CN101418233B - Method for reducing sulphur in inferior naphtha - Google Patents
Method for reducing sulphur in inferior naphtha Download PDFInfo
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- CN101418233B CN101418233B CN2007101577800A CN200710157780A CN101418233B CN 101418233 B CN101418233 B CN 101418233B CN 2007101577800 A CN2007101577800 A CN 2007101577800A CN 200710157780 A CN200710157780 A CN 200710157780A CN 101418233 B CN101418233 B CN 101418233B
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Abstract
The invention discloses a method for reducing sulfur in inferior naphtha. The method comprises the following steps: full cut naphthar is subjected to fixed-bed oxidative deodorization and then distillated to give light boiling range naphtha, mediate boiling range naphtha and heavy boiling range naphtha; the heavy boiling range naphtha is subjected to hydrodesulphurization treatment and effluent is mixed with the mediate boiling range naphtha for secondary hydrodesulphurization treatment; a fine product is mixed with the light boiling range naphtha to give a clean gasoline product; a first hydrogenation reaction and a second hydrogenation reaction are preferably carried out in different catalytic systems under different reaction conditions. Compared with the prior art, the method can reduce the content of sulfur in distillation cut of inferior naphtha to below 10mu g/g, achieves small loss of octane number, qualified mercaptan content and gives high quality clean gasoline products.
Description
Technical field
The present invention relates to a kind of method that reduces sulphur in the inferior naphtha, specifically, the present invention relates to a kind of the inferior naphtha sulphur content is reduced to the process method less than 10 μ g/g.
Background technology
Reduce content of sulfur in gasoline and can reduce the exhaust of some harmful pollutants amount significantly, therefore, countries in the world clean gasoline new standard has proposed more and more strict restriction to sulphur content.Sulphur content ≯ 50 μ the g/g of Europe IV class automobile exhaust emission standard (EU2005 standard) regulation gasoline after 2005, olefin(e) centent ≯ 18v%, sulphur content is also planned to implement in 2009 less than 10 μ g/g " sweet gasoline (ULSG) " new standard in Europe.Sulphur content ≯ 80 μ the g/g of U.S.'s U.S.EPA Tier 2-II standard code U.S.'s clean gasoline after 2006, olefin(e) centent ≯ 14v%, the sulphur content of U.S.EPA Tier 2-III standard code U.S.'s clean gasoline after 2008 ≯ 30 μ g/g; China's on July 1st, 2005, national gasoline was carried out European II emission standard (sulphur content ≯ 500 μ g/g), and European III emission standard (sulphur content ≯ 150 μ g/g) is carried out in the major area; On July 1st, 2007～2008, European III emission standard was carried out in the whole nation, and European IV emission standard (sulphur content ≯ 50 μ g/g) is carried out in the major area; On July 1st, 2010～2011, European IV emission standard was carried out in the whole nation.The sulphur content of the following gasoline in countries in the world requires will be more and more lower.
At present, catalytic cracking (FCC) is the important source of gasoline, be more than 80% like the shared ratio of FCC gasoline in the Chinese refinery gasoline product, and FCC sulfur in gasoline content is generally 200～1000 μ g/g, and mercaptans content is generally 20～100 μ g/g.Therefore, FCC gasoline sulfur and mercaptans content are all higher, and the sulphur content and the mercaptans content that reduce FCC gasoline are to satisfy the key of stricter clean gasoline specification.
Hydrogenating desulfurization (HDS) technology is the important means of effective elimination FCC gasoline sulfur and mercaptan, still, adopts conventional catalysts and technology, and in the FCC gasoline hydrodesulfurizationmethod, the alkene saturated meeting of hydrogenation significantly causes bigger loss of octane number.In order to reduce the loss of sweet gasoline octane value, develop many selective hydrodesulfurizations (HDS) raw catalyst and technology both at home and abroad.
