CN101619234A - Method for producing low sulfur gasoline by using light weight gasoline - Google Patents
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Abstract
The invention discloses a method for producing low sulfur gasoline by using light weight gasoline, which can produce the high-quality clean gasoline with the sulfur content of less than 10mu g/g. The method adopts two-stage hydrogenation technology: at the first stage, a selective hydrogenation desulfurization catalyst is used for the selective hydrogenation desulfurization of the gasoline material, reaction products enter a second stage reactor and are contacted with a hydrogenation desulfurization alcohol catalyst, and after reaction, the clean gasoline products are obtained, wherein the selective hydrogenation desulfurization catalyst used by the method takes aluminum oxide as a carrier and molybdenum and cobalt as active components, and also contains auxiliary agents of potassium and phosphorus; and the hydrogenation desulfurization alcohol catalyst used by the method takes copper and zinc as main components. The method is suitably used for hydrogenation desulfurization reactions and desulfurization alcohol reactions, and after hydrogenation, the sulfur content is less than 10mu g/g; moreover, after reaction, the yield of the liquid is high, and the loss of the octane value is less.
Description
Technical field
The present invention relates to a kind of light benzine fraction deep desulfurization and produce the method for low-sulphur oil, specifically, the present invention relates to the method for a kind of light benzine cut fraction hydrogenation desulfurization/mercaptan removal combination process being produced clean gasoline.
Background technology
Increasingly stringent along with environmental regulation, countries in the world have proposed more and more stricter requirement to gasoline products, particularly the sulphur content in the gasoline is required more and more stricter, for example China's content of sulfur in gasoline index from ≯ 800 μ g/g, ≯ 500 μ g/g are to ≯ 150 μ g/g, and will develop into ≯ 50 μ g, or even ≯ " sweet gasoline " of 10 μ g.
At present, catalytic cracking process (FCC) is the important source of gasoline, be more than 80% as 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 traditional catalyzer and technology, and in the FCC gasoline hydrodesulfurizationmethod, the alkene saturated meeting of hydrogenation significantly causes bigger loss of octane number more.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.Pat.6,692,635 have introduced a kind of low-sulphur oil production technique.Be characterized at first selectively removing diolefine in selective hydrogenation device (first reactor) 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) at first
3-CoO/Al
2O
3Hydrogenation on the catalyzer is converted into saturated sulfide (as tetramethylene sulfide or mercaptan) with unsaturated sulfide (as 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 (as thiophene and alkylated substituted thiazoline fen thereof)
2S.The desulfurization degree of this patented method 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 research octane number (RON) (RON) loss.Its shortcoming is that the product sulphur content is still higher, does not satisfy the requirement that oil refining enterprise is produced clean gasoline sulphur content ≯ 50 μ g, particularly can not satisfy the Technology Need of further production ≯ 10 μ g/g clean gasolines.
EP 1031622 discloses a kind of method of full cut FCC gasoline hydrodesulfurizationmethod.The first step is saturated with unsaturated sulfide hydrogenation in the FCC gasoline, is converted into mercaptan sulfur compounds, and second step was H with saturated sulphur compound hydrodesulfurizationconversion conversion again
2S.Its advantage is the full cut FCC gasoline of processing, does not need to carry out fractionation, and weak point is that the remaining sulphur compound major part of the finished product is a mercaptan sulfur compounds, causes in the product mercaptan sulfur defective.
CN 02133136.7 has introduced a kind of catalyst for selective hydrodesulfurizationof of gasoline and technology, is characterized in being lighting end and last running with the prefractionation of FCC gasoline earlier, and last running is at low metal/high metal content MoO
3-CoO/Al
2O
3After the hydrogenating desulfurization, mix with lighting end again on the combination catalyst.This patented method shortcoming is owing to contain H in the last running HDS product
2The more macromolecular mercaptan that S and the rearrangement reaction of alkene secondary generate on the one hand, has reduced the degree of depth of HDS, and on the other hand, the follow-up mercaptan removal that must carry out is handled.The desulfurization degree of this patented method is generally 80.0%～90.0%, the product sulphur content is generally 50 μ g/g～200 μ g/g, ≯ 2.0 units of research octane number (RON) (RON) loss do not satisfy the Technology Need that oil refining enterprise is produced clean gasoline sulphur content ≯ 10 μ g/g.
