and MCM22, and it utilizes the synergy of ZSM5 and MCM22 and is presented as higher aromizing ability (seeing comparative example 2 and embodiment 8).
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 (aluminum 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-treated makes catalyst A.Wherein spray condition is 300 ℃ of temperature ins, 250 ℃ of exhaust temperatures, and spray pressure 0.2MPa, 500 ℃ of drying temperatures, the steam-treated condition is 700 ℃ of 100% water vapor 6 hours.The catalyst A that makes, wherein the weight content of phosphorus and rare-earth Y molecular sieve is respectively 0.5% and 42%.
Comparative example 2
With a certain amount of ZSM5 molecular sieve and MCM22 molecular sieve mechanical mixture (ZSM5/MCM22=70/30, weight by weight), 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 (aluminum 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-treated makes catalyst B.Wherein spray condition is 300 ℃ of temperature ins, 250 ℃ of exhaust temperatures, and spray pressure 0.2MPa, 500 ℃ of drying temperatures, the steam-treated condition is 700 ℃ of 100% water vapor 6 hours.Make catalyst B, wherein 70 heavy %ZSM5/30 weigh %MCM22 mechanically mixing molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 7%, 0.5% and 35%.
Embodiment 1
With the heavy %MCM22 cocrystallization of a certain amount of 70 heavy %ZSM5/30 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 (aluminum 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-treated makes catalyzer C.Wherein spray condition is 300 ℃ of temperature ins, 250 ℃ of exhaust temperatures, and spray pressure 0.2MPa, 500 ℃ of drying temperatures, the steam-treated condition is 700 ℃ of 100% water vapor 6 hours.Make catalyzer C, wherein 70 heavy %ZSM5/30 weigh %MCM22 cocrystallization molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 7%, 0.5% and 35%.
Embodiment 2
With the heavy %MCM22 cocrystallization of a certain amount of 50 heavy %ZSM5/50 molecular sieve, primary ammonium phosphate, rare earth REY molecular sieve (content of rare earth accounts for 10 heavy % of rare earth REY molecular sieve), aluminium colloidal sol (aluminum 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-treated makes catalyzer D.Wherein spray condition is 450 ℃ of temperature ins, 50 ℃ of exhaust temperatures, and spray pressure 1.0MPa, drying temperature was handled 4 hours for 600 ℃, and the steam-treated condition is 700 ℃ of 100% water vapor 20 hours.Make catalyzer D, wherein 50 heavy %ZSM5/50 weigh %MCM22 cocrystallization molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 0.5%, 2.5% and 40%.
Embodiment 3
With the heavy %MCM22 cocrystallization of a certain amount of 10 heavy %ZSM5/90 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 (aluminum 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-treated makes catalyzer E.Wherein spray condition is 250 ℃ of temperature ins, 350 ℃ of exhaust temperatures, and spray pressure 0.8MPa, 400 ℃ of drying temperatures, 3 hours time, the steam-treated condition is 800 ℃ of 100% water vapor 4 hours.Make catalyzer E, wherein 10 heavy %ZSM5/90 weigh %MCM22 cocrystallization molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 10%, 1.0% and 15%.
Embodiment 4
With the heavy %MCM22 cocrystallization of a certain amount of 90 heavy %ZSM5/10 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 (aluminum 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-treated makes catalyzer F.Wherein spray condition is 320 ℃ of temperature ins, 200 ℃ of exhaust temperatures, and spray pressure 0.5MPa, 550 ℃ of drying temperatures, 4 hours time, the steam-treated condition is 700 ℃ of 100% water vapor 5 hours.Make catalyzer F, wherein 90 heavy %ZSM5/10 weigh %MCM22 cocrystallization molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 5%, 0.1% and 25%.
Embodiment 5
With the heavy %MCM22 cocrystallization of a certain amount of 70 heavy %ZSM5/30 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 (aluminum 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-treated makes catalyzer G.Wherein spray condition is 300 ℃ of temperature ins, 250 ℃ of exhaust temperatures, and spray pressure 0.2MPa, 500 ℃ of drying temperatures, the steam-treated condition is 700 ℃ of 100% water vapor 6 hours.Make catalyzer G, wherein 70 heavy %ZSM5/30 weigh %MCM22 cocrystallization molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 7%, 1.0% and 20%.
