CN103540340A - Gasoline refining method - Google Patents
Gasoline refining method Download PDFInfo
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- CN103540340A CN103540340A CN201210239982.0A CN201210239982A CN103540340A CN 103540340 A CN103540340 A CN 103540340A CN 201210239982 A CN201210239982 A CN 201210239982A CN 103540340 A CN103540340 A CN 103540340A
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- gasoline
- refining process
- process according
- benzene
- crystalline aluminosilicate
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Abstract
The invention relates to a gasoline refining method, mainly for solving the problem in the prior art that the existing inferior gasoline has high content of olefin and insufficient arene. According to the gasoline refining method, gasoline containing 2-12 carbonic olefins and benzene are taken as the raw materials. Under the condition that the reaction temperature is 100-160 DEG C, the reaction pressure is 1.0-2.8MPa, the molecular ratio of benzene and olefin is 5-15, and the gasoline weight space velocity is 0.1-1.0h<-1>, the raw materials and a catalyst come into contact to convert olefin in the gasoline into arene to obtain refined gasoline, wherein the catalyst used in the method comprises the following components by weight percentage: 30-80% of crystalline aluminosilicate material and 20-70% of inorganic oxide, and the crystalline aluminosilicate material has specific XRD (X-ray diffraction) data. The technical scheme well solves the problem in the prior art, and the gasoline refining method can be used in refining production for improving the gasoline octane value.
Description
Technical field
The present invention relates to a kind of gasoline refining process.
Background technology
The trend that the gasoline consumption of China presents high grade, cleans needs to control the olefin(e) centent in gasoline in the production of gasoline cleaning, and this will cause the loss of gasoline octane rating.The octane value of gasoline is determined by its chemical constitution, under the suitable condition of molecular size, hydro carbons octane value sorts from high to low and is: aromatic hydrocarbons > isomeric olefine, isoparaffin > normal olefine > naphthenic hydrocarbon > straight-chain paraffin.Alkene in a lot of inferior patrols, Determination of Alkane Content are many, and aromaticity content is not enough.The high gasoline combustion value that causes of olefin(e) centent is low.If can change part alkene into aromatic hydrocarbons, not only can improve the fuel value of gasoline but also can improve its octane value.Along with the demand of domestic daily chemical products is growing, the industrial scale of its raw material long-chain alkyl benzene is expanding day also, tends to be attended by the generation of part by product-inferior patrol in the production of long-chain alkyl benzene.Because its aromaticity content is extremely low, cause gasoline quality poor, can only sell as solvent oil or fuel, price is extremely low.If can be the oil quality that aromatic hydrocarbons will improve this portioned product greatly by most of conversion of olefines wherein, its sale price be by the increase that has nearly 300%.
Thereby document CN101962570A provides a kind of carries out to fraction oil of petroleum inferior the method that hydrogenation drastic cracking obtains the high-quality oil product that is rich in mononuclear aromatics.Its processing condition are high-temperature and high-pressure hydrogenation cracking, are mainly suitable for the processing of being rich in dicyclo, encircling petroleum fractions more.CN101935266A provides a kind of method that difficult cracking heavy oil feed is catalytically conveted to stop bracket gasoline and produces propylene.Aforesaid method does not all relate to the method that how poor quality oil that is rich in alkene is converted into the high-quality gasoline that is rich in aromatic hydrocarbons.