U.S 6,692, and 635 have introduced a kind of low-sulphur oil production technique.Be characterized at first selectively removing diolefine in selective hydrogenation device (first reactor drum) of full cut catalytic gasoline raw material, olefines double bond isomerizing and mercaptan are converted into higher boiling sulfur compound.Then, the fractionation in a separation column of selective hydrogenation product is lighting end and last running.Last running is the MoO in first reaction zone of hydrogenator (second reactor drum) at first
3-CoO/Al
2O
3Hydrogenation on the catalyzer is converted into saturated sulfide (like THTP or mercaptan) with unsaturated sulfide (like thiophene and alkylated substituted thiazoline fen thereof), then, and the NiO/Al in second reaction zone
2O
3Hydrogenation on the catalyzer is converted into H with saturated sulfide (like thiophene and alkylated substituted thiazoline fen thereof)
2S.The desulfurization degree of this patented process is generally 80.0%～92.0%, and the product sulphur content is generally 96 μ g/g～240 μ g/g, 1.4～3.0 units of RON (RON) loss.Its shortcoming is the Technology Need that has satisfied not oil refining enterprise production clean gasoline sulphur content ≯ 10 μ g/g.
U.S5,320,742 disclose oxidation removal mercaptan, with aftercut and the unifining combination than the heavy boiling range petroleum naphtha.Remove in the mercaptan in oxidation, mercaptan is converted into corresponding disulphide.Its shortcoming is that the desulfurization amplitude is limited, and loss of octane number is bigger, has satisfied not the Technology Need of oil refining enterprise production clean gasoline sulphur content ≯ 10 μ g/g.
CN1604956A has introduced a kind of method that reduces sulphur in the naphtha stream.Full range naphtha stream at first fractionation is light boiling range petroleum naphtha, mid range petroleum naphtha and heavy boiling range petroleum naphtha.The light boiling range petroleum naphtha adopts wet caustic wash to remove the mercaptan in the light naphthar, and bottom product is handled through first hydrogenating desulfurization, and elute combines to carry out second hydrogenating desulfurization with the petroleum naphtha that contains thiophene, thiophene and thienyl mercaptan mid range to be handled.Or range naphtha stream was passed through thioetherification before fractionation entirely, and fractionation is light boiling range petroleum naphtha, mid range petroleum naphtha and heavy boiling range petroleum naphtha again.Its advantage is to keep alkene, helps removing sulfide simultaneously; Though its shortcoming is the mercaptan that can remove in the light boiling range petroleum naphtha, in, contain H in the heavy boiling range petroleum naphtha HDS product
2The more macromolecular mercaptan that S and the rearrangement reaction of alkene secondary generate must carry out mercaptan removal and handle.The document does not disclose corresponding operational condition yet, can't obtain sulphur content and be lower than 10 μ g/g and the few clean gasoline product of loss of octane number.
In the prior art; The subject matter of FCC gasoline production low-sulfur clean gasoline product is that several respects contradiction can not take into account solution simultaneously; As sulfide under the contradiction between desulfurization depth and the loss of octane number, the hydrodesulfurizationconditions conditions remove and contradiction, deodorization and the desulfurization of mercaptan between generating between contradiction etc., make existing Technology can not obtain low-sulfur, loss of octane number is few, mercaptan is qualified clean gasoline product simultaneously.
Summary of the invention
To the deficiency of prior art, the present invention provides a kind of method that reduces sulphur in the inferior naphtha, adopts suitable technology and condition, production sulphur content ≯ 10 μ g/g, the clean gasoline product that loss of octane number is few.
The present invention reduces that the method for sulphur comprises the steps: in the inferior naphtha
(1) full cut inferior naphtha carries out the fixed bed oxidation deodorizing, and mercaptan sulfur is converted into disulphide;
(2) the full cut inferior naphtha of the deodorization cut in the step (1) is cut into light boiling range petroleum naphtha, middle boiling range naphtha stream and heavy boiling range petroleum naphtha; Wherein the cut point of light boiling range petroleum naphtha and middle boiling range naphtha stream is 45～85 ℃, and the cut point of middle boiling range naphtha stream and heavy boiling range petroleum naphtha is 130～160 ℃;
(3) carry out desulphurization reaction at first hydroconversion reaction zone in the heavy boiling range petroleum naphtha that obtains in the step (2), the middle boiling range naphtha stream that obtains in first hydrogenation reaction effluent and the step (2) is carried out desulphurization reaction at second hydroconversion reaction zone.
(4) the second hydroconversion reaction zone hydrogenating desulfurization product in the light boiling range petroleum naphtha in the step (2) and the step (3) is mixed, obtain the clean gasoline product of sulphur content less than 10 μ g/g.