Embodiment 6
With the heavy %MCM22 cocrystallization of a certain amount of 70 heavy %ZSM5/30 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 (aluminum 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-treated makes catalyzer H.Wherein spray condition is 300 ℃ of temperature ins, 250 ℃ of exhaust temperatures, and spray pressure 0.2MPa, 500 ℃ of drying temperatures, the steam-treated condition is 700 ℃ of 100% water vapor 6 hours.Make catalyzer H, wherein 70 heavy %ZSM5/30 weigh %MCM22 cocrystallization molecular sieve, and the weight content of P and rare-earth Y molecular sieve is respectively 7%, 1.0% and 27%.
Embodiment 7
With the heavy %MCM22 cocrystallization of a certain amount of 70 heavy %ZSM5/30 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 (aluminum 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-treated makes catalyst I.Wherein spray condition is 300 ℃ of temperature ins, 250 ℃ of exhaust temperatures, and spray pressure 0.2MPa, 500 ℃ of drying temperatures, 4 hours time, the steam-treated condition is 800 ℃ of 100% water vapor 4 hours.Make catalyst I, wherein 70 heavy %ZSM5/30 weigh %MCM22 cocrystallization molecular sieve, and 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 catalyzer is protected application aspect the octane value falling gasoline olefin.Dress 80g catalyzer in fixed fluidized bed reaction tubes is at N
2Be warmed up to 500 ℃ of activation under the atmosphere, then at N
2Atmosphere drops to temperature of reaction, 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 water cooler cooling carrying out gas-liquid separation.The online Shimadzu-SA stratographic analysis of gas.Product liquid is formed with Varian 3800 chromatographic system analysiss, adopts the PONA capillary column, hydrogen flame detector.Analytical results normalization method obtains dry gas, and liquefied gas and product liquid are formed.The chromatogram software that the octane value of gasoline adopts Beijing petroleum science 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 value of gasoline descend.The catalyzer (catalyzer C) of ZSM-5/MCM-22 cocrystallization molecular sieve preparation is compared with the catalyzer (catalyst B) of the mechanically mixing sample preparation of MCM-22 with ZSM-5, and the former has the higher aromaticity content and the octane value of gasoline.Catalyzer C provided by the invention, D, E, F, G, H and I have obvious reduction content of olefin in gasoline, improve the performance of gasoline octane rating.
The evaluation result of table 1 catalyzer
| Catalyzer | Raw material | A | B | C | D | E | F |
| RON | 88.8 | 86.2 | 92.7 | 94.2 | 94.2 | 92.1 | 92.5 |
| MON | 80.4 | 80.2 | 88.1 | 89.0 | 89.3 | 87.7 | 88.3 |
| 1. products distribution (wt%) | |||||||
| Dry gas | 0 | 0.44 | 0.26 | 0.72 | 0.78 | 0.48 | 0.64 |
| Liquefied gas | 1.75 | 15.11 | 15.63 | 17.65 | 17.89 | 15.85 | 17.81 |
| Liquid | 98.15 | 84.46 | 84.12 | 81.64 | 81.31 | 83.67 | 81.53 |
| 2. liquid is formed (wt%) | |||||||
| Normal paraffin | 5.35 | 6.88 | 6.44 | 6.80 | 6.83 | 7.20 | 7.52 |
| Isoparaffin | 28.20 | 56.41 | 55.27 | 52.86 | 54.04 | 54.16 | 55.39 |
| Naphthenic hydrocarbon | 6.80 | 6.43 | 5.34 | 4.57 | 4.44 | 4.70 | 4.33 |
| Alkene | 40.68 | 7.10 | 3.91 | 4.38 | 4.08 | 3.90 | 4.83 |
| Aromatic hydrocarbons | 18.86 | 23.17 | 29.05 | 31.41 | 30.58 | 30.04 | 27.91 |
Reaction conditions: 450 ℃, 2h
-1, 15 minutes.
