CN101724442A - Method for reducing octane number loss of gasoline deep hydrodesulphurization - Google Patents
Method for reducing octane number loss of gasoline deep hydrodesulphurization Download PDFInfo
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Abstract
The invention relates to a method for reducing octane number loss of gasoline deep hydrodesulphurization. The method comprises the following steps of: pre-vulcanizing a catalyst, and then carrying out the hydrodesulphurization treatment on inferior gasoline feedstock under the conditions of gasoline hydrodesulphurization. The catalyst pre-vulcanization treatment comprises the following steps of: putting the catalyst into a reactor, vulcanizing for 6-12 hours at 220-240 DEG C and vulcanizing for 6-12 hours at 240-260 DEG C, wherein the temperature of vulcanization is not higher than 260 DEG C. Compared with the prior art, the method can efficiently reduce the loss of octane number and can be applied to selective hydrodesulphurization process of all kinds of inferior gasoline feedstock while having higher desulphurization degree in the process of gasoline deep hydrodesulphurization.
Description
Technical field
The present invention relates to a kind of gasoline hydrodesulfurizationmethod method, specifically, the present invention relates to the method for inferior patrol cut selectivity deep hydrodesulfurizationof.
Background technology
The atmospheric pollution that vehicle exhaust causes is paid close attention to by people day by day.Reduce sulphur content in the gasoline and can reduce in the vehicle exhaust emission of harmful substances amounts such as sulfurous gas significantly.What therefore, oneself had all been formulated in countries in the world is the clean gasoline new standard of sign with the low-sulfur.Sulphur content as European IV vehicle exhaust standard-required European clean gasoline after 2005 is not more than 50 μ g/g, and the sulphur content of U.S. U.S.EPA Tier2 standard code U.S.'s clean gasoline after 2006 is not more than 80 μ g/g.Along with the increasingly stringent of environmental regulation, Chinese gasoline quality will progressively integrate with world developed country, and the gasoline products objectionable impurities has been proposed more and more stricter requirement, particularly requires more and more tighter to sulphur content.China's content of sulfur in gasoline index required ≯ 800 μ g/g in 2003, required ≯ 500 μ g/g in 2006, will require in 2009 ≯ 150 μ g/g, will require ≯ 50 μ g in 2012.Wherein, supply Pekinese content of sulfur in gasoline requires strict more, requires ≯ 50 μ g/g in 2008, may carry out " sweet gasoline " standard (sulphur content ≯ 10 μ g) in 2012.
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.
Hydrodesulfurization, 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 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.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 alkali desulfurization 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 20 μ g/g, ≯ 2.0 units of the anti-knock index of gasoline ((R+M)/2) loss.
Above-mentioned patented method catalyzer need be in 280 ℃ (CN 02133136.7) even the sulfuration down of 350 ℃ of (U.S.Pat.6,692,635) high temperature, with the hydrogenation active metals oxide compound, as MoO in the process of going into operation usually
3, CoO, WO
3Or NiO is converted into sulfide, as MoS
2, Co
9S
8, WS
2Or Ni
3S
2In the pre-vulcanization process, this area be it is generally acknowledged and only carry out sulfidizing under comparatively high temps, just can make the tight cure of catalyst hydrogenation activity component, and then reach the ideal use properties in device.As described in the 226th page to 231 pages described " sulfurations of catalyzer " joints of " hydrofining " book of Sinopec press publication in 2006, the hydrogenation catalyst sulfuration generally needs three phases, fs was 230 ℃ of sulfurations 8 hours, subordinate phase is 290 ℃ of sulfurations 6 hours, 320 ℃ of sulfurations 6 hours.
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 to keep rare hydrocarbon be conflicting in hydrogenation reaction, and hydrogenating desulfurization and hydrogenation of olefins is saturated all carries out on the catalyst hydrogenation activity center.People such as Jeppe V.Lauritsen (Journal of Catalysis, 249 (2007): 220～233) think MoS
2Be the hydrodesulfurization activity phase, Co is a promotor, and Co is positioned at MoS
2The edge, forms so-called Co-Mo-S structure and become the hydrodesulfurization activity center, but the Co/Mo ratio is not by the Co-Mo-S stoichiometry, Co content than the Co-Mo-S stoichiometry lack many.
The catalyst vulcanization method of state of the art is not studied at the requirement of inferior patrol selectivity deep hydrodesulfurizationof production low-sulfur, low octane rating loss gasoline products.
Summary of the invention
The invention provides a kind of inferior patrol selectivity deep hydrodesulfurizationof and produce the method for low-sulfur, low octane rating loss gasoline products, adopt the catalyst vulcanization method of optimizing, reduce the loss of gasoline products octane value when being implemented in deep desulfuration.
The method that the present invention reduces octane number loss of gasoline deep hydrodesulphurization comprises following content, at first catalyzer being carried out prevulcanized handles, carrying out the hydrogenating desulfurization of bad gasoline then under the gasoline hydrodesulfurizationmethod condition handles, wherein catalyzer carries out the following process of prevulcanized processing employing: in the catalyst-assembly reactor, vulcanized 6～12 hours down at 220 ℃～240 ℃, at (＞240 ℃) to 260 ℃ of down sulfurations 6～12 hours, curing temperature ≯ 260 ℃.