The described fixed bed oxidation deodorizing of step (1) can adopt the common method in this area to carry out, and as being that catalyzer is the oxidation deodorizing process of oxygenant with the air with sulfonation titanium cyanines cobalt, the sweet gasoline mercaptan sulfur after deodorization is handled generally can reach ≯ 10 μ g/g.
The described sweet gasoline cut of step (2) can adopt conventional distillation mode to carry out fractionation.
H in the hydrogen that the described hydrogenating desulfurization of step (3) is used
2S content ≯ 300 μ g/g, preferred ≯ 50 μ g/g, generally adopt recycle hydrogen de H
2S realizes.First hydroconversion reaction zone uses following character catalyzer: catalyzer is carrier with aluminum oxide, is reactive metal with Mo and Co, is auxiliary agent with P and K, and wherein catalyzer contains MoO
37.0-18.0wt% is preferably 10.0-16.0wt%, is preferably 10.0-15.0wt%, and CoO1.0-6.0wt% is preferably 2.0-5.0wt%, is preferably 2.0-4.0wt%.Catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g, Co/Mo atomic ratio 0.1-1.0 is preferably 0.2-0.8, is preferably 0.25-0.72, contains potassium 0.2-10.2wt%, is preferably 0.5-5.0wt%, is preferably 1.0-3.0wt%, and P/K atomic ratio 0.1-10.0 is preferably 0.8-5.0, is preferably 1.0-2.0.Second hydroconversion reaction zone uses at least two kinds of catalyzer, and first kind of catalyst property is: catalyzer is carrier with the aluminum oxide, is reactive metal with Mo and Co, is auxiliary agent with P and K, and wherein catalyzer contains MoO
37.0-18.0wt% is preferably 10.0-16.0wt%, is preferably 10.0-15.0wt%, and CoO1.0-6.0wt% is preferably 2.0-5.0wt%, is preferably 2.0-4.0wt%.Catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g, Co/Mo atomic ratio 0.1-1.0 is preferably 0.2-0.8, is preferably 0.25-0.72, contains potassium 0.2-10.2wt%, is preferably 0.5-5.0wt%, is preferably 1.0-3.0wt%, and P/K atomic ratio 0.1-10.0 is preferably 0.8-5.0, is preferably 1.0-2.0; Second kind of catalyst activity metal content is 20%～60% of first kind of catalyst activity metal content.At second hydroconversion reaction zone, through the catalyzer of low activity metal content, through the catalyzer of high activity metal content, two kinds of catalyst volume ratios are 2: 8～8: 2 to reaction mass then earlier.
In the step (3), the operational condition of first and second hydroconversion reaction zones is: the hydrogen dividing potential drop is generally 0.5MPa～5.0MPa, and temperature of reaction is generally 230 ℃～330 ℃, and volume space velocity is generally 2.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio was generally 200: 1～1000: 1; The hydrogen dividing potential drop is preferably 0.8MPa～2.5MPa, and temperature of reaction is preferably 250 ℃～300 ℃, and volume space velocity is preferably 3.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is preferably 200: 1～and 500: 1.Wherein the temperature of reaction of first hydroconversion reaction zone is higher than 3～40 ℃ of second hydroconversion reaction zones, and is preferred high 5～20 ℃.
H in the hydrogen that the described hydrogenating desulfurization of step (3) is used
2S content ≯ 300 μ g/g, preferred ≯ 50 μ g/g, generally adopt recycle hydrogen de H
2S realizes that the control hydrodesulfurization process is used H in the hydrogen
2The content of S can effectively be controlled the generation of mercaptan in the hydrogenation products.
The present invention can produce the gasoline products of total sulfur ≯ 10 μ g/g through combination process, and octane value is high, and mercaptans content is qualified, is high quality clean gasoline product.The inventive method can be handled various inferior naphtha raw materials, like catalytic cracking petroleum naphtha, coking naphtha, viscosity breaking petroleum naphtha etc.
