CN101376835A - Gasoline hydrofinishing startup method and gasoline hydrofinishing operation method - Google Patents
Gasoline hydrofinishing startup method and gasoline hydrofinishing operation method Download PDFInfo
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- CN101376835A CN101376835A CNA2007100126743A CN200710012674A CN101376835A CN 101376835 A CN101376835 A CN 101376835A CN A2007100126743 A CNA2007100126743 A CN A2007100126743A CN 200710012674 A CN200710012674 A CN 200710012674A CN 101376835 A CN101376835 A CN 101376835A
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Abstract
The invention discloses a hydrogenation refining method of gasoline with poor quality. The material of the gasoline and hydrogen pass through at least two hydrogenation refining catalyst bed layers in turn under the hydrogenation refining conditions; the active metal contents of the at least two hydrogenation refining catalyst bed layers along the material floating direction are reduced; the active metal contents in the catalyst are differed by 5.0wt to 18.0 wt percent; a liquid containing an active metal compound is adopted to dip the carrier of the catalyst for preparing at least one hydrogenation refining catalyst; then the carrier of the catalyst after being dipped is dried; no baking treatment is carried out. The invention also discloses an operation method for the hydrogenation refining of gasoline with poor quality which adopts a short low temperature curing time. The hydrogenation refining method has the advantages of good desulfurizing selectivity and less octane number loss. The method can product a clean gasoline product with low sulfur and high octane number.
Description
Technical field
The present invention relates to a kind of gasoline hydrofinishing method and gasoline hydrofinishing start-up method, specifically, the present invention relates to the start-up method of inferior patrol cut selective hydrodesulfurization method and selective hydrodesulfurization.
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 tighter, 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.
At present, catalytic cracking (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.
Hydrofining technology, particularly selective hydrodesulfurization (HDS) technology is the important means of effective elimination FCC gasoline sulfide.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.
CN 02133136.7 has introduced a kind of gasoline selective Hydrobon catalyst 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.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, and lighting end is through the soda finishing mercaptan removal, last running and hydrogen together with MoO
3-CoO/Al
2O
3The selective hydrodesulfurization reaction is carried out in the Hydrobon catalyst contact, and the 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.
The shortcoming of above-mentioned patented method is that the catalyzer that uses in the hydrodesulfurization must be converted into oxide compound by 4～10 hours metal-salts with dipping of roasting in preparation process under 450 ℃～550 ℃ high temperature, as MoO
3, CoO, WO
3Or NiO, vulcanizing 16～32 hours in the process of going into operation under 230 ℃～280 ℃ low temperature is sulfide with oxygenate conversion, as MoS
2, Co
9S
8, WS
2Or Ni
3S
2Therefore, its shortcoming is a catalytic preparation process flow process complexity, and energy consumption is higher.In the process that particularly goes into operation under the low temperature curing time long, on the one hand on-stream time is long, on the other hand, causes catalyzer HDS selectivity poor slightly, Study on product method octane value (RON) loses more.
The main purpose of FCC gasoline selective hydrogenation is that wherein sulphur is removed as far as possible, and alkene wherein is high-octane number component, should suitably keep.But desulfurization and the rare hydrocarbon of reservation are conflicting in hydrogenation reaction, hydrogenating desulfurization and hydrogenation of olefins are saturated all to carry out on the catalyst hydrogenation activity center, if the hydrogenation activity of catalyzer increases, then desulfurization degree improves, the alkene saturation exponent also improves simultaneously simultaneously, and the loss of octane number that advances the face hydrogenated products is more.Therefore, improving means such as activity of such catalysts simply improves desulfurization degree and is unwell to the requirement that selectively hydrogenating and desulfurizing inferior gasoline is produced low-sulfur, high octane gasoline products.
Summary of the invention
At the deficiencies in the prior art, the invention provides the method that low-sulfur, high-octane rating premium product are produced in a kind of inferior patrol hydrofining, and the start-up method of this hydrofinishing process.
