CN103540340B

CN103540340B - Gasoline refining process

Info

Publication number: CN103540340B
Application number: CN201210239982.0A
Authority: CN
Inventors: 周斌; 高焕新; 魏一伦; 季树芳
Original assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Current assignee: China Petroleum and Chemical Corp; Sinopec Shanghai Research Institute of Petrochemical Technology
Priority date: 2012-07-12
Filing date: 2012-07-12
Publication date: 2015-10-21
Anticipated expiration: 2032-07-12
Also published as: CN103540340A

Abstract

The present invention relates to a kind of gasoline refining process, mainly solve the problem that in prior art, in prior art inferior patrol, olefin(e) centent is high, aromaticity content is not enough.The present invention by adopt with containing the gasoline of 2 ~ 12 carbon olefins and benzene for raw material, be 100 ~ 160 DEG C in temperature of reaction, 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 and catalyst exposure, be aromatic hydrocarbons by the conversion of olefines in gasoline, obtain treated gasoline; Wherein, catalyst used comprises following component: a) the crystalline aluminosilicate material of 30 ~ 80%; B) inorganic oxide of 20 ~ 70%; The technical scheme that described crystalline aluminosilicate material has specific XRD diffraction data solves this problem preferably, can be used for improving in the refining production of gasoline octane rating.

Description

Gasoline refining process

Technical field

The present invention relates to a kind of gasoline refining process.

Background technology

The trend presenting high grade, clean consumed by the gasoline of China, 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 condition that molecular size is suitable, 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 patrol, 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 some olefin be changed into aromatic hydrocarbons, not only can improve the fuel value of gasoline but also its octane value can be improved.Along with the demand of domestic daily chemical products is growing, the industrial scale also expanding day of its raw material long-chain alkyl benzene, is often 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, the increase that its sale price will have nearly 300%.

Document CN101962570A provides and a kind ofly carries out hydrogenation depth cracking to fraction oil of petroleum inferior thus obtain the method for the high-quality oil product of mononuclear aromatics of being rich in.Its processing condition are high-temperature and high-pressure hydrogenation cracking, are mainly suitable for the process of being rich in dicyclo, many rings petroleum fractions.CN101935266A provides and a kind of difficult cracking heavy oil catalytic material is converted into stop bracket gasoline and produces the method for propylene.Aforesaid method does not all relate to the method how poor quality oil being rich in alkene being converted into the high-quality gasoline being 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, provides a kind of new gasoline refining process.The method can become aromatic hydrocarbons by after the most of olefin alkylation in inferior patrol, thus 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, with containing the gasoline of 2 ~ 12 carbon olefins and benzene for raw material, it is 100 ~ 160 DEG C in temperature of reaction, 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 and catalyst exposure, be aromatic hydrocarbons by the conversion of olefines in gasoline, obtain treated gasoline; Wherein, catalyst used comprises following component: a) the crystalline aluminosilicate material of 30 ~ 80%; B) inorganic oxide of 20 ~ 70%; 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 be selected from least one in aluminum oxide, titanium oxide, zinc oxide or zirconium white, and more preferably scheme is be selected from least one in 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 DEG C, 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 containing 2 ~ 12 carbon is 0.1 ~ 40%, and the Determination of Alkane Content containing 2 ~ 12 carbon is 40 ~ 80%, and aromaticity content is 0 ~ 20%.

The preparation method of catalyzer used in the inventive method is as follows:

1) crystalline aluminosilicate material is prepared.

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 DEG C 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 ammonium salt is exchanged, make the content of alkalimetal ion wherein in 0.05% (weight) below, 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 being rich in alkene can be converted into the high-quality gasoline being rich in aromatic hydrocarbons, after process, the octane value of gasoline can improve 6%, achieves 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 vigorous stirring, continue stirring 2 hours, add 500g water and stir 1 hour, the above-mentioned solution mixed is formed jelly at 10 DEG C after aging 100 hours, for subsequent use.