In the prior art, the subject matter of FCC gasoline production low-sulfur clean gasoline product is that the conversion of mercaptan in the light boiling range petroleum naphtha, hydrodesulfurization process loss of octane number are many, hydrodesulfurization process is followed mercaptan generation etc.Sulfur compound in the light boiling range petroleum naphtha mainly is a mercaptan, and mainly is thiophene and other heterocycle sulfocompounds than the sulfocompound of heavy boiling range petroleum naphtha, can not remove mercaptan so separate through fractionation separately.If think the clean gasoline of production sulphur content ≯ 10 μ g/g, must the mercaptan in the light boiling range petroleum naphtha be removed or transform the sulfide of attaching most importance to.Adopt method of hydrotreating selectively removing mercaptan, because with olefin saturation, so certainly will cause loss of octane number more.The fixed bed oxidation deodorizing method can be removed mercaptan, and octane value do not lose basically, but because the just transformation of sulfocompound form generally can not reduce total sulfur content.In order to make catalytically cracked gasoline product mercaptans content qualified, generally with last one technology of oxidation deodorizing as the gasoline processing, but the oxidation deodorizing process just changes the form of sulfide, does not fall doctor negative content.Therefore flow process is adjusted into and carries out catalytic gasoline of whole fraction fixed bed oxidation deodorizing earlier, and most of mercaptan is converted into disulphide, and fractionation is light boiling range petroleum naphtha, middle boiling range naphtha stream and heavy boiling range petroleum naphtha then.Inferior naphtha through after the deodorization processing is divided into light boiling range petroleum naphtha, middle boiling range naphtha stream and heavy boiling range petroleum naphtha through separation column, to the characteristics of different boiling ranges petroleum naphtha, handles targetedly.Behind the light boiling range petroleum naphtha process fixed bed oxidation deodorizing; Sulfocompound wherein is converted into the higher sulfide of boiling point, and sulphur content is very low in the light boiling range petroleum naphtha after the fractionation, does not need further to handle again; And, avoided the problem of following process loss octane value because its octane value is higher.Heavy boiling range petroleum naphtha sulphur content is high, olefin(e) centent is low, and the hydrodesulfurizationconditions conditions that the employing condition is harsh relatively can reach the deep desulfuration effect; Because its olefin(e) centent is low; Loss of octane number is limited, selects suitable catalyzer and processing condition simultaneously, and its loss of octane number further reduces.In in the boiling range naphtha stream sulphur all be starkly lower than the heavy boiling range petroleum naphtha with olefin(e) centent, wherein sulfocompound is easy to remove, the present invention adopts the catalyst system and the operational condition of optimization, when reaching deeply the desulfurization degree, loss of octane number is less.Flow out first hydroconversion reaction zone into also introducing second hydroconversion reaction zone simultaneously, can the sulfur-bearing chemical combination such as a small amount of mercaptan that generate under the first reaction zone severe condition further be removed, make final hydrogenation products not need other processing can make mercaptans content reach requirement.Hydrogenation products mixes with the light boiling range petroleum naphtha can obtain low-sulfur, high-octane high quality clean gasoline product.The inventive method can be handled various raw materials of different nature, has flexibility and handiness widely, and Technology is ripe, and safety is high.
Description of drawings
Fig. 1 is a method flow synoptic diagram provided by the invention.
Wherein 10 are separation column, 30 attach most importance to boiling range naphtha stream hydrodesulfurizationreaction reaction zone, 40 attach most importance to boiling range naphtha stream and middle boiling range naphtha stream mixing oil hydrodesulfurizationreaction reaction zone for oxidation deodorizing reactor drum, 20;
A be raw material, B be light boiling range petroleum naphtha, C be middle boiling range naphtha stream, D attach most importance to boiling range naphtha stream, E be in, heavy boiling range naphtha products, F for light, in, heavy boiling range petroleum naphtha mixing oil product.
Embodiment
Bad gasoline according to the invention is FCC (FCC) gasoline, catalytic cracking gasoline, coker gasoline, pressure gasoline etc. or its mixture.The preferred raw material of the present invention is a FCC gasoline.Said inferior patrol hydrogenating materials can be full cut FCC gasoline, and boiling range is generally 30 ℃～220 ℃, particularly 30 ℃～180 ℃.
Fixed bed oxidation deodorizing technology of the present invention can adopt arbitrary form of the prior art, as adopting alkali-free sweetening treatment process etc.Fixed bed oxidation deodorizing technology explains in many patent documentations, like U.S.4033806, and U.S.4481106, U.S 4746494; U.S.5741415, U.S.5849656, U.S.5858212, U.S.5961819; CN1028765C, CN1031854A, CN1670134A etc.Therefore, any those of ordinary skill in the art can handle according to existing method.
