CN1317547A - FCC catalyst for reducing olefin content in gasoline and its preparing process - Google Patents
FCC catalyst for reducing olefin content in gasoline and its preparing process Download PDFInfo
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Abstract
A FCC catalyst for decreasing the olefin content in gasoline is prepared from zeolite-type active component, amorphous silicon aluminium oxide and kaolin through mixing composite molecular sieve, oxide adhesive and kaolin, spraying, solidifying, washing and drying. Said active component contains ZSM-5, rare-earth Y-zeolite, phosphorus and compoiste rare-earth modified utlra-stable Y-zeolite. Its is high effect while not changing the octane value.
Description
The present invention relates to a kind of preparation method of catalytic cracking catalyst, exactly is a kind of FCC Preparation of catalysts method that can reduce content of olefin in gasoline.
State Bureau of Environmental Protection is since issue in 1997 banned use of doped fuel after 2000, further regulation has been made in oil composition to fuel vapor again, promptly after in July, 2000, require some areas to take the lead in adopting olefin(e) centent to be not more than 35% (v/v) fuel gasoline, because the fuel aftertreatment means deficiency of China, in addition catalytic gasoline account for more than 70% of gasoline product, so the alkene ability of falling of FCC catalyzer has been proposed new requirement.
From the market of the FCC catalyzer of the world, famous AKZO catalyst Co. and GRACE company have corresponding catalyst prod, but the relevant patent report of Shang Weiyou.The people such as the graduate Tan-no of COSMO of Japan had once issued two similar patents [USP5646082, USP5705142], the technology of its core is to have adopted a kind of super stable molecular sieve, preparation technology's more complicated of this molecular sieve, especially the thermal oscillation of molecular sieve is handled and is difficult to realize in industrial production, has limited this Application of Catalyst.
The purpose of this invention is to provide a kind of for industrial operation, technology is fairly simple, cost is lower, do not influence catalyzer other optionally have the FCC Catalysts and its preparation method of obvious reduction content of olefin in gasoline under the prerequisite.
It is as follows that the FCC catalyzer of the reduction content of olefin in gasoline of the present invention's preparation is formed (ratio of each component is the weight percent that accounts for the FCC catalyzer): phosphorus and the composite modified Y zeolite of rare earth (PREY) of the heavy %ZSM-5 zeolite of 0.5-5, the heavy % rare earth exchanged Y zeolite of 0.5-15, the heavy % of 20-40, the heavy % of total zeolite content 20-50, all the other 50-80 are heavy, and % is a matrix components, matrix contains components such as activated alumina, binding agent, kaolin, the heavy % of alumina content 10-30, the heavy % of binder content 10-20, the heavy % of kaolin content 20-40.Content of rare earth in the rare earth exchanged Y zeolite accounts for the heavy % of 12-20 of rare earth exchanged Y zeolite, relative crystallinity is greater than 50 heavy %, content of rare earth in the composite modified Y zeolite of phosphorus and rare earth accounts for the heavy % of 2-12 of PREY zeolite, unit cell parameters is 2.445-2.465nm, phosphorus content accounts for the heavy % (in P) of 0.2-3 of PREY zeolite, consider from the component of catalyzer, reduce the olefin(e) centent of gasoline and take following compounding technology:
(1) hydrogen transfer activity of increase catalyzer comprises and adopts the big modified Y zeolite of brilliant chest size to improve the acid density of molecular sieve, reduces the matrix activity of catalyzer.
(2) the selective splitting ability of the gasoline olefin of increase catalyzer.
(3) improve the activity stability of molecular sieve in the catalyzer.
(4) zeolite content of molecular sieve in the raising catalyzer.