Inferior patrol hydrofinishing process of the present invention comprises following content: gasoline stocks and hydrogen pass through at least two Hydrobon catalyst beds successively under the hydrofining condition, described at least two Hydrobon catalyst beds reduce along Flow of Goods and Materials direction active metallic content, reaction mass is earlier by the high Hydrobon catalyst of active metallic content, then by the low Hydrobon catalyst of active metallic content, active metallic content can differ (in active metal oxide) 5.0wt%～18.0wt% in the catalyzer, preferably differ 8.0wt%～15.0wt%, hydrogenation active metals generally is selected from W, Mo, among Ni and the Co one or more, can contain conventional auxiliary agent, as K, Ca, P, Si, F, B, among Ti and the Zr one or more.At least a described Hydrobon catalyst adopts the solution impregnated catalyst carrier preparation that contains active metallic compound, the dipping back 80 ℃～160 ℃ dry 6～20 hours down, do not carry out calcination process.Preferred employed Hydrobon catalyst all adopts the method preparation of not roasting after dipping, the drying.
The inferior patrol hydrofinishing process process of going into operation of the present invention comprises following content: in the catalyst-assembly reactor, vulcanized 6～12 hours under 200 ℃～260 ℃ low temperature, vulcanized 6～12 hours under 300 ℃～380 ℃ high temperature, obtain the sulphided state catalyzer.After the sulfuration bed temperature is adjusted to temperature requiredly, carries out the hydrofining reaction of bad gasoline.
In the inferior patrol hydrofinishing process of the present invention, be used by the Hydrobon catalyst that adopts the different activities metal content, Hydrobon catalyst adopts special preparation method's preparation (after being support of the catalyst dipping reactive metal simultaneously, only carry out drying, do not carry out calcination process), particularly through sulfuration of the present invention go into operation (promptly reducing the cryogenic vulcanization time) after the process, obtained beyond thought technique effect, promptly improved the hydrodesulfurization performance of bad gasoline, reduce the saturated performance of hydrogenation of olefins in the gasoline stocks simultaneously, reached the double goal that deep desulfuration and loss of octane number reduce.
Embodiment
In the inferior patrol hydrofinishing process of the present invention, the hydrofining reaction condition can specifically be determined by this area general knowledge according to stock oil character and product requirement.The general technology condition 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
-1～12.0h
-1, hydrogen to oil volume ratio is generally 200:1～1000:1; The hydrogen dividing potential drop is preferably 0.8MPa～3.0MPa, and temperature of reaction is preferably 250 ℃～280 ℃, and volume space velocity is preferably 3.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is preferably 200:1～700:1.
In the inferior patrol hydrofinishing process of the present invention, active metal oxide content is 8.0wt%～20.0wt% in the described high-activity hydrofining catalyst, is preferably 10.0wt%～18.0wt%; Auxiliary agent content is 1.0wt%～6.0wt%, particularly 1.5wt%～5.0wt%; Active metal oxide content is 1.0wt%～12.0wt%, particularly 3.0wt%～10.0wt% in the SA Hydrobon catalyst, and auxiliary agent content is 1.0wt%～6.0wt%, particularly 1.5wt%～5.0wt%.Reactive metal is selected from one or more among W, Mo, Ni and the Co in the described catalyzer, preferably contains group vib metal (W and/or Mo) and VIII family metal (Ni and/or Co) simultaneously, and VIII family metal is 0.1-1.0 with group vib atoms metal ratio.
This catalyzer can adopt immersion process for preparing, can adopt step impregnation method, also can adopt co-impregnation.Adsorptive capacity such as preferred is flooded altogether.
Contain urea in the Hydrobon catalyst dipping solution of the present invention, urea/VIII family metal molar is preferably 0.20:1～1.0:1 than 0.10:1～1.5:1.
The supported catalyst of Hydrobon catalyst of the present invention descended dry 6～20 hours at 80 ℃～160 ℃, obtained dry catalyst.Drying is 8～12 hours under being preferably in 100 ℃～130 ℃, obtains dry catalyst.
In the gasoline stocks hydrofinishing process of the present invention, two kinds of different activities Hydrobon catalysts of general employing are used in combination and get final product, be that high reactivity/low activity catalyst is used in combination, its volume percent is 20/80～80/20, wherein highly active Hydrobon catalyst is positioned at the upstream of SA Hydrobon catalyst, promptly reduces along the logistics direction is active.