CN 02121594.4 has introduced a kind of method of producing low-sulphur oil.This method is that gasoline stocks is cut into lighting end and last running, lighting end is through the soda finishing mercaptan removal, last running contacts with Hydrobon catalyst together with hydrogen, carry out the selective hydrodesulfurization reaction, gasoline fraction behind the hydrogenation carries out hydrogenation or non-hydro-sweetening, light, last running after the desulfurization is mixed obtaining gasoline products.This method can the production sulphur content be lower than 200 μ g/g, ≯ 2.0 units of the anti-knock index of gasoline ((R+M)/2) loss.Its shortcoming is to satisfy the Technology Need that oil refining enterprise is produced clean gasoline sulphur content ≯ 10 μ g/g.
In above-mentioned technology, organic sulfide can generate a large amount of hydrogen sulfide (H in hydrodesulfurization process
2S) by product, generally, H in the hydrogen of reactant
2S content is 1000～5000 μ g/g.Owing to still contain the alkene of high level in the HDS product, H
2The secondary rearrangement reaction takes place and generates more macromolecular mercaptan once more in S and alkene easily.Zhao Le equality people [seeing " refining of petroleum and chemical industry ", 2006,37 (7): 1～5] is even result of study is thought H
2H in the gas
2S is 1700 μ g/g, compares with raw material, and the C7 mercaptan sulfur content increases by 46.6% in the product.Though the conventional fixed bed oxidation deodorizing technology (as Merox technology) of process can be reduced to mercaptan sulfur and be lower than 10 μ g/g, but, deodorizing technology only is mercaptan sulfur is converted into disulphide and is present in the product, do not reduce the total sulfur content of product, therefore, limit the desulfurization depth of final product, do not satisfied the Technology Need that oil refining enterprise is produced clean gasoline sulphur content ≯ 10 μ g/g.
CN1119398C has introduced a kind of method for transformation of hydrocarbon ils.This method is that gasoline is contacted under the processing condition of hydro-sweetening with a kind of Hydrobon catalyst, described Hydrobon catalyst contains Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, the content of described Tungsten oxide 99.999 and/or molybdenum oxide is that 4.0wt% is extremely less than 10.0wt%, nickel oxide content is 1.0wt%～5.0wt%, cobalt oxide content is 0.01wt%～1.0wt%, nickel and cobalt total atom number and nickel, cobalt, tungsten and or the ratio of the total atom number of molybdenum be 0.3～0.9.When this method is handled FCC gasoline, mercaptans content is reduced to 10 μ g/g by 212 μ g/g, 3.3 units of research octane number (RON) (RON) loss, 3.0 units of motor-method octane number (MON) loss, therefore, this method shortcoming is that loss of octane number is more when handling FCC gasoline, can not obtain the high standard gasoline products.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of method that the combination process of light benzine desulfurization/mercaptan removal is produced clean gasoline, this method not only can make inferior patrol deep desulfuration and mercaptan removal, and its product loss of octane number is less.
The method of production low-sulphur oil provided by the invention, comprise that gasoline stocks carries out selective hydrodesulfurization in the presence of catalyst for selectively hydrodesulfurizing, reaction product contacts with the hydrogenating desulfurization alcohol catalyst again, obtain the low-sulphur oil product after the reaction, or even sulphur content is lower than the low-sulphur oil product of 10 μ g/g.
Catalyst for selectively hydrodesulfurizing wherein comprises concrete the composition: the weight with catalyzer is benchmark, and catalyzer contains MoO
31.0～18.0w%, CoO 0.1～6.0w%, Co/Mo atomic ratio 0.1～1.0, catalyzer contains potassium and phosphorus component simultaneously, contain potassium 0.2～10.2w%, P/K atomic ratio 0.1～10.0, it is carrier that catalyzer reaches the bigger aluminum oxide of pore volume more greatly with specific surface area, catalyzer pore volume 0.3～1.3ml/g, specific surface area 150～300m
2/ g.Selective desulfurization catalyst can adopt the catalyzer of patent CN1488721A invention.