Because molecular sieve is to the effect greater than matrix of the hydrogen transference ability of alkene and splitting action, so the quality of performance that reduces the catalyzer of content of olefin in gasoline directly depends on the performance of main active component.The PREY molecular sieve that this catalyzer adopted is a kind of special super stable molecular sieve, be different from simple hyperastable Y-type RE molecular sieve (USP4218307, CN87104086, CN86107531A, CN86107598A) and phosphorated super stable molecular sieve (JP62212219, EP0252761, USP4970183, but a kind of molecular sieve that had not only contained rare earth but also contained phosphorus compound combined modification USP5576258).
The composite modified Y zeolite of phosphorus and rare earth (PREY) is the NaY zeolite after rare earth and ammonium salt mix exchange and handle through hydrothermal calcine, with the phosphorus compound reaction, carries out calcination process preparation for the second time then.RE wherein
2O
3/ Y zeolite is 0.02～0.18, ammonium salt/Y zeolite is 0.1～1.0, the P/Y zeolite is 0.003～0.05,250～750 ℃ of maturing temperatures, water vapor condition 5～100%, 0.2～3.5 hour time, phosphorus compound is selected from ortho-phosphoric acid, phosphorous acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tetra-sodium.The PREY molecular sieve has following feature: phosphorus content 0.2-3% (in P), unit cell parameters 2.445-2.465nm, degree of crystallinity 60-80%, content of rare earth 2-12%.The purpose of introducing exchanged rare earth in the PREY molecular sieve is the unit cell dimension that increases molecular sieve, improves its hydrogen transfer activity, and the introducing of phosphorus is the intensity and the density of regulating its acid sites, reduces lytic activity and improves the ratio of hydrogen transfer reactions and cracking reaction.
The effect of ZSM-5 is cracking ability and the isomerization ability that increases gasoline olefin in the catalyzer, and compensation causes the loss of gasoline octane rating owing to the minimizing of gasoline olefin.ZSM-5 can be the ZSM-5 of ordinary silicon aluminum ratio, also can be high silica alumina ratio ZSM-5 or pure silicon ZSM-5, the performance of the ZSM-5 of high silica ZSM-5 and ordinary silicon aluminum ratio has certain difference, and the isomerization ability of high silica ZSM-5 is stronger, and the ZSM-5 of ordinary silicon aluminum ratio has stronger cracking ability.
The effect of rare earth exchanged Y zeolite is the hydrogen transference effect that adds powerful catalyst, and the content of rare earth of this rare earth exchanged Y zeolite is 12-20%, and relative crystallinity is greater than 50%.
Phosphorus and the composite modified Y zeolite of rare earth with the heavy %ZSM-5 zeolite of 0.5-5, the heavy % rare earth exchanged Y zeolite of 0.5-15, the heavy % of 20-40, the heavy % aluminum oxide of 10-30, the heavy % binding agent of 10-20, the heavy % kaolin of 20-40 mix the back spray shaping, through overcuring, washing, drying, make catalyzer of the present invention, wherein spray condition is 300～800 ℃ of temperature ins, 50～350 ℃ of exhaust temperatures, spray pressure 0.5～15Mpa: condition of cure is 200～750 ℃ of temperature, and the time is 0.05～4 hour; Wash conditions is: water/catalyst weight ratio is 1～35, and phosphorus (in P)/catalyzer is 0.001-0.1,20～100 ℃ of wash temperatures, 0.1～2 hour time.
The preparation of example 1 HY molecular sieve
Take by weighing 3.0kg NaY zeolite, join in the stainless steel reaction jar, add 1.5kg ammonium sulfate and 30kg deionized water, under agitation condition, switching architecture is adjusted to 3.0-3.5 with sulfuric acid or hydrochloric acid, be warming up to 95-100 ℃, exchange 0.5-1 hour, after filtration, washing makes once the Y zeolite of exchange.To exchange good molecular sieve then and carry out the super steady processing of hydro-thermal, 600 ℃ of treatment condition.Repeat above exchange and roasting process again and obtain two friendships, two roasting HY molecular sieves.