A kind of concrete preparation process of Hydrobon catalyst of the present invention is as follows:
1, dipping: will contain the salt (as ammonium molybdate, Xiao Suangu, metatungstic acid or nickelous nitrate etc.) of required active metal component and the steeping fluid that dispersion agent urea is made into, load to on one or more the carrier in aluminum oxide, siliceous aluminum oxide or the titanium-contained aluminum oxide, obtain supported catalyst.
2, drying: the supported catalyst in the step 1 was descended dry 6～20 hours at 80 ℃～160 ℃, promptly obtain dry catalyst.
Hydrobon catalyst start-up method of the present invention:
1, dress agent: the catalyzer of step preparation is packed in the reactor by the processing method requirement.
2, sulfuration: in reactor, in the presence of vulcanizing agent, vulcanized 6～12 hours down, vulcanized 6～12 hours down, obtain the sulphided state catalyzer at 310 ℃～350 ℃ at 220 ℃～240 ℃.
3, advance stock oil: the sulfuration rear catalyst is reduced to temperature of reaction, and the swap-in bad gasoline is adjusted to suitable hydrogenation desulphurization reaction condition then and carried out hydrofining reaction.
The vulcanizing agent of the vulcanisation step of start-up method of the present invention is generally easy decomposition and and H
2Can form H
2The sulfide of S, particularly CS
2Or dimethyl disulfide (DMDS); Sulfuration can be adopted wet method sulfuration or dry method sulfuration, and wet method sulfuration or dry method sulfurized process are well known to those skilled in the art.When for example adopting the wet method sulfuration, vulcanizing agent is dissolved in the vulcanized oil, vulcanized oil is generally hydrocarbonylation thing, particularly straight-run spirit, virgin kerosene or the hydrotreated naphtha that does not contain alkene.The content of vulcanizing agent in vulcanized oil is generally 0.5m%～3.0m%, is preferably 0.8m%～2.0m%.
Vulcanization process condition of the present invention is: sulfide stress is generally 0.5MPa～4.0MPa, and curing temperature is 200 ℃～260 ℃ and vulcanized 4～12 hours down that 300 ℃～380 ℃ were vulcanized 4～12 hours down, and volume space velocity is generally 1.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is generally 200:1～1000:1; Hydrogen sulfide sectional pressure is preferably 0.8MPa～2.0MPa, and curing temperature is preferably 220 ℃～240 ℃ and vulcanized 6～10 hours down, and 310 ℃～350 ℃ were vulcanized 6～10 hours down, and volume space velocity is preferably 2.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is preferably 200:1～700:1.
Bad gasoline of the present invention is fluid catalytic cracking (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.Described inferior patrol hydrogenating materials can be full cut FCC gasoline, and boiling range is generally 30 ℃～220 ℃, particularly 30 ℃～180 ℃.Also can be for being lighting end and last running with the prefractionation of FCC gasoline, the cut point temperature is 40 ℃～100 ℃, preferred 50～90 ℃, the yield of lighting end is respectively the 20.0wt%～50.0wt% of gasoline stocks, processing such as mercaptan removal are carried out in lighting end, last running adopts the inventive method to carry out hydrofining, and both mixing obtain final gasoline products then.
The filling characteristics of Hydrobon catalyst system provided by the invention in reactor are that high activated catalyst is positioned at the upstream along the logistics direction, and low activity catalyst is positioned at the downstream, and reaction mass contacts with high activated catalyst earlier, and the back contacts with low activity catalyst.Hydrodesulfurization process can produce a large amount of reaction heat, makes reactor lower part temperature higher (beds temperature rise), and industrial generally is to come the temperature rise of control catalyst bed by the method for injecting a large amount of cold hydrogen at the reactor middle part.The present invention will be placed on the downstream than the catalyzer of low catalytic activity, can annotate cold hydrogen less, even not use cold hydrogen, not only save hydrogen usage, effectively utilized system thermal, but also realized avoiding under the high temperature hydrogenation excessive, it is saturated to suppress hydrogenation of olefins, reduces the purpose of loss of octane number.