The evaluation result of table 2 catalyzer
| Catalyzer | G | H | I | ||||||
| Temperature/℃ | 400 | 420 | 450 | 400 | 420 | 450 | 400 | 420 | 450 |
| RON | 91.1 | 92.5 | 94.5 | 90.0 | 91.2 | 93.4 | 89.6 | 90.9 | 93.4 |
| MON | 85.8 | 87.3 | 89.1 | 85.4 | 86.5 | 88.7 | 85.1 | 86.3 | 88.9 |
| 1. products distribution (wt%) | |||||||||
| Dry gas | 0.05 | 0.32 | 0.56 | 0.07 | 0.25 | 0.79 | 0.06 | 0.25 | 0.80 |
| Liquefied gas | 9.67 | 12.05 | 14.96 | 9.71 | 12.33 | 17.36 | 9.20 | 11.57 | 16.36 |
| Liquid | 90.30 | 87.59 | 84.48 | 90.20 | 87.42 | 81.84 | 90.74 | 88.19 | 82.81 |
| 2. liquid is formed (wt%) | |||||||||
| Normal paraffin | 6.10 | 6.27 | 6.66 | 6.22 | 6.37 | 6.83 | 6.24 | 6.36 | 6.84 |
| Isoparaffin | 53.00 | 53.69 | 52.30 | 55.31 | 54.70 | 54.71 | 56.12 | 55.63 | 54.67 |
| Naphthenic hydrocarbon | 6.58 | 6.08 | 5.18 | 6.45 | 5.94 | 4.60 | 6.47 | 5.84 | 4.60 |
| Alkene | 8.89 | 8.05 | 7.12 | 6.61 | 5.84 | 4.91 | 6.26 | 6.14 | 4.40 |
| Aromatic hydrocarbons | 25.44 | 25.87 | 28.75 | 25.39 | 27.15 | 28.93 | 24.92 | 26.03 | 29.45 |
Reaction conditions: 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 (6)
1. catalyzer that is used for gasoline upgrading, contain and account for whole catalyst weight per-cent: 0.5-10% rare earth-ZSM5/ZSM22 cocrystallization molecular sieve, the 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-weight rare earths content accounts for the 0.5-20% of rare-earth Y molecular sieve;
The aluminum oxide that contains 20-80% in the matrix components, the kaolin of 80-20%.
2. the catalyzer of claim 1 is characterized in that, Y molecular sieve comprises among USY, REY and the REHY one or more mixture.
3. the catalyzer of claim 1 is characterized in that, having ZSM5 crystal phase structure part in rare earth-ZSM5/ZSM22 cocrystallization molecular sieve is 0.05-20 with the weight ratio with ZSM22 crystal phase structure part.
4. method for preparing the described catalyzer of claim 1, rare earth-ZSM5/ZSM22 cocrystallization molecular sieve, phosphorus, rare-earth Y molecular sieve, aluminum oxide, kaolin and water are mixed, solid/water is by weight=0.3-0.5 in the mixing solutions, spray shaping, dry, steam-treated gets catalyzer;
Wherein: spray condition is temperature in 250-450 ℃, exhaust temperature 50-350 ℃, spray pressure 0.2-1.0MPa, drying temperature 400-600 ℃, time 2-4 hour, the steam-treated condition be 700-800 ℃ 100% water vapor 4-20 hour.
5. the method for claim 4 is characterized in that, aluminum oxide derives from aluminium colloidal sol.
6. the method for claim 4 is characterized in that, phosphorus is selected from one or more mixture aqueous solutions of phosphoric acid, phosphorous acid, phosphoric anhydride, ammonium hydrogen phosphate, primary ammonium phosphate, ammonium phosphite.
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|---|---|---|---|
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|---|---|---|---|
| CNB2004101018051A CN1331990C (en) | 2004-12-23 | 2004-12-23 | Catalyst for modifying gasoline and preparation thereof |
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| CN1331990C true CN1331990C (en) | 2007-08-15 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488724A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Aromatization modifying catalyst for catalytic gasoline and preocess |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1488724A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Aromatization modifying catalyst for catalytic gasoline and preocess |
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