CN100529025C - Catalytic convertion method of liquified petroleum gas and gasoline feeding at same time - Google Patents
Catalytic convertion method of liquified petroleum gas and gasoline feeding at same time Download PDFInfo
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- CN100529025C CN100529025C CNB2005100061928A CN200510006192A CN100529025C CN 100529025 C CN100529025 C CN 100529025C CN B2005100061928 A CNB2005100061928 A CN B2005100061928A CN 200510006192 A CN200510006192 A CN 200510006192A CN 100529025 C CN100529025 C CN 100529025C
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- molecular sieve
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Abstract
This invention relates to a method for catalyzing and transforming method for feeding liquefied gas and gasoline, in which, the raw material oil and liquefied gas enter from the lower part of the riser/fluidized bed to contact with the catalyst and the reacted oil gas enters into a cold water condenser for gas and liquid separation in the following reaction conditions: temperature: 300-500deg.C, weight space velocity: 0.2-4h<SUP>-1</SUP>, the weight ratio of the liquefied gas and the raw material oil: 80:20-3:97, which reduces content of olefin and increases aromatics greatly.
Description
Technical field
The present invention relates to a kind of catalysis conversion method of petroleum hydrocarbon, particularly relate to the catalysis conversion method of a kind of liquefied gas and gasoline feeding at same time.
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.
On the other hand, " enforcement of West-east Gas plan and civil natural gas pipework; made original just superfluous liquefied gas; further overstock; be badly in need of finding new outlets; especially wherein contained C 4 olefin consumption more than 50% is littler, and the existence of high-content alkene in refinery's liquefied gas have influence on the production (the QJ/DSH712-1999 standard-required olefin(e) centent of motor liquified gas LPG is less than 5%) of motor liquified gas LPG in China.
Disclosed a kind of catalyst cracking method that reduces content of olefin in gasoline among the CN00134119.7, it is characterized in that the light gasoline fraction extracted out with the condensed oil of rich gas compressor and/or by stabilizer tower top upstream injecting lift pipe reactor by the stock oil feed nozzle, perhaps with stock oil by stock oil feed nozzle injecting lift pipe reactor, make it to contact with regenerated catalyst and react, temperature of reaction is 600-700 ℃.
CN99109193.0 has disclosed a kind of catalysis conversion method that reduces olefin(e) centent in liquefied gas and the gasoline, it is characterized in that the bottom that stock oil after the preheating enters the compound reactor that constitutes by riser tube or by the riser tube fluidized-bed contacts with catalyzer, the oil gas that the reaction back generates catalyzer up and after the cooling contacts proceeds reaction, temperature of reaction is 460-620 ℃, the weight ratio 0.03-0.3 of water vapor and stock oil: 1.Described activity of such catalysts component is selected from Y or the HY type zeolite that contains or do not contain rare earth, contains or do not contain the ultrastable Y of rare earth, ZSM-5 series zeolite or have the supersiliceous zeolite of five-membered ring structure, a kind of in the BETA zeolite, two or three.
Summary of the invention
The purpose of this invention is to provide a kind of industrial operation that supplies, technology is fairly simple, the catalysis conversion method of liquefied gas and gasoline feeding at same time.
Method provided by the invention both can be implemented in riser reactor, also can implement on fluidized-bed.
Method particular content provided by the invention is:
The stock oil of preheating and liquefied gas enter from the bottom of riser tube/fluidized-bed, contact with catalyzer, and reacted oil gas enters water ice condenser and carries out gas-liquid separation.
Reaction conditions is: temperature of reaction: 300-500 ℃, weight space velocity is 0.2-4h
-1, the weight ratio 80 of liquefied gas and stock oil: 20-3: 97.
The used stock oil of the present invention specifically is selected from catalytically cracked gasoline, catalytic cracking gasoline, pyrolysis gasoline, the mixture of one or more in the coker gasoline.
The used liquefied gas of the present invention specifically can derive from the liquefied gas behind catalytic cracking/catalytic pyrolysis, and the liquefied gas after pure gasoline catalyzing transforms also can be selected from liquefied gas and the gasoline feeding at same time liquefied gas after mixing one or more mixture.
The catalyzer that the present invention is suitable for is: one or more in the catalyzer of ZSM5 molecular sieve, MCM22 molecular sieve, ZSM35 molecular sieve, ZSM11 molecular sieve, ZSM35/MCM22 cocrystallization molecular sieve, ZSM5/ZSM11 cocrystallization molecular sieve, rare-earth Y molecular sieve.
The preferable catalyzer of the present invention is one or more in the catalyzer of ZSM35/MCM22 cocrystallization molecular sieve, ZSM5/ZSM11 cocrystallization molecular sieve, rare-earth Y molecular sieve and ZSM35/MCM22 cocrystallization molecular sieve, rare-earth Y molecular sieve and ZSM5/ZSM11 cocrystallization molecular sieve.