Further specify the solution of the present invention and effect below by embodiment, but therefore do not limit the present invention.
Example 1
This example step impregnation method prepares a kind of high reactivity MoO
3(13.0wt%)-CoO (4.0wt%)-P
2O
5(1.5wt%)-K
2O-(2.0wt%)/Al
2O
3Catalyzer.
Take by weighing 1000g and intend thin water-aluminum hydroxide powder (Al
2O
3Contents on dry basis is 78wt%), adding accounts for Al
2O
3The sesbania powder extrusion aid of butt 5wt%, mass concentration are 10% aqueous nitric acid 200ml, mix and roll being mixed into plastic powder, prepare the cylinder bar that diameter is 1.5mm with banded extruder, drying is 8 hours under 120 ℃, support of the catalyst is prepared in 500 ℃ of following roastings 5 hours;
Press P on the catalyzer
2O
5Content is 1.5wt%, K
2O content is 2.0wt%, gets quantitative phosphoric acid, saltpetre, adds deionized water, is made into the 120ml steeping fluid, then, sprays on the said catalyst carrier of 160g.120 ℃ dry 10 hours down, P is prepared in 500 ℃ of following roastings 5 hours
2O
5(1.5wt%)-K
2O-(2.0wt%)/Al
2O
3Catalyst intermediate.
Press MoO on the catalyzer
3Content is that 13.0wt%, CoO content are 4.0wt%, gets quantitative molybdenum oxide, cobaltous dihydroxycarbonate, joins the deionized water of ammonia content 8%.Then according to urea/CoO mol ratio 0.80:1 weighing urea and join above-mentioned MoO
3In-CoO the solution, be made into the 60ml steeping fluid.Then, spray on the above-mentioned catalyst intermediate of 80g.Drying is 8 hours under 120 ℃, prepares high activated catalyst, is called for short HAC.
Example 2
This example co-impregnation prepares a kind of low activity MoO
3(3.0wt%)-CoO (1.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyzer.
Support of the catalyst is with reference to example 1 preparation.
Press MoO on the catalyzer
3Content is that 3.0wt%, CoO content are 1.0wt%, K
2O content is 2.0wt% and urea/CoO mol ratio 0.30:1, gets quantitative ammonium molybdate, Xiao Suangu, saltpetre and urea, adds the deionized water of ammonia content 16%, is made into the 110ml steeping fluid, then, sprays on the said catalyst carrier of 165g.Drying is 8 hours under 120 ℃, prepares low activity catalyst, is called for short LAC.
Comparative example 1
This comparative example co-impregnation prepares a kind of MoO
3(8.0wt%)-CoO (3.5wt%)-P
2O
5(2.0wt%)-K
2O (2.0wt%)/Al
2O
3Catalyzer.
Support of the catalyst is with reference to example 1 preparation.
Press MoO on the catalyzer
3Content is that 8.0wt%, CoO content are 3.5wt%, P
2O
5Content is 2.0wt%, K
2O content is 2.0wt%, gets quantitative ammonium molybdate, Xiao Suangu, phosphoric acid and saltpetre, adds the deionized water of ammonia content 13%, is made into the 110ml steeping fluid, then, sprays on the said catalyst carrier of 165g.Drying is 8 hours under 120 ℃, and drying is 8 hours under 500 ℃, prepares relatively catalyzer of burning attitude, abbreviation OCC.
Example 3
This example provides a kind of FCC gasoline desulfur effect inferior.
(1), stock oil lighting end, last running cutting
With 70 ℃ be the cut point temperature FCC gasoline is separated into＜70 ℃ of lighting ends and 70 ℃ of last running, table 1 listed FCC gasoline,＜70 ℃ of lighting ends and the character of 70 ℃ of last running.
The character of FCC gasoline, lighting end and last running in table 1 example 3
(2),〉70 ℃ of heavy fractioning hydrogenation desulfurization
Evaluation test is to carry out on the device of fixed-bed reactor, pack in the reactor 50ml high reactivity HAC and a kind of low activity LAC catalyzer.The former with the latter volume ratio is 50/50.
