CN1224679C - Method for producing low sulfur gasoline - Google Patents
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- CN1224679C CN1224679C CN 02121594 CN02121594A CN1224679C CN 1224679 C CN1224679 C CN 1224679C CN 02121594 CN02121594 CN 02121594 CN 02121594 A CN02121594 A CN 02121594A CN 1224679 C CN1224679 C CN 1224679C
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Abstract
The present invention relates to a method for producing low sulfur gasoline, which includes the following steps: cutting a gasoline raw material into a light fraction and a heavy fraction; making the light fraction undergo the processes of alkali refining treatment and mercaptan removal; making the heavy fraction and hydrogen come into contact with a hydrodesulfurization catalyst to carry out selective hydrodesulfurization reaction; making the hydrogenated gasoline fractions undergo the process of hydrogenation or non-hydrogenation to remove mercaptan; mixing the desulfurized light fraction and heavy fraction so as to obtain the desired gasoline product. By using the method, the olefin saturation ratio is lower than 30%, under the condition of maximal desulfurization rate of the gasoline, the antiknock index loss of the gasoline is lower than two units, and the sulfur content in the gasoline is lower than 200 ppm.
Description
Technical field
The invention belongs in the method that has refining hydrocarbon ils under the situation of hydrogen, more particularly, is the method for hydrotreating that belongs to a kind of gasoline fraction.
Background technology
Along with the continuous enhancing of people to environmental consciousness, the specification of motor spirit index such as oxygen level, vapour pressure, benzene content, aromatic hydrocarbons total content, boiling point, olefin(e) centent and sulphur content will be more and more stricter, especially sulphur content.At present, 90～99% sulphur comes catalytic cracking (FCC) gasoline in the domestic gasoline product, and therefore, reducing sulfur content of catalytic cracking gasoline is the key point that reduces the finished product content of sulfur in gasoline.The method of external existing production low-sulphur oil is a lot, and the combination that mainly contains FCC raw material hydrogenation pre-treatment (front-end hydrogenation), the aftertreatment of FCC gasoline and two kinds of methods is used.
The hydrotreatment of FCC raw material can reduce finished product sulfur in gasoline content significantly, but reduces in the method for FCC content of sulfur in gasoline at all, and FCC raw materials pretreatment investment is the highest, is difficult to economically bear; When requiring sulfur in gasoline content further to be reduced to 30ppm when following, front-end hydrogenation technology obviously is difficult to meet the demands, and still needs newly-built gasoline hydrogenation device; Simultaneously, should be noted that the FCC raw materials pretreatment does not reduce olefin(e) centent in the FCC gasoline.Like this, if olefin(e) centent is too high in the FCC gasoline, will need other technological process.
FCC gasoline is handled obviously its unique advantage, is being lower than the pre-treatment of FCC raw material hydrogenation aspect plant investment, production cost and the hydrogen consumption.And its different desulfurization depth can satisfy the gasoline of different sulphur content specifications.But catalytic gasoline olefin(e) centent height, especially domestic gasoline, olefin(e) centent is higher than external gasoline far away.Adopt traditional hydrodesulfurizationprocess process can be because of the saturated gasoline octane rating that reduces of a large amount of hydrogenation of alkene.Therefore, a kind of to invest low, as not lose octane value low-sulphur oil production technology extremely urgent in exploitation.
US5,906,730 disclose a kind of method of FCC gasoline segmentation desulfurization.First section keeps desulfurization degree 60～90%, processing condition: 200～350 ℃ of temperature, hydrogen dividing potential drop 5～30kg/cm
2, liquid hourly space velocity 2～10h
-1, hydrogen-oil ratio 500～3,000scf/bbl (i.e. 89～534Nm
3/ m
3), H
2S concentration control＜1000ppm.Second section control desulfurization degree 60～90%, processing condition: 200～300 ℃ of temperature, hydrogen dividing potential drop 5～15kg/cm
2, liquid hourly space velocity 2～10h
-1, hydrogen-oil ratio 1,000～3,000scf/bbl (i.e. 178～534Nm
3/ m
3), H
2S concentration control＜500ppm.If second section desulfurization still do not reach intended purposes, two sections desulfurization outlet effluents are continued desulfurization, its processing condition are identical with two sections sulfur removal technology conditions.Concentration of hydrogen sulfide in the necessary strict Control Circulation hydrogen of each step.
EP1031622 discloses a kind of method of full cut FCC gasoline hydrodesulfurizationmethod.The first step is saturated with unsaturated sulphur compound hydrogenation in the FCC gasoline, is converted into mercaptan sulfur compounds, and second step is again with saturated sulphur compound hydrogenating desulfurization.Its advantage is the full cut FCC gasoline of processing, does not need to carry out fractionation.Weak point is that sulphur compound major part remaining in the finished product is a mercaptan sulfur compounds, causes in the product mercaptan sulfur defective.