Wherein the hydrogenating desulfurization alcohol catalyst is composed as follows: the weight with catalyzer is benchmark, and cupric oxide is 20.0wt%～50.0wt%, is preferably 30.0wt%～40.0wt%; Zinc oxide is 50.0wt%～80.0wt%, is preferably 60.0wt%～70.0wt%; Cupric oxide and zinc oxide weight ratio scope are 2: 1～1: 4, and optimum range is 1: 1～1: 2; The BET specific surface area is 30～60m
2/ g, optimum range are 35～45m
2/ g; Pore volume is 0.1～0.25cm
3/ g, optimum range are 0.15～0.20cm
3/ g; Average pore diameter is 10～25nm, and optimum range is 15～20nm.
The hydro-sweetening Preparation of catalysts method that is provided is: the co-precipitation solution of soluble copper salt and zinc salt is mixed with a kind of organic acid soln or organic acid ammonium salt solution precipitator, co-precipitation goes out the mixture of a kind of insoluble mantoquita and zinc salt, obtain filter cake through aging, filtration, drying, roasting obtain cupric oxide and zinc oxide mixture again, be pressed into the gasoline fraction mercaptan-eliminating catalyst at last, catalyzer can be sheet, column, strip, spherical or other suitable shape.
Described soluble copper salt and zinc salt are one or more in chlorate, vitriol, acetate, the nitrate; The organic acid coprecipitator is one or more in oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid and the ammonium salt thereof.
The selective hydrodesulfurization reaction conditions is: 200～400 ℃ of temperature of reaction, hydrogen dividing potential drop are 0.5～4.0MPa, and volume space velocity is 1.0～5.0h
-1The hydro-sweetening reaction conditions is: reaction pressure is generally 0.5MPa～4.0MPa, and temperature of reaction is generally 160 ℃～300 ℃, and volume space velocity is generally 0.5～10h during liquid
-1During actually operating, above-mentioned processing condition can be according to feedstock property by this area general knowledge adjustment to produce the gasoline products of required quality index.
Light benzine raw material of the present invention comprises catalytically cracked gasoline, coker gasoline or pressure gasoline etc., can be a kind of, also can be two or more mixture, and its boiling range is 30～220 ℃.The preferred raw material of the present invention is the FCC gasoline that sulphur content is lower than 700 μ g/g.
Adopt method of the present invention can handle full cut FCC gasoline, gasoline stocks does not need fractionation, sepn process in the middle of also not needing after the selective hydrodesulfurization, and flow process is simple, and is easy to operate, and production cost is low.Certainly, carry out operations such as sepn process after also can adopting raw material fractionation or selective desulfurization if desired.
The inventive method is handled by suitable selective desulfurization and special mercaptan removal, total sulfur content in the gasoline stocks can be reduced to below the 10 μ g/g, mercaptan sulfur in the product is reduced to below the 5.0 μ g/g, and research octane number (RON) (RON) loss is lower than 2.0 units, also can require to produce the cleaning product of different sulphur contents according to quality product.
Embodiment
In the inventive method, selective desulfurization catalyst needs prevulcanized to handle before use, can adopt method for pre-sulphuration in outer prevulcanized of device or the device, and this area ordinary method is adopted in prevulcanized.Pre-vulcanization process and condition are as follows in a kind of concrete device: vulcanized oil is a straight-run spirit, and vulcanizing agent is CS
2, CS
2Concentration is 1.0 quality %; Sulfide stress is 0.5～4.0MPa, and hydrogen to oil volume ratio is 100: 1～500: 1, and the vulcanized oil volume space velocity is 1.0～5.0h
-1, be 100～300 ℃ of following constant temperature 5～20 hours in temperature, 200～400 ℃ of following constant temperature 5～20 hours.
Hydrogenating desulfurization alcohol catalyst mantoquita of the present invention and zinc salt coprecipitation process are as follows:
With soluble copper salt and zinc salt is that preparation of raw material becomes co-precipitation work salts solution, and strength of solution is 0.1M～0.8M, preferably 0.3M～0.5M; With organic acid or organic acid ammonium salt preparation precipitant solution, strength of solution is 0.1M～0.8M, best 0.3M～0.5M, and its pH value is 3～7, is preferably 4～6; Salts solution and the precipitant solution of will working respectively then is heated to 15 ℃～70 ℃, is preferably 25 ℃～45 ℃.Under insulation and agitation condition, they are mixed, obtain the coprecipitate that suspends, step such as wear out, filter, dry and obtain the coprecipitate filter cake through being incubated again.The precipitation agent consumption is preferably 10%～15% (by weight percentage) for being precipitated out 5%～20% (by weight percentage) that required chemical reaction measures fully above cupric ion in the work salts solution and zine ion.The organic acid coprecipitator is one or more in oxalic acid, propanedioic acid, Succinic Acid, pentanedioic acid and the ammonium salt thereof.