The preparation of example 2 phosphorous PHY molecular sieves
Take by weighing 3.0kg NaY zeolite, join in the stainless steel reaction jar, add 1.5kg ammonium sulfate, 0.4kg ammonium phosphate and 30kg deionized water, under agitation condition, switching architecture is adjusted to 3.0-3.5 with sulfuric acid or hydrochloric acid, be warming up to 95-100 ℃, exchange 0.5-1 hour, after filtration, washing makes once the Y zeolite of exchange.To exchange good molecular sieve then and carry out the super steady processing of hydro-thermal, 600 ℃ of treatment condition.Repeat above exchange and roasting process again and obtain two friendships, two roasting PHY molecular sieves.
Example 3 contains the preparation of rare earth REUSY-1 molecular sieve
Take by weighing 3.0kg NaY zeolite, join in the stainless steel reaction jar, add 1.5kg ammonium sulfate, rare earth (by rare earth oxide) 60g and 30kg deionized water, under agitation condition, switching architecture is adjusted to 3.5 with hydrochloric acid, be warming up to 95-100 ℃, exchange 0.5-1 hour, after filtration, washing makes once the Y zeolite of exchange.To exchange good molecular sieve then and carry out the super steady processing of hydro-thermal, 600 ℃ of treatment condition.Repeat above exchange and roasting process again and obtain two friendships, two roasting REUSY-1 molecular sieves.
Example 4 contains the preparation of rare earth REUSY-2 molecular sieve
Take by weighing 3.0kg NaY zeolite, join in the stainless steel reaction jar, add 1.5kg ammonium sulfate, rare earth (by rare earth oxide) 210g and 30kg deionized water, under agitation condition, switching architecture is adjusted to 3.5 with hydrochloric acid, be warming up to 95-100 ℃, exchange 0.5-1 hour, after filtration, washing makes once the Y zeolite of exchange.To exchange good molecular sieve then and carry out the super steady processing of hydro-thermal, 600 ℃ of treatment condition.Repeat above exchange and roasting process again and obtain two friendships, two roasting REUSY-2 molecular sieves.
The preparation of example 5 phosphoric acid rare earth PREY-1 molecular sieves
Take by weighing 3.0kg NaY zeolite, join in the stainless steel reaction jar, add 1.5kg ammonium sulfate, 0.4kg ammonium phosphate and 30kg deionized water, under agitation condition, switching architecture is adjusted to 3-3.5, is warming up to 95-100 ℃, exchange 0.5-1 hour with sulfuric acid or hydrochloric acid, the pH of system is transferred to 7.0, add the 120g rare earth oxide, stirred 5 minutes, after filtration, washing makes the phosphorous Y-shaped molecular sieve containing rare earth that once exchanges.To exchange good molecular sieve then and carry out the super steady processing of hydro-thermal, 600 ℃ of treatment condition.Repeat above exchange and roasting process again and obtain two friendships, two roasting PREY-1 molecular sieves.
The preparation of example 6 phosphoric acid rare earth PREY-2 molecular sieves
Take by weighing 3.0kg NaY zeolite, join in the stainless steel reaction jar, add 1.5kg ammonium sulfate, 280g rare earth oxide and 30kg deionized water, under agitation condition, switching architecture is adjusted to 3.0-3.5 with hydrochloric acid, be warming up to 95-100 ℃, exchange 0.5-1 hour, after filtration, washing makes once the Y-shaped molecular sieve containing rare earth of exchange.To exchange good molecular sieve then and carry out the super steady processing of hydro-thermal, 600 ℃ of treatment condition.The molecular sieve process exchange for the second time again that roasting is good, give-and-take conditions are: 1.5kg ammonium sulfate, 30kg deionized water, 400g ammonium phosphate, pH are 3.0-3.5, temperature 95-100 ℃, 0.5-1 hour swap time.Afterwards, pH is transferred to about 7, add the 120g rare earth oxide, after filtration, washing, dry back be in the hydrothermal calcine treating processes of carrying out 600 ℃, obtain two at last and hand over two roasting PREY-2 molecular sieves with ammoniacal liquor.