Summary of the invention
Technical problem to be solved by this invention is the problem that in prior art inferior patrol, olefin(e) centent is high, aromaticity content is not enough, and a kind of new gasoline refining process is provided.The method can will become aromatic hydrocarbons after the most of olefin alkylation in inferior patrol, thereby greatly improves the oil quality of these inferior patrols, has the advantages that temperature of reaction is low, changing effect good, gasoline octane rating is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of gasoline refining process, gasoline and the benzene of take containing 2～12 carbon olefins are raw material, in temperature of reaction, it is 100～160 ℃, reaction pressure is 1.0～2.8MPa, benzene alkene molecular ratio is 5～15, and gasoline weight space velocity is 0.1～1.0 hour
-1under condition, raw material contacts with catalyzer, by the conversion of olefines in gasoline, is aromatic hydrocarbons, obtains treated gasoline; Wherein, catalyzer used comprises following component by weight percentage: a) 30 ~ 80% crystalline aluminosilicate material; B) 20 ~ 70% inorganic oxide; Described crystalline aluminosilicate material has following XRD diffraction data:
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100） |
| 6.5 0 | 28.8±0.1 |
| 7.2 0 | 17.3±0.1 |
| 8.8 0 | 15.4±0.1 |
| 9.7 0 | 53.8±0.1 |
| 13.5 0 | 39.4±0.1 |
| 14 0 | 28.8±0.1 |
| 14.3 0 | 19.2±0.1 |
| 15.4 0 | 23.1±0.1 |
| 19.5 0 | 34.6±0.1 |
| 22.2 0 | 69.2±0.1 |
| 23.8 0 | 23.1±0.1 |
| 25.5 0 | 100±0.1 |
| 26.2 0 | 65.4±0.1 |
| 27.5 0 | 46.7±0.1 |
| 31 0 | 27.9±0.1 |
| 35.8 0 | 15.4±0.1 |
In technique scheme, described crystalline aluminosilicate material specific surface area preferable range is 500 ~ 600 meters
2/ gram, pore volume preferable range is 0.45 ~ 0.60 ml/g.Described inorganic oxide preferred version is at least one being selected from aluminum oxide, titanium oxide, zinc oxide or zirconium white, and more preferably scheme is at least one being selected from aluminum oxide or zinc oxide.By weight percentage, the consumption preferable range 50 ~ 70% of crystalline aluminosilicate material, the consumption preferable range of inorganic oxide is 30 ~ 50%.Temperature of reaction preferable range is 120～160 ℃, and reaction pressure preferable range is 1.3～2.5MPa, and benzene alkene molecular ratio preferable range is 6～12, and gasoline weight space velocity preferable range is 0.10～0.85 hour
-1.It is characterized in that described containing in the gasoline of 2～12 carbon olefins, by weight percentage, the olefin(e) centent that contains 2 ~ 12 carbon is 0.1～40%, and the Determination of Alkane Content that contains 2 ~ 12 carbon is 40～80%, and aromaticity content is 0 ~ 20%.
In the inventive method, the preparation method of catalyzer used is as follows:
1) prepare crystalline aluminosilicate material.
After silicon source (silicon sol, water glass etc.), aluminium source (sodium aluminate, Tai-Ace S 150 etc.) are mixed with organic ammonium (hexanediamine, hexa-methylene imonium), caustic soda, water, under the effect of directed agents organic ammonium at 140～180 ℃ crystallization 50～200 hours, filter, washing, dry and obtain finished product crystalline aluminosilicate material.Wherein material molar ratio is as follows: (molecular ratio, M refers to organic ammonium)
SiO
2∶Al
2O
3＝20～200
SiO
2∶Na
2O＝100～200
SiO
2∶H
2O＝0.01～0.1
SiO
2∶M＝2～8
The charging capacity of directed agents is 0.1%～10% of silicon source weight.
2) above-mentioned crystalline aluminosilicate material is exchanged with ammonium salt, make the content of alkalimetal ion wherein below 0.05% (weight), then dry.Wherein ammonium salt used can be conventional ammonium salt, such as ammonium chloride, ammonium nitrate or ammonium phosphate etc.
3) the qualified crystalline aluminosilicate material of exchange is mixed with inorganic oxide, add shaping assistant, kneading, extrusion, oven dry roasting, then pelletizing obtains finished catalyst.
Adopt the inventive method, the inferior patrol that is rich in alkene can be converted into the high-quality gasoline that is rich in aromatic hydrocarbons, after processing, the octane value of gasoline can improve 6%, has obtained good technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
[embodiment 1]
1500g water glass (modulus=2.8) and 500g hexamethylene imine are mixed evenly, 50g sodium aluminate and 25g sodium hydroxide are mixed evenly in 500g water.Above-mentioned two kinds of solution are mixed evenly under violent stirring, continue stir 2 hours, add 500g water to stir 1 hour, the above-mentioned solution having mixed is formed to jelly at 10 ℃ after aging 100 hours, standby.
25g sodium aluminate and 20g sodium hydroxide are dissolved and are mixed evenly in 500g water, adding 500g(40%wt) silicon sol stirs, adding 800g pure water to stir is mixed evenly again, the colloidal sol 50g that adds above-mentioned preparation, continue to stir after 2 hours and proceed in crystallizing kettle, at 165 ℃, stir crystallization 100 hours, filtration washing is to pH=7～9,150 ℃ of oven dry.The specific surface area of gained sample is 550m
2/ g, pore volume is 0.5ml/g, XRD diffraction data is as shown in table 1.