Sweet gasoline cut according to the invention is cut into light boiling range petroleum naphtha, middle boiling range naphtha stream and heavy boiling range petroleum naphtha, and a kind of concrete cutting scheme is: the light boiling range petroleum naphtha is＜C
6Cut, middle boiling range naphtha stream are C
6～145 ℃ of cuts, heavy boiling range petroleum naphthas are＞145 ℃ of cuts, the lighting end total sulfur that the oxidation deodorizing fractionation obtains ≯ 10 μ g/g.
The H that takes off of the present invention
2The S recycle hydrogen is preferably controlled H
2S content ≯ 300 μ g/g.Recycle hydrogen de H
2The S method is generally conventional hydramine method.The flow process of hydramine method technology is generally: from the H that contains of reactive system
2S hydrogen stream and hydramine adsorption solvent (like terepthaloyl moietie amine) counter current contact in adsorption tower is taken off H
2The hydrogen of S is discharged from cat head, after recycle compressor boosts, gets into reactive system; The hydramine adsorption solvent of discharging from the adsorption tower bottom enters into solvent regeneration tower through after the manipulation of regeneration, returns and continues in the adsorption tower to use.The above-mentioned H that takes off
2The S method is this area general knowledge, and those skilled in the art can handle according to existing method.
Hydrobon catalyst of the present invention is carrier with the aluminum oxide; With Mo and Co is reactive metal, is auxiliary agent with P and K, and catalyzer can be selected commercial catalyst; FGH catalyst series like Fushun Petrochemical Research Institute's development and production also can prepare by state of the art.
The inventive method can be under the situation of ≯ 2.0 units of RON (RON) loss the clean gasoline of production sulphur content ≯ 10 μ g/g.
Below in conjunction with accompanying drawing 1 and further the inventive method process of embodiment and effect.Logistics and each unit operation carry out along the direction of arrow in order.
Fig. 1 gasoline stocks A air sweetening in fixed bed oxidation desulfur reaction device 10, the mercaptan removal product gets in the separation column 20.Wherein petroleum naphtha is three kinds of cuts by fractionation.Contain most light boiling range petroleum naphtha and be removed, because air sweetening contains very small amount of organosulfur in the light boiling range petroleum naphtha as the cat head elute.Boiling range is C
6～145 ℃ middle boiling range naphtha stream is removed as sideing stream, and contains main thiophene and part mercaptan.Be＞145 ℃ heavy boiling range petroleum naphtha at the bottom of the tower, contain the part thiophene and than the organic sulfide of heavy boiling range.＞145 ℃ heavy boiling range petroleum naphtha carries out hydrogenating desulfurization in first reactor drum 30; All thiophene are converted into hydrogen sulfide with most of organic sulfide than heavy boiling range, and first reactor drum, 30 elutes and middle boiling range naphtha stream are mixed in second reactor drum 40 and carry out hydrogenating desulfurization subsequently.Basically main thiophene and the residue organic sulfide in part mercaptan and the heavy boiling range petroleum naphtha are converted into hydrogen sulfide in the middle boiling range naphtha stream, light, in, the heavy boiling range petroleum naphtha becomes the gasoline products of total sulfur ≯ 10 μ g/g after mixing.
Further specify scheme of the present invention and effect through embodiment below, but therefore do not limit the present invention.
Embodiment
This instance provides a kind of catalytically cracked gasoline sweetening effectiveness.Those skilled in the art can be according to feedstock property and quality product requirement; Confirm the corresponding operating condition of other raw material and product requirement through simple experiment in conjunction with this area knowledge; For example if feed sulphur content is higher; Heavy boiling range petroleum naphtha hydrogenation reaction can be used the higher catalyzer of active metallic content, and operate down at higher reaction pressure, temperature of reaction, lower volume space velocity etc.
Catalyzer is the commercial catalysts that Wenzhou Hua Hua group company produces.