Example 7-14 different components Preparation of Catalyst
After mixing in 35%HY, PHY, REUSY-1, REUSY-2, PREY-1, PREY-2,15% aluminium colloidal sol, 50% kaolinic ratio and an amount of water, make catalyst A, B, C, D, E, F respectively through spraying, washing, drying.
After mixing by 7.5%REY, 2%ZSM-5,30%PREY-2,21% aluminum oxide, 12% aluminium colloidal sol, 27.5% kaolin and appropriate amount of deionized water, make catalyzer G through spraying, curing, washing, drying.After mixing by 5.0%REY, 1.5%ZSM-5,34%PREY-2,21% aluminum oxide, 11% aluminium colloidal sol, 27.5% kaolin and appropriate amount of deionized water, make catalyzer H through spraying, curing, washing, drying.
The analysis of catalyst A, B, C, D, E, F, G, H and the evaluation result of recirculation reactor are listed in table 1 and the table 2 respectively.
The analytical results of table 1 catalyzer
| Catalyzer | A | ?B | ?C | ?D | ?E | ?F | ?G | ?H |
| Sodium oxide, m% | ??0.2 | ?0.22 | ?0.31 | ?0.19 | ?0.30 | ?0.29 | ?0.27 | ?0.25 |
| Rare earth oxide, m% | ????0 | ????0 | ?0.4 | ?1.7 | ?1.1 | ?2.8 | ?3.5 | ?2.7 |
| Phosphorus content, m% | ????/ | ??1.2 | ?0.7 | ?0.8 | ?1.2 | ?1.2 | ?1.3 | ?1.4 |
| Specific surface, m 2/g | ?280 | ?260 | ?277 | ?250 | ?280 | ?275 | ?300 | ?295 |
| Active (800 ℃/4h), m% | ?69 | ?72 | ?74 | ?78 | ?73 | ?77 | ?80 | ?82 |
The evaluation result of table 2 catalyzer
| Catalyzer | A | ?B | ?C | ?D | ?E | ?F | ?G | ?G | ?H |
| Temperature of reaction, ℃ | 500 | ?500 | ?500 | ?500 | ?500 | ?500 | ?500 | ?490 | ?500 |
| Agent-oil ratio | 6.5 | ?6.5 | ?6.5 | ?6.6 | ?6.5 | ?6.7 | ?6.5 | ?8.8 | ?6.6 |
| Dry gas, m% | 2.0 | ?1.8 | ?2.1 | ?2.3 | ?2.0 | ?2.3 | ?2.3 | ?2.2 | ?2.0 |
| Liquefied gas, m% | 14.5 | ?15.0 | ?15.8 | ?16.2 | ?15.2 | ?16.2 | ?18.0 | ?20.0 | ?17.5 |
| Gasoline, m% | 46.5 | ?47.2 | ?48.0 | ?48.2 | ?46.9 | ?48.1 | ?47.9 | ?48.3 | ?48.5 |
| Diesel oil, m% | 21.0 | ?20.3 | ?19.4 | ?18.8 | ?20.4 | ?17.9 | ?19.6 | ?18.0 | ?19.5 |
| Heavy oil, m% | 11.0 | ?10.7 | ?9.2 | ?9.5 | ?9.8 | ?9.5 | ?8.0 | ?7.2 | ?7.8 |
| Coke, m% | 5.0 | ?5.0 | ?5.5 | ?5?8 | ?5.0 | ?6.0 | ?6.2 | ?6.3 | ?6.4 |
| Transformation efficiency, m% | 68.3 | ?69.0 | ?71.4 | ?72.5 | ?69.1 | ?72.6 | ?74.4 | ?76.8 | ?74.4 |
| Gasoline RON | ?89.1 | ?90.3 | ?90.0 | ?89.9 | ?91.0 | ?89.0 | ?90.5 | ?90.9 | ?90.4 |
| Gasoline olefin, v% | 50.2 | ?49.8 | ?48.3 | ?45.3 | ?46.6 | ?43.2 | ?40.8 | ?33.5 | ?39.9 |
By the data of table 2 as can be seen, adopt the PREY molecular sieve catalyst G of composite molecular screen technology, phosphorus and the preparation of rare earth composite modification technology and the high performance of olefin(e) centent that H has transformation efficiency height, gasoline, the agent-oil ratio of association reaction and the variation of temperature of reaction, the olefin(e) centent of gasoline can be reduced to below 35% (v/v).