Above-mentioned co-precipitation mode can be that the work salts solution is joined in the precipitant solution, or precipitant solution is joined in the work salts solution, also can be after they are heated respectively, joins in the settling bath simultaneously.
Above-mentioned coprecipitation process can be work salt to be joined respectively in two parallel header tanks with precipitant solution be heated to 15～70 ℃, is preferably 25～45 ℃, joins simultaneously in the low level settling bath under insulation and agitation condition.
Hydro-sweetening Preparation of catalysts process provided by the invention is:
Gained coprecipitate filter cake is earlier dry, and roasting again mixes resulting cupric oxide and zinc oxide mixture and pressing aid agent then, and compression moulding promptly makes catalyzer.The pressing aid agent is 2～5% with the ratio of above-mentioned cupric oxide and zinc oxide mixture weight; The pressing aid agent can be graphite, stearic acid etc.; Drying temperature is 80
℃～150 ℃, be preferably 100 ℃～120 ℃, 6～10 hours time, be preferably 8～10 hours; Maturing temperature is 300 ℃～500 ℃, is preferably 340 ℃～370 ℃, and the time is 2～6 hours, is preferably 4～5 hours.
Above-mentioned cupric oxide and zinc oxide mixture through step gained such as super-dry, roastings also can be mixed together evenly with pressing aid agent and tackiness agent, are pressed into catalyzer.Tackiness agent can be aluminum oxide, zeolite, silicon carbide, silicon-dioxide, silica-alumina, silicate, aluminate and borate etc.Certainly, the hydrogenating desulfurization alcohol catalyst of the present invention's use can also adopt other proper method preparation.
Can contain other auxiliary agent in the hydrogenating desulfurization alcohol catalyst, to improve catalyst performance, common auxiliary agent comprises chromic oxide, manganese oxide, magnesium oxide, barium oxide, aluminum oxide etc.
Mercaptan-eliminating catalyst need reduce before reaction, and reduction is adopted the method for capable territory routine and carried out.A kind of concrete catalyst reduction process and condition are: in the catalyst-assembly reactor, at pure hydrogen or contain under the hydrogen and nitrogen gas, be generally 0.5MPa～4.0MPa at reacting system pressure, hydrogen catalyst volume ratio was generally 100: 1～500: 1, and reduction temperature is generally 160 ℃～300 ℃ following constant temperature reduction and was generally 1～10 hour.
Hydrogenating desulfurization provided by the invention/mercaptan removal composite reaction system is carried out in two sections tandem reactors.In first section reactor a kind of catalyst for selectively hydrodesulfurizing is housed, a kind of hydrogenating desulfurization alcohol catalyst is housed in second section reactor.Gasoline stocks enters first section reactor and carries out the selective hydrodesulfurization reaction, reaction product enters second section reactor again and contacts with the hydrogenating desulfurization alcohol catalyst, the gasoline products sulphur content that obtains after the reaction is lower than 5.0 μ g/g less than 10 μ g/g, mercaptan sulfur, and research octane number (RON) (RON) loss is lower than 2.0 units.
Further specify the solution of the present invention and effect below by embodiment, but therefore do not limit the present invention.
Example 1
95.6 gram cupric nitrates and 235 gram zinc nitrates are mixed with 2000 milliliters of work salts solutions, 170 gram oxalic acid are mixed with 3000 milliliters of precipitant solution, and its pH value is adjusted to 3.0, join respectively then in two parallel high level tanks and be heated to 20 ℃, when treating low level settling bath heating in water bath to 20 ℃, start agitator, under strong mixing, two kinds of solution and flowing in the settling bath in 30 minutes, under weak stirring, wore out 0.5 hour then, then throw out is emitted, filter, spend the night and dry, obtain the coprecipitate filter cake, 110 ℃ dry 8 hours down, rose to 360 ℃ by room temperature in 6 hours then, 360 ℃ of following constant temperature calcinings 4 hours, make catalyst Precursors, add an amount of graphite then, mix the back compression molding, promptly get mercaptan-eliminating catalyst of the present invention, be numbered RM-1.RM-1 catalyzer rerum natura is listed in table 1.