The catalyzer that the present invention is suitable for is one or both in the catalyzer of the catalyzer, rare-earth Y molecular sieve and ZSM5/ZSM11 cocrystallization molecular sieve and the phosphorus that contain rare-earth Y molecular sieve and ZSM35/MCM22 cocrystallization molecular sieve and phosphorus, and wherein P accounts for the heavy % of 0.05-3 of catalyzer.
The invention has the advantages that:
1. the mixing temperature of reaction of gasoline and liquefied gas is lower, and 300-500 ℃, reacted liquid yield height.
2. but the equal catalyzed conversion of liquefied gas and gasoline, gasoline is compared height with the mixing reacted liquid yield of liquefied gas with the catalyzed conversion of pure raw material, under certain conditions, can guarantee that the liquid yield that reacts after product maintains an equal level even increase with the liquid in the charge raw material.
3. when obviously reducing the feed gasoline olefin(e) centent, the gasoline products aromatic hydrocarbons behind liquefied gas and the gasoline feeding at same time catalyzed conversion is increased substantially.
Embodiment
Below in conjunction with preferable comparative example and embodiment the present invention is further elaborated.
Embodiment 1
Catalyst A adopts the heavy %MCM22 cocrystallization of 50 heavy %ZSM35/50 molecular sieve.This catalyzer of dress 80g 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 condition as shown in table 1, and raw material is liquefied gas and a catalytic cracking petroleum naphtha after the catalytic cracking, 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-8A 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.
By the result of table 1 as seen, the mixing result of petroleum naphtha and liquefied gas charging simultaneously with calculate in theory similar, explanation can mixing mutually inhibition mutually, under this temperature, the amount that dry gas produces seldom can obviously reduce the olefin(e) centent in the petroleum naphtha, and the aromatic hydrocarbons in the product increases considerably.
The mixing reaction result of petroleum naphtha and liquefied gas charging simultaneously on table 1 catalyst A
Reaction conditions: 330 ℃ of temperature; Weight space velocity 0.30h
-1Reaction times: 15 minutes; * be calculated value
Embodiment 2
Catalyst B adopted the heavy %ZSM11 mixed crystal of 80 heavy %ZSM5/20 molecular sieves, through 550 ℃ of steam-treated 2 hours.Under the pre-treatment and product analysis condition identical with embodiment 1, carry out reaction as shown in table 2, raw material is liquefied gas and a catalytic cracking full distillate gasoline after the catalytic cracking, concrete become to be grouped into see Table 2.
By the result of table 2 as seen, the mixing result of full distillation gasoline and liquefied gas charging simultaneously with calculate in theory similar, under this temperature, the amount that dry gas produces seldom, can obviously reduce the olefin(e) centent in the petroleum naphtha, the a little higher than charge raw material liquid yield of liquid yield in the product, the aromatic hydrocarbons in the product increases considerably.
Full distillation gasoline and the mixing reaction result of liquefied gas charging simultaneously on table 2 catalyst B
Reaction conditions: weight space velocity 3.5h
-115 minutes reaction times; 390 ℃ of temperature; * be calculated value
Embodiment 3
Catalyst A and B see embodiment 1 and 2, then catalyst A and B are got catalyzer C in 50 heavy %/50 heavy % ratio mechanically mixing.Under the pre-treatment and product analysis condition identical with embodiment 1, carry out reaction as shown in table 3, raw material is liquefied gas and a catalytic cracking full distillate gasoline after the catalytic cracking, concrete become to be grouped into see Table 3.
By the result of table 3 as seen, it is mixing to carry out the charging simultaneously of full distillation gasoline and liquefied gas in 370-450 ℃ scope, and the amount that dry gas produces seldom can obviously reduce olefin content in gasoline, liquid yield is higher than the charge raw material liquid yield in the product, and the aromatic hydrocarbons in the product increases considerably.
Table 3 catalyzer C goes up full distillation gasoline and the mixing reaction result of liquefied gas charging simultaneously
Reaction conditions: weight space velocity 2h
-1390 ℃ of temperature; 15 minutes reaction times; Feeding manner 85 oil/15 gas (weight by weight)
Embodiment 4
Catalyzer D, the heavy %ZSM11 cocrystallization of the heavy %ZSM5/10 of its middle-weight rare earths-90 molecular sieve, the weight content of P and rare-earth Y molecular sieve is respectively 5%, 0.1% and 25%.Under the pre-treatment and product analysis condition identical with embodiment 1, carry out reaction as shown in table 4, raw material is liquefied gas and catalytic cracking full distillate gasoline, concrete become to be grouped into see Table 4.
By the result of table 4 as seen, under full distillation gasoline of difference and the mixing situation of liquefied gas ratio charging simultaneously, the amount that dry gas produces seldom can obviously reduce olefin content in gasoline, liquid yield is higher than the charge raw material liquid yield in the product, and the aromatic hydrocarbons in the product increases considerably.