Table 1 catalyzer physico-chemical property
| Project | FGH-20 | FGH-11 | |
| Shape | Ball-type | Cylinder shape | |
| Size/mm | Diameter 2.5～3.5 | Diameter 1.3～1.5; Length 3.0～8.0 | |
| Metal is formed | MoO 3，wt％ | 4.0～4.5 | 10.0～12.0 |
| CoO，wt％ | 1.0～1.5 | 2.5～3.5 | |
| Pore volume/mLg -1 | ≮0.55 | ≮0.45 | |
| Specific surface area/m 2·g -1 | ≮220 | ≮1?80 | |
1), raw oil mercaptan removal
Raw oil mercaptan removal oxygenant adopts commodity AFS-12 catalyzer (University of Petroleum's production), at pressure 0.5MPa, 35 ℃～45 ℃ of temperature, volume space velocity 2.0h
-1, gas and oil volume ratio (air/petroleum naphtha) condition under carries out deodorization at 4: 1.
2), raw oil cutting data
The sweet gasoline cut is cut into light boiling range petroleum naphtha, middle boiling range naphtha stream and heavy boiling range petroleum naphtha, and its cut is respectively＜C
6, C
6～145 ℃,＞145 ℃.
The character of each component of table 2 catalytically cracked gasoline cutting back
| Project | FCC gasoline | ＜C 6 | ?C 6～145℃ | ＞145℃ |
| The cutting ratio, wt% | ?100 | 25.6 | 38.2 | 36.2 |
| Density, g/ml | ?0.7232 | 0.6423 | 0.7102 | 0.7802 |
| Sulphur content, μ g/g | ?460 | 7 | 350 | 830 |
| Mercaptans content, μ g/g | ?34.2 | 2 | 5 | 5 |
| Olefin(e) centent, v% | ?25.6 | 40.0 | 23.0 | 10.0 |
| RON, RON | ?92.4 | 94.6 | 89.8 | 91.0 |
| Boiling range, ℃ (over point～final boiling point) | ?32～188 | 30～52 | 50～140 | 138～188 |
3),＞145 ℃ heavy boiling range petroleum naphtha and C
6Boiling range naphtha stream hydrogenating desulfurization in～145 ℃
The first reaction zone processing condition:
Hydrogen dividing potential drop 1.6MPa; 280 ℃ of temperature of reaction; Volume space velocity 2.0h
-1Hydrogen to oil volume ratio 300: 1, hydrogen sulfide content is controlled to be 40 μ g/g in the recycle hydrogen.
Catalyzer is FGH-11.
The second reaction zone processing condition:
Hydrogen dividing potential drop 1.6MPa; 270 ℃ of temperature of reaction; Volume space velocity 3.0h
-1Hydrogen to oil volume ratio 300: 1, hydrogen sulfide content is controlled to be 40 μ g/g in the recycle hydrogen.
Catalyzer is FGH-20: FGH-11=30%: 70% (volume).
4), the light boiling range petroleum naphtha and in, the heavy boiling range petroleum naphtha mixes
＞145 ℃ of heavy fractioning hydrogenation products and prefrationation light boiling range petroleum naphtha are according to the cutting mixed.Table 3 has been listed raw material catalytic cracking gasoline and the character of handling back clean gasoline product.
The character of table 3 embodiment oil product
| Project | FCC gasoline | Lighting end | In, the heavy fractioning hydrogenation product | Mixing oil |
| The cutting ratio, wt% | 25.6 | 74.4 | 100 | |
| Density, g/ml | 0.7232 | 0.6423 | 0.7551 | 0.7228 |
| Sulphur content, μ g/g | 460 | 7 | 8.0 | 8.0 |
| Mercaptan sulfur content, μ g/g | 34.2 | 2 | 6.0 | 4.8 |
| Olefin(e) centent, v% | 25.6 | 40.0 | 9.3 | 20.0 |
| RON (RON) | 92.4 | 94.6 | 87.5 | 91.2 |
| C 5 +Yield, wt% | 99.8 | 99.9 |
From table 3, can find out: method of the present invention can be reduced to 8 μ g/g by 460 μ g/g with the sulphur content of FCC gasoline; Mercaptan sulfur content is reduced to 4.8 μ g/g by 34.2 μ g/g; Olefin(e) centent is reduced to 20.0v% by 25.6v%, and RON RON loses 1.2 units, C
5 +Yield of gasoline 99.9wt% can be processed as sulphur content ≯ 10 μ g/g high-quality cleaning product with FCC gasoline inferior.
Comparative Examples
This Comparative Examples provides a kind of catalytically cracked gasoline sweetening effectiveness.