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 1.6MPa, and hydrogen to oil volume ratio is 300:1, and the vulcanized oil volume space velocity is 3.0h
-1, be 230 ℃ of following constant temperature 10 hours in temperature, 320 ℃ of following constant temperature 10 hours;
After sulfuration finishes, be cooled to 280 ℃, change 70 ℃ of double distilleds are divided into stock oil, the hydrogen dividing potential drop is 1.6MPa, volume space velocity is 4.0h
-1, hydrogen to oil volume ratio is 300:1.Steady running sampling analysis in 100 hours.
(3),〉70 ℃ of heavy fractioning hydrogenation desulfurization mix with＜70 ℃ of lighting ends
70 ℃ of heavy fractioning hydrogenation desulphurization reaction things with presort distilled＜70 ℃ lighting end according to the cutting mixed.Table 2 has been listed raw material FCC gasoline and the character of handling back clean gasoline product.
The character of table 2 example 3 oil products
As can be seen from Table 2: method of the present invention can be reduced to 26 μ g/g (HDS leads 96.1%) by 660 μ g/g with the sulphur content of FCC gasoline, olefin(e) centent is reduced to 26.2v% (alkene saturation exponent 15.5%) by 31.0v%, research octane number (RON) RON loses 0.6 unit, C
5 +Yield of gasoline 99.9wt% can be processed as FCC gasoline inferior the high-quality cleaning product of sulphur content ≯ 50 μ g/g.
Comparative example 2
This comparative example provides a kind of FCC gasoline desulfur effect inferior of catalyst treatment in the comparative example 1.
(1), stock oil lighting end, last running cutting
With 70 ℃ be the cut point temperature FCC gasoline is separated into＜70 ℃ of lighting ends and 70 ℃ of last running, table 1 listed FCC gasoline,＜70 ℃ of lighting ends and the character of 70 ℃ of last running.
(2),〉70 ℃ of heavy fractioning hydrogenation desulfurization
Evaluation test is to carry out on the device of fixed-bed reactor, OCC catalyzer in the 50ml comparative example 1 of packing in the reactor.
Airtight qualified after, at first carry out catalyst vulcanization.Vulcanized oil is a virgin kerosene, and vulcanizing agent is dimethyl disulfide (DMDS), and DMDS concentration is 1.5m%; Sulfide stress is 1.6MPa, and hydrogen to oil volume ratio is 300:1, and the vulcanized oil volume space velocity is 3.0h
-1, be 230 ℃ of following constant temperature 16 hours in temperature, 280 ℃ of following constant temperature 12 hours;
After sulfuration finishes, change 70 ℃ of double distilleds are divided into stock oil, the hydrogen dividing potential drop is 1.6MPa, volume space velocity is 4.0h
-1, hydrogen to oil volume ratio is 300:1.Steady running sampling analysis in 100 hours.
(3),〉70 ℃ of heavy fractioning hydrogenation desulfurization mix with＜70 ℃ of lighting ends
70 ℃ of heavy fractioning hydrogenation desulphurization reaction things with presort distilled＜70 ℃ lighting end according to the cutting mixed.Table 3 has been listed raw material FCC gasoline and the character of handling back clean gasoline product.
The character of table 3 comparative example 2 oil products
As can be seen from Table 2: method of the present invention can be reduced to 41 μ g/g (HDS leads 93.8%) by 660 μ g/g with the sulphur content of FCC gasoline, olefin(e) centent is reduced to 25.5v% (alkene saturation exponent 18.7%) by 31.0v%, research octane number (RON) RON loses 0.9 unit, C
5 +Yield of gasoline 99.9wt% can be processed as FCC gasoline inferior the high-quality cleaning product of sulphur content ≯ 50 μ g/g.
From the comparing result of example 3 and comparative example 2 as can be seen, with identical raw material and in identical processing condition, compare with traditional catalyst preparation method and start-up method, method for preparing catalyst of the present invention and start-up method, HDS leads by 93.8% and brings up to 96.1%, the alkene saturation exponent is reduced to 15.5% by 18.7%, and research octane number (RON) RON loss reduces to 0.6 unit by 0.9 unit.