Get above-mentioned synthetic aluminosilicate material 100g, add 0.5M ammonium nitrate solution, be warming up to 95 ℃ of exchanges 2 hours, repeatedly exchange 6 times, make the alkali metal ion content measured in pure aluminium silicate be less than 100ppm.Pure aluminium silicate 90g and 25g aluminum oxide, 10g zinc oxide that above-mentioned exchange is good are mixed evenly, add 170ml5% salpeter solution, 5g pseudo-ginseng powder to mediate extruded moulding after 1 hour, the catalyzer of forming, 150 ℃ of oven dry, is then warming up to 580 ℃ of roastings and within 4 hours, obtains finished catalyst under air atmosphere.
Table 1
| 2 θ diffraction angle | Diffraction peak intensity (I/I 0×100） |
| 6.5 0 | 28.8 |
| 7.2 0 | 17.2 |
| 8.8 0 | 15.5 |
| 9.7 0 | 53.9 |
| 13.5 0 | 39.5 |
| 14 0 | 28.8 |
| 14.3 0 | 19.1 |
| 15.4 0 | 23.2 |
| 19.5 0 | 34.6 |
| 22.2 0 | 69.2 |
| 23.8 0 | 23.1 |
| 25.5 0 | 100 |
| 26.2 0 | 65.3 |
| 27.5 0 | 46.7 |
| 31 0 | 27.8 |
| 35.8 0 | 15.4 |
[embodiment 2]
The catalyst powder of preparation in [embodiment 1] is broken into 20～60 object particles, gets 5.0g catalyzer and in fixed-bed reactor, carry out the liquid phase alkylation reaction of gasoline and benzene, wherein gasoline used has the composition of table 2.Reaction conditions is, gasoline air speed=0.1hr
-1, temperature of reaction=150 ℃, reaction pressure=2.5MPa, reaction product is the mixture of gasoline and benzene, the olefin conversion > 95% in gasoline.React and within one month, do not observe catalyst activity loss, will after above-mentioned product separation benzene, measure gasoline octane rating (RON) than 6 units of the front raising of reaction.
Table 2
| Component | wt% |
| Propane | 0.581 |
| Normal butane | 2.573 |
| Skellysolve A | 5.971 |
| Methyl cyclobutane | 2.623 |
| 1-hexene | 0.735 |
| Hexane | 10.294 |
| 2-hexene | 1.534 |
| Methylcyclopentane | 0.344 |
| Benzene | 3.147 |
| Hexanaphthene | 0.45 |
| Tetrahydrobenzene | 0.302 |
| 1-nhepene | 2.171 |
| 3-nhepene | 3.161 |
| Normal heptane | 9.323 |
| 2-nhepene | 4.509 |
| 3-nhepene | 2.73 |
| Methylcyclohexane | 0.33 |
| Ethyl cyclopentenes | 0.52 |
| Toluene | 3.288 |
| 2-methylheptane | 0.33 |
| 1-octene | 1.95 |
| The positive octene of 4-(instead) | 1.107 |
| The positive octene of 3-(E) | 2.082 |
| Octane | 9.28 |
| 2-octene (E) | 3.092 |
| 2-octene (E) | 1.588 |
| Ethylbenzene | 5.213 |
| M-toluene | 0.679 |
| O-toluene | 0.836 |
| 1-nonene | 0.496 |
| 4-nonene | 0.441 |
| 3-nonene (E) | 0.585 |
| Positive nonane | 5.638 |
| Cis-2-nonene | 0.633 |
| Isopropyl benzene | 0.404 |
| N-proplbenzene | 1.787 |
| Trans-4-certain herbaceous plants with big flowers alkene | 0.636 |
| Certain herbaceous plants with big flowers alkane n-C 10H 22 | 7.933 |
| n-C 11H 24 | 0.7 |
[embodiment 3]
With [embodiment 1], just reaction conditions is, gasoline air speed=0.1hr
-1, temperature of reaction=120 ℃, reaction pressure=2.0Mpa, reaction product is the mixture of gasoline and benzene, olefin conversion > 93% in gasoline, react and within 1000 hours, do not observe catalyst activity loss, will after product separation benzene, measure gasoline octane rating (RON) than 5 units of the front raising of reaction.