Claims (4)
1, a kind of FCC catalyzer that can reduce content of olefin in gasoline, it is characterized in that it is the heavy %ZSM-5 zeolite of 0.5-5 that catalyzer contains three kinds of zeolite component, 0.5-15 heavy % rare earth exchanged Y zeolite, phosphorus and the composite modified Y zeolite of rare earth (PREY) of the heavy % of 20-40, all the other 50-80 are heavy, and % is a matrix components, matrix components contains the heavy % aluminum oxide of 10-30, the heavy % binding agent of 10-20, the heavy % kaolin of 20-40, content of rare earth in the rare earth exchanged Y zeolite accounts for the heavy % of 12-20 of rare earth exchanged Y zeolite, relative crystallinity is greater than 50 heavy %, content of rare earth in the composite modified Y zeolite of phosphorus and rare earth accounts for the heavy % of 2-12 of PREY zeolite, unit cell parameters is 2.445-2.465nm, and phosphorus content accounts for the heavy % (in P) of 0.2-3 of PREY zeolite.
2, catalyzer according to claim 1, it is characterized in that the composite modified Y zeolite of described phosphorus and rare earth be by the NaY zeolite after rare earth and ammonium salt mix exchange and handle through hydrothermal calcine, with phosphorus compound reaction, carry out calcination process preparation for the second time then, wherein RE
2O
3The weight ratio of/Y zeolite is 0.02～0.18, and the weight ratio of ammonium salt/Y zeolite is 0.1～1.0, and the weight ratio of P/Y zeolite is 0.003～0.05,250～750 ℃ of maturing temperatures, water vapor condition 5～100%, 0.2～3.5 hour time.
3, catalyzer according to claim 1 is characterized in that ZSM-5 can be the ZSM-5 of ordinary silicon aluminum ratio, also can be high silica alumina ratio ZSM-5 or pure silicon ZSM-5.
4, a kind of FCC Preparation of catalysts method that can reduce content of olefin in gasoline, it is characterized in that preparation process comprises: (1) preparation phosphorus and the composite modified Y zeolite of rare earth: with the NaY zeolite after rare earth and ammonium salt mix exchange and handle through hydrothermal calcine, react with phosphorus compound, carry out the calcination process second time, wherein RE then
2O
3The weight ratio of/Y zeolite is 0.02～0.18, and the weight ratio of ammonium salt/Y zeolite is 0.1～1.0, and the weight ratio of P/Y zeolite is 0.003～0.05,250～750 ℃ of maturing temperatures, water vapor condition 5～100%, 0.2～3.5 hour time; (2) with the heavy %ZSM-5 zeolite of 0.5-5,0.5-15 heavy % rare earth exchanged Y zeolite, phosphorus and the composite modified Y zeolite of rare earth of the heavy % of 20-40, the heavy % aluminum oxide of 10-30, the heavy % binding agent of 10-20, the heavy % kaolin of 20-40 mixes the back spray shaping, through overcuring, washing, dry, make catalyzer of the present invention, spray condition is 300～800 ℃ of temperature ins, 50～350 ℃ of exhaust temperatures, spray pressure 0.5～15Mpa, condition of cure is 200～750 ℃ of temperature, time is 0.05～4 hour, and wash conditions is: water/catalyst weight ratio is 1～35, and phosphorus (in P)/catalyzer is 0.001-0.1,20～100 ℃ of wash temperatures, 0.1～2 hour time.
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