EP940464 with FCC gasoline cut into gently, in, weigh three sections cuts, with the heavy fractioning hydrogenation desulfurization, with the cooling of first bed outlet effluent, be mixed into the second bed hydrogenating desulfurization at first bed then with middle runnings.This method provides a kind of thinking of the FCC of solution quality of gasoline.But this method first bed temperature of reaction too high (weighted average bed temperature WABT is 360 ℃), alkene is all saturated, and the second bed temperature of reaction WABT is 302 ℃, and the alkene saturation exponent is up to 57%, and this method cutting cut is many, the technology relative complex.
Because the final boiling point of domestic FCC gasoline is lower than external FCC gasoline final boiling point, the FCC content of olefin in gasoline increases along with the boiling point lowering of gasoline fraction, and therefore the olefin(e) centent of domestic FCC gasoline is higher.Use above-mentioned prior art that domestic FCC gasoline is carried out hydrogenating desulfurization, alkene is saturated too many, makes loss of octane number bigger.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of producing low-sulphur oil, guarantee that simultaneously the anti-knock index loss of gasoline is minimum.
Method provided by the invention comprises the following steps:
(1), gasoline stocks is cut into light gasoline fraction, heavy naphtha, wherein the cut point of light gasoline fraction and heavy naphtha is respectively 80 ℃～100 ℃, and the yield of light gasoline fraction and heavy naphtha is respectively the heavy % in 30 heavy %～60 and the heavy % in 40 heavy %～70 of gasoline stocks;
(2), light gasoline fraction removes wherein mercaptan through alkali cleaning refining desulfurization alcohol;
(3), heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carries out the selective hydrodesulfurization reaction, separates hydrogenated oil and obtains lighter hydrocarbons and gasoline fraction, hydrogen-rich gas recycles;
(4), step (3) gained gasoline fraction is carried out hydrogenation or non-hydro-sweetening;
(5), the heavy naphtha after the desulfurization with refining after light gasoline fraction mix and obtain gasoline products.
The present invention's alkene under the situation of gasoline desulfur rate maximum is saturated minimum, and the anti-knock index loss of gasoline is minimum, and sulfur in gasoline content is lower than 200ppm.
Description of drawings
Accompanying drawing is the method synoptic diagram of production low-sulphur oil provided by the invention.
Embodiment
Method provided by the invention is so concrete enforcement:
(1), gasoline stocks is cut into light gasoline fraction, heavy naphtha under 80 ℃～100 ℃, the yield of light gasoline fraction, heavy naphtha is respectively the heavy % in the heavy % in 30 heavy %～60,40 heavy %～70 of gasoline stocks;
(2), light gasoline fraction is through the refining mercaptan that removes wherein of alkali extracting;
(3), heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carries out the selective hydrodesulfurization reaction, separates hydrogenated oil and obtains lighter hydrocarbons and gasoline fraction, hydrogen-rich gas recycles;
(4), step (3) gained gasoline fraction is carried out hydrogenation or non-hydro-sweetening;
(5), the heavy naphtha after the desulfurization with refining after light gasoline fraction mix and obtain gasoline products.
The used gasoline stocks of the present invention is FCC gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline or its mixture, the final boiling point of this raw material ≯ 220 ℃, and sulphur content is not more than 1500ppm.
Used alkali is sodium hydroxide solution etc. in the step (2).
The reaction conditions of selective hydrodesulfurization is in the step (3): hydrogen dividing potential drop 1.0～3.2MPa, 200 ℃～320 ℃ of temperature of reaction, liquid hourly space velocity 2.0～6.0h
-1, hydrogen-oil ratio 200～600Nm
3/ m
3The used Hydrobon catalyst of this step is VIB or the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, and preferred catalyzer contains one or more and the alumina host in molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, macropore and the mesopore zeolite; In oxide compound and with the total catalyst weight is benchmark, and the content of described molybdenum and/or tungsten is that the content of 3～20 heavy %, nickel and/or cobalt is that 0.3～2 heavy %, auxiliary agent Mg content are 1～7 heavy %, and the content of described zeolite is 5～60 heavy %.This catalyzer has very high selective desulfurization function, and less to the saturation of alkene.
Step (3) is though the gasoline fraction total sulfur behind the hydrogenation of gained is qualified, and mercaptan sulfur is still higher, so must take steps (4) carry out hydro-sweetening or non-hydro-sweetening to the gasoline fraction behind the hydrogenation.Hydro-sweetening can adopt Hydrobon catalyst and technology, and non-hydro-sweetening is with the mercaptans content in the method reduction cut of oxidation deodorizing.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.But it is not thereby limiting the invention.