(1), raw oil lighting end, last running cutting
With 50 ℃ is that the cut point temperature is divided into catalytically cracked gasoline＜50 ℃ of light boiling range petroleum naphthas and＞50 ℃ of heavy boiling range petroleum naphthas.Table 4 has been listed the character of each cut.
The character of each cut in table 4 Comparative Examples
| Project | FCC gasoline | ＜50 ℃ of light boiling range petroleum naphthas | ＞50 ℃ of heavy and light boiling range naphtha stream |
| The cutting ratio, wt% | 100 | 25.8 | 74.2 |
| Density, g/ml | 0.7232 | 0.6456 | 0.7550 |
| Sulphur content, μ g/g | 460 | 40 | 580 |
| Mercaptans content, μ g/g | 34.2 | 32 | 20 |
| Olefin(e) centent, v% | 25.6 | 35.0 | 16.0 |
| RON, RON | 92.4 | 94.8 | 90.5 |
| Boiling range, ℃ (over point～final boiling point) | 32～188 | 30～52 | 50～188 |
(2), ℃ heavy boiling range hydrodesulfurizationof of naphtha＞50
The reactor process condition:
Hydrogen dividing potential drop 1.6MPa; 280 ℃ of temperature of reaction; Volume space velocity 2.0h
-1Hydrogen to oil volume ratio 300: 1.
Catalyzer is FGH-11.
(3), light boiling range petroleum naphtha and heavy boiling range petroleum naphtha mix
＞50 ℃ of heavy boiling range hydrodesulfurizationof of naphtha reactants with presort distilled boiling range naphtha stream cut according to the cutting mixed.
(4), mixing oil mercaptan removal
Scheme according to embodiment is carried out the mixing oil air sweetening.Table 5 has been listed raw material catalytic cracking gasoline and the character of handling back clean gasoline product.
The character of table 5 Comparative Examples oil product
| Project | FCC gasoline | ＞50 ℃ of heavy fractioning hydrogenation products | Mixing oil |
| Density, g/ml | 0.7232 | 0.7551 | 0.7233 |
| Sulphur content, μ g/g | 460 | 12.0 | 30.0 |
| Mercaptan sulfur content, μ g/g | 34.2 | 11.0 | 5.6 |
| Olefin(e) centent, v% | 25.6 | 7.8 | 18.0 |
| RON (RON) | 92.4 | 85.5 | 90.2 |
| C 5 +Yield, wt% | 99.8 | 99.9 |
Can the sulphur content of catalytically cracked gasoline be reduced to 30 μ g/g by 460 μ g/g from the method for table 5 Comparative Examples; Mercaptans content is reduced to 5.6 μ g/g by 34.2 μ g/g; Olefin(e) centent is reduced to 18.0v% by 25.6v%, and RON RON loses 2.2 units, C
5 +Yield of gasoline 99.9wt%.
Can find out,, not reduce the total sulfur content of product owing to deodorizing technology only is mercaptan to be converted into disulphide be present in the product; Be fractionated into two cuts in addition, independent heavy boiling range petroleum naphtha reaches identical desulfurization degree because olefin(e) centent is higher; Saturated more of alkene is unfavorable for bringing into play the hydrogenating desulfurization selectivity, mainly shows as loss of octane number and obviously strengthens; Therefore, limited the desulfurization depth of final product.
Claims (9)
1. a method that reduces sulphur in the inferior naphtha comprises the steps:
(1) full cut inferior naphtha carries out the fixed bed oxidation deodorizing;
(2) the full cut inferior naphtha of the deodorization cut in the step (1) is cut into light boiling range petroleum naphtha, middle boiling range naphtha stream and heavy boiling range petroleum naphtha; Wherein the cut point of light boiling range petroleum naphtha and middle boiling range naphtha stream is 45～85 ℃, and the cut point of middle boiling range naphtha stream and heavy boiling range petroleum naphtha is 130～160 ℃;
(3) the heavy boiling range petroleum naphtha that obtains in the step (2) carries out desulphurization reaction at first hydroconversion reaction zone, and the middle boiling range naphtha stream that obtains in first hydrogenation reaction effluent and the step (2) is carried out desulphurization reaction at second hydroconversion reaction zone;
(4) the second hydroconversion reaction zone hydrogenating desulfurization product in the light boiling range petroleum naphtha in the step (2) and the step (3) is mixed, obtain the clean gasoline product of sulphur content less than 10 μ g/g;
Wherein step (3) first hydroconversion reaction zones use following character catalyzer: catalyzer is carrier with aluminum oxide, is reactive metal with Mo and Co, is auxiliary agent with P and K, and wherein catalyzer contains MoO
37.0-18.0wt%, CoO1.0-6.0wt%, Co/Mo atomic ratio 0.1-1.0 contains potassium 0.2-10.2wt%, P/K atomic ratio 0.1-10.0, catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g.