Claims (9)
1. a gasoline refining process, gasoline and the benzene of take containing 2～12 carbon olefins are raw material, in temperature of reaction, are 100～160 ℃, and reaction pressure is 1.0～2.8MPa, and benzene alkene molecular ratio is 5～15, and gasoline weight space velocity is 0.1～1.0 hour
-1under condition, raw material contacts with catalyzer, by the conversion of olefines in gasoline, is aromatic hydrocarbons, obtains treated gasoline; Wherein, catalyzer used comprises following component by weight percentage: a) 30 ~ 80% crystalline aluminosilicate material; B) 20 ~ 70% inorganic oxide; Described crystalline aluminosilicate material has following XRD diffraction data:
。
2. gasoline refining process according to claim 1, is characterized in that described crystalline aluminosilicate material specific surface area is 500 ~ 600 meters
2/ gram, pore volume is 0.45 ~ 0.60 ml/g.
3. gasoline refining process according to claim 1, is characterized in that described inorganic oxide is selected from least one in aluminum oxide, titanium oxide, zinc oxide or zirconium white.
4. gasoline refining process according to claim 3, is characterized in that described inorganic oxide is selected from least one in aluminum oxide or zinc oxide.
5. gasoline refining process according to claim 1, is characterized in that by weight percentage the consumption 50 ~ 70% of crystalline aluminosilicate material.
6. gasoline refining process according to claim 1, is characterized in that by weight percentage, and the consumption of inorganic oxide is 30 ~ 50%.
7. gasoline refining process according to claim 1, is characterized in that temperature of reaction is 120～160 ℃, and reaction pressure is 1.3～2.5MPa, and benzene alkene molecular ratio is 6～12, and gasoline weight space velocity is 0.1～0.85 hour
-1.
8. gasoline refining process according to claim 1, is characterized in that the described gasoline containing 2～12 carbon olefins is from the inferior patrol producing in long-chain alkyl benzene production process.
9. gasoline refining process according to claim 1, it is characterized in that described containing in the gasoline of 2～12 carbon olefins, by weight percentage, the olefin(e) centent that contains 2 ~ 12 carbon is 0.1～40%, Determination of Alkane Content containing 2 ~ 12 carbon is 40～80%, and aromaticity content is 0 ~ 20%.
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|---|---|---|---|
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|---|---|---|---|
| CN201210239982.0A CN103540340B (en) | 2012-07-12 | 2012-07-12 | Gasoline refining process |
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| CN103540340B CN103540340B (en) | 2015-10-21 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1137022A (en) * | 1994-12-30 | 1996-12-04 | 中国石油化工总公司 | Rare-earth-ZSM5/ZSM11 cocrystallization zeolite |
| EP0780458A2 (en) * | 1995-12-21 | 1997-06-25 | SUN COMPANY, INC. (R&M) | Process for upgrading petroleum fractions containing olefins and aromatics |
| EP0688308B1 (en) * | 1993-03-08 | 2000-04-05 | Mobil Oil Corporation | Benzene reduction in gasoline by alkylation with higher olefins |
| US20040162454A1 (en) * | 2002-02-05 | 2004-08-19 | Abb Lummus Global Inc. | Hydrocarbon conversion using nanocrystalline zeolite Y |
| CN1590508A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Method of reducing olefine and benzene content in gasoline |
-
2012
- 2012-07-12 CN CN201210239982.0A patent/CN103540340B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0688308B1 (en) * | 1993-03-08 | 2000-04-05 | Mobil Oil Corporation | Benzene reduction in gasoline by alkylation with higher olefins |
| CN1137022A (en) * | 1994-12-30 | 1996-12-04 | 中国石油化工总公司 | Rare-earth-ZSM5/ZSM11 cocrystallization zeolite |
| EP0780458A2 (en) * | 1995-12-21 | 1997-06-25 | SUN COMPANY, INC. (R&M) | Process for upgrading petroleum fractions containing olefins and aromatics |
| US20040162454A1 (en) * | 2002-02-05 | 2004-08-19 | Abb Lummus Global Inc. | Hydrocarbon conversion using nanocrystalline zeolite Y |
| CN1590508A (en) * | 2003-08-29 | 2005-03-09 | 中国石油化工股份有限公司 | Method of reducing olefine and benzene content in gasoline |
| WO2005077866A1 (en) * | 2004-02-09 | 2005-08-25 | Abb Lummus Global Inc. | Hydrocarbon alklyation using a nanocrystalline zeolite y catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 周斌等: "丙烯和苯液相烷基化反应中分子筛性能的研究", 《石油化工》, vol. 31, no. 11, 30 November 2002 (2002-11-30) * |
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