Comparative example 1
It is coprecipitator with yellow soda ash that this example adopts the method for US4876402.
The solution (16 liters) of 417 gram copper (adding with the cupric nitrate form) and 858 gram zinc (adding with the zinc nitrate form) are heated to about 43 ℃, spray into and be in the mechanical stirring constant temperature also in 12.75 liters of the sodium carbonate solutions of 60 ℃ 15.7% (weight).The pH value about 7.9～8.5 that precipitation mixture is last.After precipitation, copper-zinc subcarbonate is filtered, wash with 37.8 ℃～48.8 ℃ deionized water making beating then, the washing four times of filtering so repeatedly, pull an oar to remove sodium salt wherein, makes that the sodium content in the filter cake after the roasting reduces to 0.1～0.15% (weight).Press step and condition drying, roasting and the moulding of example 1 then, make the comparative catalyst, be numbered RM-C.RM-C catalyzer rerum natura is listed in table 1.
Example 2
95.6 gram cupric nitrates and 235 gram zinc nitrates are mixed with 700 milliliters of work salts solutions, 160 gram ammonium oxalate are mixed with 1500 milliliters of precipitant solution, its pH value is about 7.0.Then salts solution is joined in the Lower tank, coprecipitator solution joins in the high level tank, be heated to 55 ℃ simultaneously, under insulation and agitation condition in 15 minutes, precipitant solution is joined the work salts solution, carry out drying, roasting, moulding by the program of example 1 and condition then and make mercaptan-eliminating catalyst, be numbered RM-2.RM-2 catalyzer rerum natura is listed in table 1.
Example 3
151.8 gram cupric nitrates and 182.7 gram zinc nitrates are mixed with 2000 milliliters of work salts solutions, 230 gram oxalic acid are mixed with 3000 milliliters of precipitant solution, the pH value is 4.0.The salts solution of will working joins in the high level tank, precipitant solution is put in the low level settling bath, the salts solution of will working is heated to 45 ℃, precipitant solution is heated to 65 ℃, under insulation and agitation condition, the salts solution of will working in 20 minutes joins in the precipitant solution, presses step and condition drying, roasting and the moulding of example 1 then, make mercaptan-eliminating catalyst, be numbered RM-3.RM-3 catalyzer rerum natura is listed in table 1.
Table 1 catalyzer of the present invention and the contrast of reference agent rerum natura
Example 4
A kind of moderate sulfur content of the RM-1 catalyst treatment of this case expedition example 1 and medium olefin(e) centent FCC gasoline desulfur inferior and mercaptan removal effect.Reaction conditions is lower than ≯ 2.0 unit controls of 5.0 μ g/g, research octane number (RON) RON loss by product total sulfur content ≯ 10 μ g/g, mercaptan sulfur, and the product sulphur content index of Sheng Chaning is higher if desired, can corresponding reduction operating severity.
1), FCC gasoline hydrodesulfurizationmethod
Evaluation test is to carry out on the device of fixed-bed reactor, and 60ml MoO packs in the reactor A
3(8.0wt%)-CoO (3.5wt%)-P
2O
5(2.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyzer.
Airtight qualified after, at first carry out catalyst vulcanization.Vulcanized oil is a straight-run spirit, and vulcanizing agent is CS
2, CS
2Concentration is 1.0m%; Sulfide stress is 1.0MPa, and hydrogen to oil volume ratio is 400: 1, and the vulcanized oil volume space velocity is 2.0h
-1, be 240 ℃ of following constant temperature 7 hours in temperature, 330 ℃ of following constant temperature 7 hours.
Sulfuration is cooled to 280 ℃ after finishing.The full cut FCC of a kind of poor quality of swap-in gasoline stocks oil, the hydrogen dividing potential drop is 1.0MPa, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 400: 1.
2), RM-1 catalyst desulfurizing alcohol
Pack in the reactor B 30 milliliters of RM-1 catalyzer, granularity is 20～40 orders.Earlier logical hydrogen (gas agent ratio is 400: 1), hydrogen pressure is 1.0MPa, rises to 260 ℃ by room temperature in 6 hours, then constant temperature reductase 12 hour.