Table 4 catalyzer D goes up full distillation gasoline and the mixing reaction result of liquefied gas charging simultaneously
Reaction conditions: weight space velocity 2h
-1420 ℃ of temperature; 15 minutes reaction times
Embodiment 5
Catalyzer E, 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%.Under the pre-treatment and product analysis condition identical with embodiment 1, carry out as table 5 and the reaction shown in the table 6, gas raw material is the liquefied gas of pure gasoline upgrading after product in the table 5, and gas raw material is gasoline/liquefied gas (liquefied gas of the mixing upgrading after product of 85/15 (weight by weight) in the table 6.
By the result of table 5 and table 6 as seen, the amount that dry gas produces seldom can obviously reduce olefin content in gasoline, and the aromatic hydrocarbons in the product increases considerably.
Table 5 catalyzer E goes up full distillation gasoline and the mixing reaction result of liquefied gas charging simultaneously
Reaction conditions: weight space velocity: 2h
-1420 ℃; Reaction times: 15 minutes
Table 6 catalyzer E goes up full distillation gasoline and the mixing reaction result of liquefied gas charging simultaneously
Reaction conditions: weight space velocity: 2h
-1420 ℃; Reaction times: 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. the catalysis conversion method of liquefied gas and gasoline feeding at same time, stock oil and liquefied gas enter from the bottom of riser tube/fluidized-bed, contact with catalyzer, and reacted oil gas enters water ice condenser and carries out gas-liquid separation; Temperature of reaction 300-500 ℃, weight space velocity is 0.2-4h
-1, the weight ratio 80 of liquefied gas and stock oil: 20-3: 97;
Described catalyzer is one or more in ZSM5 molecular sieve, MCM22 molecular sieve, ZSM35 molecular sieve, ZSM11 molecular sieve, ZSM35/MCM22 cocrystallization molecular sieve, ZSM5/ZSM11 cocrystallization molecular sieve, the rare-earth Y molecular sieve.
2. the method for claim 1 is characterized in that, stock oil is selected from one or more the mixture in catalytically cracked gasoline, catalytic cracking gasoline, pyrolysis gasoline, the coker gasoline.
3. the method for claim 1 is characterized in that, liquefied gas derives from one or more the mixture in liquefied gas, liquefied gas, liquefied gas and gasoline feeding at same time behind the pure gasoline upgrading behind the catalytic cracking/catalytic pyrolysis liquefied gas after mixing.
4. the method for claim 1, it is characterized in that used catalyzer is one or more in ZSM35/MCM22 cocrystallization molecular sieve, ZSM5/ZSM11 cocrystallization molecular sieve, rare-earth Y molecular sieve and ZSM35/MCM22 cocrystallization molecular sieve, rare-earth Y molecular sieve and the ZSM5/ZSM11 cocrystallization molecular sieve.
5. claim 1 or 4 method, it is characterized in that, used catalyzer is to contain in rare-earth Y molecular sieve and ZSM35/MCM22 cocrystallization molecular sieve and phosphorus catalyst, rare-earth Y molecular sieve and ZSM5/ZSM11 cocrystallization molecular sieve and the phosphorus catalyst one or both, and wherein phosphorus accounts for the heavy % of 0.05-3 of catalyzer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2005100061928A CN100529025C (en) | 2005-01-31 | 2005-01-31 | Catalytic convertion method of liquified petroleum gas and gasoline feeding at same time |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100061928A CN100529025C (en) | 2005-01-31 | 2005-01-31 | Catalytic convertion method of liquified petroleum gas and gasoline feeding at same time |
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| CN1814713A CN1814713A (en) | 2006-08-09 |
| CN100529025C true CN100529025C (en) | 2009-08-19 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102226102A (en) * | 2011-05-10 | 2011-10-26 | 山东金诚石化集团有限公司 | Method for producing gasoline blended component with high octane number from refinery gas and light hydrocarbons |
| CN103289739A (en) * | 2012-02-29 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for modification by coupling hydrodesulfurization of FCC (Fluid Catalytic Cracking) gasoline and aromatization of liquefied petroleum gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6395949B1 (en) * | 1998-08-03 | 2002-05-28 | Phillips Petroleum Company | Acid treated zeolite containing phosphorus used as a catalyst in processes for converting hydrocarbons, and use of binary hydrocarbon mixtures as diluents in processes for converting hydrocarbons |
| CN1356372A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Catalytic cracking process for reducing content of olefin in gasoline |
| JP2004105963A (en) * | 1995-05-25 | 2004-04-08 | Nippon Oil Corp | Catalyst for converting aromatic hydrocarbon compound and conversion method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004105963A (en) * | 1995-05-25 | 2004-04-08 | Nippon Oil Corp | Catalyst for converting aromatic hydrocarbon compound and conversion method |
| US6395949B1 (en) * | 1998-08-03 | 2002-05-28 | Phillips Petroleum Company | Acid treated zeolite containing phosphorus used as a catalyst in processes for converting hydrocarbons, and use of binary hydrocarbon mixtures as diluents in processes for converting hydrocarbons |
| CN1356372A (en) * | 2000-12-05 | 2002-07-03 | 中国石油化工股份有限公司 | Catalytic cracking process for reducing content of olefin in gasoline |
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