Example 4
This example provides the full cut FCC of a kind of poor quality gasoline hydrodesulfurizationmethod effect.
Evaluation test is to carry out on the device of fixed-bed reactor, pack in the reactor 50ml high reactivity HAC and a kind of low activity LAC catalyzer.The former with the latter volume ratio is 60/40.
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 1.2MPa, and hydrogen to oil volume ratio is 500:1, and the vulcanized oil volume space velocity is 5.0h
-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 1.3MPa, volume space velocity is 5.0h
-1, steady running sampling analysis in 100 hours.
Table 4 has been listed raw material FCC gasoline and the character of handling back clean gasoline product.
The character of table 4 example 4 oil products
As can be seen from Table 4: method of the present invention can be reduced to 28 μ g/g by 460 μ g/g with the sulphur content of full cut FCC gasoline, and olefin(e) centent is reduced to 19.6v% by 25.6v%, and research octane number (RON) RON loses 1.2 units, C
5 +Yield of gasoline 99.9wt% can be processed as the full cut FCC of poor quality gasoline sulphur content ≯ 50 μ g/g high-quality cleaning product, and research octane number (RON) RON loses ≯ 1.2 units.
Example 5
According to the method for preparing catalyst of example 1 and example 2, just in catalyst preparation process, dipping solution does not contain urea, obtains catalyzer HAC-1 and LAC-1.According to the 3 described processes of enforcement, use HAC-1 and LAC-1 catalyzer, the results are shown in Table 5.
Table 5 example 5 reaction results
Example 6
According to the method for preparing catalyst of example 1 and example 2, adjust the composition of catalyzer, obtain catalyzer HAC-2 and LAC-2, the HAC-2 active metallic content is MoO
3(10.0wt%)-and CoO (2.0wt%), the LAC-2 active metallic content is MoO
3(6.0wt%)-and CoO (2.0wt%), press example 4 described processes, temperature of reaction is adjusted into 300 ℃, the results are shown in Table 6.
The character of table 6 example 6 oil products
Claims (14)
1, a kind of inferior patrol hydrofinishing process, comprise following content: gasoline stocks and hydrogen pass through at least two Hydrobon catalyst beds successively under the hydrofining condition, described at least two Hydrobon catalyst beds reduce along Flow of Goods and Materials direction active metallic content, reaction mass is earlier by the high Hydrobon catalyst of active metallic content, then by the low Hydrobon catalyst of active metallic content, active metallic content differs 5.0wt%～18.0wt% in the catalyzer, at least a described Hydrobon catalyst adopts the solution impregnated catalyst carrier preparation that contains active metallic compound, dipping is back to be descended dry 6～20 hours at 80 ℃～160 ℃, did not carry out calcination process.
2, in accordance with the method for claim 1, the metal content that it is characterized in that the Hydrobon catalyst that Hydrobon catalyst that described active metallic content is high and active metallic content are low differs 8.0wt%～15.0wt%.
3, in accordance with the method for claim 1, it is characterized in that described hydrofining reaction condition is: 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
-1～12.0h
-1, hydrogen to oil volume ratio is 200:1～1000:1.
4, in accordance with the method for claim 1, it is characterized in that described hydrofining reaction condition is: the hydrogen dividing potential drop is 0.8MPa～3.0MPa, and temperature of reaction is 250 ℃～280 ℃, and volume space velocity is 3.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is 200:1～700:1.
5, in accordance with the method for claim 1, it is characterized in that active metal oxide content is 8.0wt%～20.0wt% in the high Hydrobon catalyst of described active metallic content, active metal oxide content is 1.0wt%～12.0wt% in the low Hydrobon catalyst of active metallic content, described reactive metal contain W in the group vib metal and/or the Ni in Mo and the VIII family metal and/Co, VIII family metal is 0.1～1.0 with group vib atoms metal ratio.
6, in accordance with the method for claim 5, it is characterized in that containing urea in the solution that contains active metallic compound of catalyst preparation process.
7, in accordance with the method for claim 6, the consumption that it is characterized in that containing urea in the active metallic compound solution is that urea/VIII family metal molar is than 0.10:1～1.5:1.