Be cooled to 220 ℃ after the reduction, advance reactor A hydrogenating desulfurization product, the gasoline volume space velocity is 2.0h
-1, the hydrogen dividing potential drop is 1.0MPa, hydrogen to oil volume ratio is 400: 1.After oil-feed is stablized 100 hours, sampling analysis.Table 2 has been listed the main character of raw material and product.
Table 2RM-1 catalyst treatment full cut FCC gasoline stocks and product characteristics
Comparative example 2
This comparative example investigate comparative example 1 RM-C catalyst treatment example 4 FCC gasoline desulfur inferior and mercaptan removal effect.
The Hydrobon catalyst that adopts is identical with example 4, estimates the method according to example 4.Table 3 has been listed the main character of raw material and product.
Table 3RM-C catalyst treatment full cut FCC gasoline stocks and product characteristics
From table 2 and table 3 as can be seen: method of the present invention can be reduced to 9.0 μ g/g by 480 μ g/g with the sulphur content of full cut FCC gasoline, mercaptans content is reduced to 2.0 μ g/g by 38 μ g/g, olefin(e) centent is reduced to 19.2v% by 25.0v%, and research octane number (RON) RON loses 1.5 units, C
5 +Yield of gasoline 99.9wt%; The catalyzer of reference can be reduced to 18.5 μ g/g by 480 μ g/g with the sulphur content of full cut FCC gasoline, and mercaptans content is reduced to 6.0 μ g/g by 38 μ g/g, and olefin(e) centent is reduced to 18.2v% by 25.0v%, and research octane number (RON) RON loses 2.3 units, C
5 +Yield of gasoline 99.9wt%.
Example 5
A kind of low-sulfur of RM-2 catalyst treatment of this case expedition example 2, the FCC gasoline desulfur inferior and the mercaptan removal effect of high olefin content.
Evaluation is according to the method for example 4.Table 4 has been listed the main character of raw material and product.
Table 4RM-2 catalyst treatment full cut FCC gasoline stocks and product characteristics
As can be seen from Table 4: method of the present invention can be reduced to 3.0 μ g/g by 192 μ g/g with the sulphur content of low-sulfur, high olefin FCC gasoline, mercaptans content is reduced to 0.7 μ g/g by 24 μ g/g, olefin(e) centent is reduced to 39.5v% by 47.6v%, and research octane number (RON) RON loses 1.6 units, C
5 +Yield of gasoline 99.9wt%.
Example 6
A kind of high sulfur content of RM-3 catalyst treatment of this case expedition example 3, the FCC gasoline desulfur inferior and the mercaptan removal effect of low olefin-content.
Evaluation is according to the method for example 4.Table 5 has been listed the main character of raw material and product.
Table 5RM-3 catalyst treatment full cut FCC gasoline stocks and product characteristics
As can be seen from Table 5: method of the present invention can be reduced to 10.0 μ g/g by 660 μ g/g with the sulphur content of high-sulfur, low alkene FCC gasoline, mercaptans content is reduced to 2.0 μ g/g by 32 μ g/g, olefin(e) centent is reduced to 24.5v% by 31.0v%, and research octane number (RON) RON loses 1.8 units, C
5 +Yield of gasoline 99.9wt%.
Therefore, the selective hydrodesulfurization that this invention provides/mercaptan removal combination process can be processed as the full cut FCC of poor quality gasoline the high-quality cleaning product that sulphur content ≯ 10 μ g/g, mercaptan sulfur are lower than 5.0 μ g/g, and research octane number (RON) RON loses ≯ 2.0 units.
Claims (10)
1, a kind of method of producing low sulfur gasoline by using light weight gasoline, comprise that gasoline stocks carries out selective hydrodesulfurization in the presence of catalyst for selectively hydrodesulfurizing, reaction product contacts with the hydrogenating desulfurization alcohol catalyst again, obtain the low-sulphur oil product after the reaction, it is characterized in that described hydrogenating desulfurization alcohol catalyst is benchmark with weight, cupric oxide content is 20.0wt%～50.0wt%, and zinc oxide content is 50.0wt%～80.0wt%.