Accompanying drawing is the method synoptic diagram of production low-sulphur oil provided by the invention.For simplicity, light gasoline fraction mercaptan removal and heavy naphtha hydrogenated oil mercaptan removal part does not mark in the drawings.
The method flow of producing low-sulphur oil is as follows:
Gasoline stocks enters separation column 2 through pipeline 1 and is cut into light gasoline fraction, heavy naphtha, wherein light gasoline fraction removes mercaptan removal through pipeline 3, heavy naphtha enters pump 5 through pipeline 4, heavy naphtha after boosting through pipeline 6 with after hydrogen from pipeline 18 mixes, enter process furnace 8 through pipeline 7, material after the heating enters reactor 10 through pipeline 9 and contacts with Hydrobon catalyst, hydrogenated oil enters high-pressure separator 12 through pipeline 11, the hydrogen-rich gas that comes out from separator 12 tops enters compressor 15 through pipeline 14, hydrogen-rich gas after the compression through pipeline 16 or with from the additional fresh hydrogen of pipeline 17 through pipeline 18, mix dereaction with heavy naphtha from pipeline 6.The liquid product that comes out from separator 12 bottoms enters stabilizer tower 19 through pipeline 13, separates the lighter hydrocarbons and the heavy naphtha that obtain and draws through pipeline 20,21 respectively, and wherein the heavy naphtha from pipeline 21 removes mercaptan removal.Light gasoline fraction, heavy naphtha behind the mercaptan removal are mixed into gasoline products.
Method provided by the invention alkene saturation exponent under the situation of gasoline desulfur rate maximum is lower than 30%, and the anti-knock index loss of gasoline is lower than 2 units, and sulfur in gasoline content is lower than 200ppm.
The following examples will give further instruction to method provided by the invention, but therefore not limit the present invention.
The trade names of used Hydrobon catalyst are respectively RSDS-1 and CH-18 in embodiment and the Comparative Examples, and these two kinds of catalyzer are produced by Sinopec Group's Chang Ling oil-refining chemical head factory catalyst plant.
Comparative Examples
With FCC gasoline A is raw material, earlier raw material is cut, and cut point is 96 ℃, and heavy naphtha accounts for 43.1 weight % of raw material, and the character of heavy naphtha is as shown in table 1.Heavy naphtha, hydrogen contact with catalyzer RSDS-1 and carry out hydrogenating desulfurization.Processing condition and product property are as shown in table 2.As can be seen from Table 2, though desulfurization degree is about 95%, the alkene saturation exponent is up to 58.78%.
Compare with Comparative Examples, differently under all identical situation of raw material, hydrogen dividing potential drop, liquid hourly space velocity, hydrogen-oil ratio be to use traditional Hydrobon catalyst CH-18.Heavy naphtha character behind processing condition and the hydrogenation is as shown in table 2.As can be seen from Table 2, reach identical desulfurization depth, present embodiment is lower 10 ℃ than Comparative Examples, but the alkene saturation exponent only is 29.01%, than low 29.77 percentage points of Comparative Examples.Illustrate that catalyst performance of the present invention is far superior to traditional hydrogenation catalyst performance.Simultaneously, the sulphur content of heavy naphtha only is 82ppm behind the hydrogenation.Gasoline products character after heavy naphtha behind the hydrogenation and the light gasoline fraction blending is listed in table 3, and as can be seen from Table 3, the full cut of gasoline is that final gasoline products anti-knock index loses only 0.8 unit.
With FCC gasoline B is raw material, earlier raw material is cut, and cut point is 100 ℃, and heavy naphtha accounts for 49.1 weight % of raw material, and the character of heavy naphtha is as shown in table 1.Heavy naphtha, hydrogen contact with catalyzer RSDS-1 and carry out hydrogenating desulfurization.Heavy naphtha character behind processing condition and the hydrogenation is as shown in table 2.As can be seen from Table 2, the hydrogenating desulfurization rate was up to 94.79% o'clock, and the alkene saturation exponent only is 26.63 weight %.The sulphur content of heavy naphtha only is 76ppm behind the hydrogenation.Gasoline products character after heavy naphtha behind the hydrogenation and the light gasoline fraction blending is listed in table 3, and as can be seen from Table 3, the full cut of gasoline is that final gasoline products anti-knock index loses only 1.2 units.