2. according to the described method of claim 1, it is characterized in that the described fixed bed oxidation deodorizing of step (1) for being catalyzer with sulfonation titanium cyanines cobalt, is the oxidation deodorizing process of oxygenant with the air.
3. according to the described method of claim 1, it is characterized in that H in the hydrogen that step (3) hydrogenating desulfurization uses
2S content ≯ 300 μ g/g.
4. according to the described method of claim 1, it is characterized in that the H in step (3) the hydrogenating desulfurization use hydrogen
2S content ≯ 50 μ g/g adopts recycle hydrogen de H
2S realizes.
5. according to the described method of claim 1; It is characterized in that step (3) second hydroconversion reaction zones use two kinds of catalyzer at least, first kind of catalyst property is: catalyzer is carrier with the aluminum oxide, is reactive metal with Mo and Co; With P and K is auxiliary agent, and wherein catalyzer contains MoO
37.0-18.0wt%, CoO1.0-6.0wt%, Co/Mo atomic ratio 0.1-1.0 contains potassium 0.2-10.2wt%, P/K atomic ratio 0.1-10.0, catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g; Second kind of catalyst activity metal content is 20%～60% of first kind of catalyst activity metal content; Reaction mass passes through the catalyzer of low activity metal content earlier; Through the catalyzer of high activity metal content, two kinds of catalyst volume ratios are 2: 8～8: 2 then.
6. according to the described method of claim 1, it is characterized in that the operational condition of first and second hydroconversion reaction zones is in the step (3): the hydrogen dividing potential drop is 0.5MPa～5.0MPa, and temperature of reaction is 230 ℃～330 ℃, and volume space velocity is 2.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is 200: 1～1000: 1.
7. according to the described method of claim 1, it is characterized in that the operational condition of first and second hydroconversion reaction zones is in the step (3): the hydrogen dividing potential drop is 0.8MPa～2.5MPa, and temperature of reaction is 250 ℃～300 ℃, and volume space velocity is 3.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is 200: 1～500: 1.
8. according to claim 1,6 or 7 described methods, it is characterized in that the temperature of reaction of first hydroconversion reaction zone is higher than 3～40 ℃ of the second hydroconversion reaction zone temperature of reaction.
9. according to claim 1,6 or 7 described methods, it is characterized in that the temperature of reaction of first hydroconversion reaction zone is higher than 5～20 ℃ of the second hydroconversion reaction zone temperature of reaction.
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| CN103756722B (en) * | 2014-01-21 | 2016-02-24 | 湖北金鹤化工有限公司 | A kind of deodorization-extraction-hydrogenation combination technique producing low-sulphur oil |
| CN112786118B (en) * | 2019-11-06 | 2024-05-03 | 中国石油化工股份有限公司 | Memory, corrosion risk assessment method, device and equipment for hydrogenation reaction effluent |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360532A (en) * | 1991-08-15 | 1994-11-01 | Mobil Oil Corporation | Gasoline upgrading process |
| CN1319644A (en) * | 2000-03-29 | 2001-10-31 | 法国石油公司 | Gasoline desulfurating method containing process for rectifying of at least three fractions and intermediate fraction desulfurating |
| CN1604956A (en) * | 2001-12-12 | 2005-04-06 | 催化蒸馏技术公司 | Process for sulfur reduction in naphtha streams |
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2007
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5360532A (en) * | 1991-08-15 | 1994-11-01 | Mobil Oil Corporation | Gasoline upgrading process |
| CN1319644A (en) * | 2000-03-29 | 2001-10-31 | 法国石油公司 | Gasoline desulfurating method containing process for rectifying of at least three fractions and intermediate fraction desulfurating |
| CN1604956A (en) * | 2001-12-12 | 2005-04-06 | 催化蒸馏技术公司 | Process for sulfur reduction in naphtha streams |
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