2, in accordance with the method for claim 1, it is characterized in that described catalyst for selectively hydrodesulfurizing composition comprises: the weight with catalyzer is benchmark, and catalyzer contains MoO
31.0～18.0w%, CoO0.1～6.0w%, Co/Mo atomic ratio 0.1～1.0, catalyzer contain potassium and phosphorus component simultaneously, contain potassium 0.2～10.2w%, P/K atomic ratio 0.1～10.0.
3, according to claim 1 or 2 described methods, the pore volume that it is characterized in that described catalyst for selectively hydrodesulfurizing is 0.3～1.3ml/g, and specific surface area is 150～300m
2/ g.
4, in accordance with the method for claim 1, it is characterized in that described hydrogenating desulfurization alcohol catalyst is benchmark with weight, cupric oxide content is 30.0wt%～40.0wt%, and zinc oxide content is 60.0wt%～70.0wt%.
5, in accordance with the method for claim 1, it is characterized in that cupric oxide and zinc oxide weight ratio are 2: 1～1: 4 in the described hydrogenating desulfurization alcohol catalyst.
6, in accordance with the method for claim 1, the specific surface area that it is characterized in that described hydrogenating desulfurization alcohol catalyst is 30～60m
2/ g, pore volume are 0.1～0.25cm
3/ g, average pore diameter is 10～25nm.
7, in accordance with the method for claim 1, the specific surface area that it is characterized in that described hydrogenating desulfurization alcohol catalyst is 35～45m
2/ g, pore volume are 0.15～0.20cm
3/ g, average pore diameter is 15～20nm.
8, in accordance with the method for claim 1, it is characterized in that the selective hydrodesulfurization reaction conditions is: 200～400 ℃ of temperature of reaction, hydrogen dividing potential drop are 0.5～4.0MPa, and volume space velocity is 1.0～5.0h
-1
9, in accordance with the method for claim 1, it is characterized in that the hydro-sweetening reaction conditions is: reaction pressure is 0.5MPa～4.0MPa, and temperature of reaction is 160 ℃～300 ℃, and volume space velocity is 0.5～10h during liquid
-1
10, in accordance with the method for claim 1, it is characterized in that described gasoline stocks comprises catalytically cracked gasoline, coker gasoline or pressure gasoline.
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| CN102041062B (en) * | 2009-10-16 | 2013-07-24 | 中国石油化工股份有限公司 | Hydrodesulfurization method for light oil |
| CN101940936A (en) * | 2010-08-20 | 2011-01-12 | 上海胜帮煤化工技术有限公司 | Coal tar hydrogenation protective agent and preparation method thereof |
| CN101940936B (en) * | 2010-08-20 | 2013-04-24 | 陕西煤业化工集团(上海)胜帮化工技术有限公司 | Coal tar hydrogenation protective agent and preparation method thereof |
| CN102451693A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation mercaptan-removal catalyst and its preparation method and use |
| CN102451693B (en) * | 2010-10-15 | 2014-04-02 | 中国石油化工股份有限公司 | Hydrogenation mercaptan-removal catalyst and preparation method and use thereof |
| CN102399588A (en) * | 2011-09-28 | 2012-04-04 | 大连理工大学 | Method for reducing sulfur content in sulfur-containing light oil |
| CN104650965A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for catalyzing deep desulfurization of gasoline by using Ni-Mo-Co-containing catalyst |
| CN104650964A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for catalyzing gasoline desulfurization by Ni-Mo-containing catalyst |
| CN104650967A (en) * | 2013-11-22 | 2015-05-27 | 中国石油天然气股份有限公司 | Method for catalyzing deep desulfurization of gasoline by Ni-containing catalyst |
| CN104650965B (en) * | 2013-11-22 | 2017-01-11 | 中国石油天然气股份有限公司 | Method for catalyzing deep desulfurization of gasoline by using Ni-Mo-Co-containing catalyst |
| CN105670688A (en) * | 2014-11-19 | 2016-06-15 | 中国海洋石油总公司 | Preparation method of sulfur-free gasoline |
| CN105670688B (en) * | 2014-11-19 | 2017-07-11 | 中国海洋石油总公司 | A kind of method for producing sweet gasoline |
| CN108018075A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | A kind of method of gasoline desulfurization and the device of gasoline desulfurization |
| CN108018075B (en) * | 2016-10-31 | 2020-04-28 | 中国石油化工股份有限公司 | Gasoline desulfurization method and gasoline desulfurization device |
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