Table 1
| The last running of raw material A | The last running of raw material B | |
| Density (20 ℃), g/cm 3 | 0.7855 | 0.7705 |
| Sulphur content, ppm | 1680 | 1700 |
| Olefin(e) centent, weight % | 23.68 | 28.84 |
| Boiling range, ℃ | ||
| Initial boiling point | 92 | 92 |
| 5％ | 105 | 106 |
| 50％ | 135 | 132 |
| Final boiling point | 190 | 173 |
| RON | 90.8 | 85.2 |
| MON | 79.8 | 76.1 |
| Anti-knock index | 85.3 | 80.7 |
Table 2
| | Embodiment | 1 | | |
| The hydrogen dividing potential drop, MPa | 1.6 | 1.6 | 1.6 | |
| T，℃ | 280 | 290 | 285 | |
| Liquid hourly space velocity, h -1 | 4.0 | 4.0 | 4.0 | |
| Hydrogen-oil ratio, Nm 3/m 3 | 200 | 200 | 400 | |
| Heavy naphtha character behind the hydrogenation | ||||
| Density (20 ℃), g/cm 3 | 0.7725 | 0.7803 | 0.7658 | |
| Sulphur, ppm | 84 | 82 | 76 | |
| Group composition, weight % | ||||
| Paraffinic hydrocarbons | 38.99 | 36.16 | 35.42 | |
| Alkene | 9.76 | 10.5 | 21.16 | |
| Naphthenic hydrocarbon | 11.14 | 9.62 | 11.07 | |
| Aromatic hydrocarbons | 39.82 | 43.25 | 31.83 | |
| Desulfurization degree, % | 94.99 | 95.12 | 94.79 | |
| The alkene saturation exponent, % | 58.78 | 29.01 | 26.63 | |
| RON | 77.7 | 85.2 | 78.9 | |
| MON | 72.8 | 77.4 | 73.2 | |
| Anti-knock index | 75.3 | 81.3 | 76.1 | |
| The anti-knock index loss | 10.0 | 4.0 | 4.6 |
Table 3
| | | |||
| Raw material A | Blended product | Raw material B | Blended product | |
| Density (20 ℃), g/cm 3 | 0.7149 | 0.7138 | 0.7147 | 0.7135 |
| Sulphur content, ppm | 902 | 167 | 1184 | 182 |
| Group composition, v% | ||||
| Stable hydrocarbon | 43.4 | 48.1 | 48.0 | 53.9 |
| Alkene | 41.5 | 36.5 | 40.0 | 34.7 |
| Aromatic hydrocarbons | 15.1 | 15.4 | 12.0 | 11.4 |
| RON | 93.2 | 92.0 | 89.4 | 87.7 |
| MON | 81.1 | 80.7 | 79.6 | 78.9 |
| Anti-knock index | 87.2 | 86.4 | 84.5 | 83.3 |
| The anti-knock index loss | - | 0.8 | - | 1.2 |
Claims (3)
1, a kind of method of producing low-sulphur oil comprises the following steps:
(1), gasoline stocks is cut into light gasoline fraction, heavy naphtha under 80 ℃～100 ℃, wherein the yield of light gasoline fraction and heavy naphtha is respectively the heavy % in 30 heavy %～60 and the heavy % in 40 heavy %～70 of gasoline stocks;
(2), light gasoline fraction removes wherein mercaptan through alkali cleaning refining desulfurization alcohol;
(3), heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carry out the selective hydrodesulfurization reaction, separate hydrogenated oil and obtain heavy naphtha behind lighter hydrocarbons and the hydrogenation, hydrogen-rich gas recycles, and described Hydrobon catalyst contains molybdenum and/or tungsten, nickel and/or cobalt, auxiliary agent magnesium, large pore zeolite and/or mesopore zeolite and alumina host; In oxide compound and with the total catalyst weight is benchmark, and the content of described molybdenum and/or tungsten is that the content of 3～20 heavy %, nickel and/or cobalt is that 0.3～2 heavy %, auxiliary agent Mg content are 1～7 heavy %, and the content of described zeolite is 5～60 heavy %;
(4), heavy naphtha behind step (3) the gained hydrogenation is carried out hydrogenation or non-hydro-sweetening;
(5), the heavy naphtha behind the mercaptan removal with refining after light gasoline fraction mix and obtain gasoline products.
2,, it is characterized in that described gasoline stocks is one or more in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and the pressure gasoline according to the method for claim 1.
3,, it is characterized in that the reaction conditions of selective hydrodesulfurization in the described step (3) is: hydrogen dividing potential drop 1.0～3.2MPa, 200 ℃～320 ℃ of temperature of reaction, liquid hourly space velocity 2.0～6.0h according to the method for claim 1
-1, hydrogen-oil ratio 200～600Nm
3/ m
3
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| CN 02121594 CN1224679C (en) | 2002-06-27 | 2002-06-27 | Method for producing low sulfur gasoline |
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|---|---|---|---|
| CN 02121594 CN1224679C (en) | 2002-06-27 | 2002-06-27 | Method for producing low sulfur gasoline |
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| CN1224679C true CN1224679C (en) | 2005-10-26 |
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2002
- 2002-06-27 CN CN 02121594 patent/CN1224679C/en not_active Expired - Lifetime
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