25g sodium aluminate and 20g sodium hydroxide are dissolved in 500g water and is mixed evenly, adding 500g(40%wt) silicon sol stirs, add the stirring of 800g pure water to be again mixed evenly, add the colloidal sol 50g of above-mentioned preparation, continuing stirring proceeded in crystallizing kettle after 2 hours, stir crystallization 100 hours at 165 DEG C, filtration washing to pH=7 ~ 9,150 DEG C of oven dry.The specific surface area of gained sample is 550m ²/ g, pore volume is that 0.5ml/g, XRD diffraction data is as shown in table 1.

Get the aluminosilicate material 100g of above-mentioned synthesis, add 0.5M ammonium nitrate solution, be warming up to 95 DEG C and exchange 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 good for above-mentioned exchange and 25g aluminum oxide, 10g zinc oxide are mixed evenly, add 170ml5% salpeter solution, 5g pseudo-ginseng powder mediates extruded moulding after 1 hour, by the catalyzer of forming 150 DEG C of oven dry, be then warming up to 580 DEG C of roastings in air atmosphere and obtain finished catalyst in 4 hours.

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, and get the liquid phase alkylation reaction that 5.0g catalyzer carries out gasoline and benzene in fixed-bed reactor, wherein gasoline used has the composition of table 2.Reaction conditions is, gasoline air speed=0.1hr ^-1, temperature of reaction=150 DEG C, reaction pressure=2.5MPa, reaction product is the mixture of gasoline and benzene, the olefin conversion > 95% in gasoline.Reacting and do not observe a loss of catalyst activity in month, improving 6 units by measuring gasoline octane rating (RON) after above-mentioned product separation benzene than before 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
Ethylcyclopentene	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
		N-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 DEG C, reaction pressure=2.0Mpa, reaction product is the mixture of gasoline and benzene, olefin conversion > 93% in gasoline, reacting and do not observe loss of catalyst activity in 1000 hours, improving 5 units by measuring gasoline octane rating (RON) after product separation benzene than before reaction.

Claims

1. a gasoline refining process, with containing the gasoline of 2 ~ 12 carbon olefins and benzene for raw material, be 100 ~ 160 DEG C in temperature of reaction, 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 and catalyst exposure, be aromatic hydrocarbons by the conversion of olefines in gasoline, obtain treated gasoline; Wherein, catalyst used comprises following component: a) the crystalline aluminosilicate material of 30 ~ 80%; B) inorganic oxide of 20 ~ 70%; Described crystalline aluminosilicate material specific surface area is 500 ~ 600 meters ²/ gram, pore volume is 0.45 ~ 0.60 ml/g; Described crystalline aluminosilicate material has following XRD diffraction data:

2 θ diffraction angle Diffraction peak intensity (I/I ₀×100) 6.5° 28.8±0.1 7.2° 17.3±0.1 8.8° 15.4±0.1 9.7° 53.8±0.1 13.5° 39.4±0.1 14° 28.8±0.1 14.3° 19.2±0.1 15.4° 23.1±0.1 19.5° 34.6±0.1 22.2° 69.2±0.1 23.8° 23.1±0.1 25.5° 100±0.1 26.2° 65.4±0.1 27.5° 46.7±0.1 31° 27.9±0.1 35.8° 15.4±0.1

。

2. 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.

3. gasoline refining process according to claim 2, is characterized in that described inorganic oxide is selected from least one in aluminum oxide or zinc oxide.

4. gasoline refining process according to claim 1, is characterized in that by weight percentage, the consumption 50 ~ 70% of crystalline aluminosilicate material.

5. gasoline refining process according to claim 1, it is characterized in that by weight percentage, the consumption of inorganic oxide is 30 ~ 50%.

6. gasoline refining process according to claim 1, it is characterized in that temperature of reaction is 120 ~ 160 DEG C, 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.

7. gasoline refining process according to claim 1, is characterized in that the described gasoline containing 2 ~ 12 carbon olefins is from the inferior patrol produced in long-chain alkyl benzene production process.

8. 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 containing 2 ~ 12 carbon is 0.1 ~ 40%, Determination of Alkane Content containing 2 ~ 12 carbon is 40 ~ 80%, and aromaticity content is 0 ~ 20%.