8, in accordance with the method for claim 6, the drying temperature that it is characterized in that catalyst preparation process is 100 ℃～130 ℃.
9, in accordance with the method for claim 1, it is characterized in that adopting two kinds of Hydrobon catalyst combinations, promptly high reactivity/low activity catalyst is used in combination, and its volume percent is 20/80～80/20.
10, in accordance with the method for claim 1, it is characterized in that described gasoline stocks is among fluid catalytic cracking gasoline, catalytic cracking gasoline, coker gasoline and pressure gasoline a kind of or several.
11, the start-up method of the described inferior patrol hydrofinishing process of the arbitrary claim of a kind of claim 1 to 10, comprise following content: in the catalyst-assembly reactor, under 200 ℃～260 ℃ low temperature, vulcanized 6～12 hours, under 300 ℃～380 ℃ high temperature, vulcanized 6～12 hours, obtain the sulphided state catalyzer, bed temperature is adjusted in the sulfuration back, carries out the hydrofining reaction of bad gasoline.
12, in accordance with the method for claim 11, it is characterized in that described cryogenic vulcanization temperature is 220 ℃～240 ℃, described high temperature vulcanized temperature is 310 ℃～350 ℃.
13, in accordance with the method for claim 11, it is characterized in that described sulfuration adopts wet method to vulcanize or dry method is vulcanized.
14, in accordance with the method for claim 13, it is characterized in that described wet method vulcanization process condition is: sulfide stress is 0.5MPa～4.0MPa, and volume space velocity is 1.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio is 200:1～1000:1.
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| CN 200710012674 CN101376835B (en) | 2007-08-27 | 2007-08-27 | Gasoline hydrofinishing startup method and gasoline hydrofinishing operation method |
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| CN102311759A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrodesulfurization of diesel |
| CN103361111A (en) * | 2012-04-04 | 2013-10-23 | 中国石油化工股份有限公司 | Catalyst sulfurization method of gasoline hydrotreating technique |
| CN103357449A (en) * | 2012-04-04 | 2013-10-23 | 中国石油化工股份有限公司 | Catalyst sulfurization method of diesel hydrotreating technique |
| CN104650963A (en) * | 2013-11-19 | 2015-05-27 | 中国石油天然气股份有限公司 | Operation start method of FCC gasoline hydrogenation catalyst |
| CN105582963A (en) * | 2014-10-22 | 2016-05-18 | 中国石油化工股份有限公司 | Preparation method for sulfuration-type gasoline selective hydrodesulfurization catalyst |
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| CN1035775C (en) * | 1994-03-28 | 1997-09-03 | 中国石油化工总公司 | Rifining method for catalylic cracking gasoline by adding hydrogen |
| CN1056784C (en) * | 1996-06-28 | 2000-09-27 | 中国石油化工总公司 | Catalyst treated by distillate added with hydrogen and preparation method thereof |
| CN1252222C (en) * | 2002-10-10 | 2006-04-19 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and process |
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| CN102311759A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for hydrodesulfurization of diesel |
| CN102311759B (en) * | 2010-07-07 | 2015-02-18 | 中国石油化工股份有限公司 | Method for hydrodesulfurization of diesel |
| CN103361111A (en) * | 2012-04-04 | 2013-10-23 | 中国石油化工股份有限公司 | Catalyst sulfurization method of gasoline hydrotreating technique |
| CN103357449A (en) * | 2012-04-04 | 2013-10-23 | 中国石油化工股份有限公司 | Catalyst sulfurization method of diesel hydrotreating technique |
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| CN105582963B (en) * | 2014-10-22 | 2017-11-24 | 中国石油化工股份有限公司 | A kind of preparation method of vulcanization type catalyst for selective hydrodesulfurizationof of gasoline |
| CN109777515A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method of heavy-oil hydrogenation high-knock rating gasoline |
| CN116515526A (en) * | 2022-01-20 | 2023-08-01 | 中国石油化工股份有限公司 | Hydrogenation-active metal desulfurization combined process for catalytically cracked gasoline |
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