In the inventive method, the hydrodesulfurization 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 was 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～and 700: 1.
In the inventive method, can use single a kind of Hydrobon catalyst, preferably two or more Hydrobon catalyst is used.When using two or more Hydrobon catalyst, gasoline stocks and hydrogen pass through at least two Hydrobon catalyst beds successively under hydrodesulfurizationconditions conditions, 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.
In the inventive method, other condition of presulfiding of catalyst adopts content well known to those skilled in the art, as the prevulcanized of adopting suitable vulcanizing agent and suitable pre-vulcanization process condition to carry out Hydrobon catalyst is handled.Vulcanizing agent 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 mass content of vulcanizing agent in vulcanized oil is generally 0.5m%～3.0m%, is preferably 0.8m%～2.0m%.Wet method pre-vulcanization process condition is: pressure is generally 0.5MPa～4.0MPa, and volume space velocity is generally 1.0h during liquid
-1～10.0h
-1, hydrogen to oil volume ratio was generally 200: 1～1000: 1; Pressure is preferably 0.8MPa～2.0MPa, and volume space velocity is preferably 2.0h during liquid
-1～6.0h
-1, hydrogen to oil volume ratio is preferably 200: 1～and 700: 1.
The present invention is directed to the selectivity requirement in the gasoline hydrodesulfurizationmethod process, promptly the hydrogenating desulfurization rate wants high on the one hand, the Alkene hydrogenation saturation exponent is low on the other hand, determined and the different optimal conditions of common hydrogenation catalyst presulfiding of catalyst condition, obtain beyond thought technique effect, reached the double goal that deep hydrodesulfurizationof and loss of octane number reduce.
The inventive method adopts and has now the interior prevulcanized diverse ways of hydrogenating catalyst and carries out prevulcanized, because overall pre-curing temperature is far below the pre existing vulcanization process, those skilled in the art can think that hydrogenation active metals may vulcanize insufficient, but in fact activity of such catalysts is more or less the same, but desulfuration selectivity obviously improves, reason may be the crystalline state difference of the metallic sulfide that obtains during prevulcanized under the different condition, MoS when high temperature vulcanized
2Structure will be converted into low dispersive grains (Crystals), MoS by family's shape (Clusters) of high dispersing
2Big, buttress (Slabs) number of plies increase that granularity becomes, reduction has the active surface C o-Mo-S of direct hydrogenating desulfurization (DDS) active centre figure place most greatly, causes catalyzer HDS selectivity poor slightly, and Study on product method octane value (RON) loss is more.
Embodiment
In the inferior patrol deep hydrodesulfurizationof method of the present invention, the Hydrobon catalyst of use can be the commercial goods, also can prepare by this area public technology.Active metal oxide content is 8.0wt%～20.0wt% in the described high activity hydrogenation and desulphurization 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 was preferably 0.20: 1～1.0: 1 than 0.10: 1～1.5: 1.
In the gasoline stocks hydrodesulfurizationprocess 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.
3, roasting: the supported catalyst in the step 2 was descended dry 6～20 hours at 450 ℃～550 ℃, promptly obtain oxidized 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, 220 ℃～240 ℃ down sulfurations 6～12 hours, vulcanized 6～12 hours down being higher than 240 ℃ to 260 ℃, curing temperature ≯ 260 ℃ obtain the sulphided state catalyzer.
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 hydrodesulfurization reaction.
Bad gasoline of the present invention is one or more in fluid catalytic cracking (FCC) gasoline, catalytic cracking gasoline, coker gasoline and the pressure gasoline etc.The preferred raw material of the present invention is a FCC gasoline.Described inferior patrol hydrogenating materials can be the full cut of bad gasoline, and boiling range is generally 30 ℃～220 ℃, particularly 30 ℃～180 ℃.Also can be for being lighting end and last running with the bad gasoline prefractionation, 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 hydrogenating desulfurization, 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-K
2O/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/0.80: 1 weighing urea of CoO mol ratio 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 ℃, 510 ℃ of following roastings 8 hours, 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 ℃, 480 ℃ of following roastings 8 hours, prepares low activity catalyst, is called for short LAC.
Example 3
This example provides a kind of FCC gasoline deep hydrodesulphurization effect inferior.
Table 1 has been listed the character of FCC gasoline.
Table 1FCC gasoline stocks character
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
2Mass concentration 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, 230 ℃ of following constant temperature sulfurations 8 hours, 250 ℃ of following constant temperature sulfurations 10 hours.
Sulfuration is changed FCC gasoline stocks oil after finishing, and the hydrogen dividing potential drop is 1.8MPa, and volume space velocity is 3.0h
-1, hydrogen to oil volume ratio is 300: 1, in 280 ℃ of following steady runnings sampling analysis in 100 hours.
Table 2 has been listed raw material FCC gasoline and the character of handling back clean gasoline product.
Example 4
Experimental raw is with example 3.
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 70/30.
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 10 hours in temperature, 250 ℃ of following constant temperature 8 hours.
Sulfuration is changed FCC gasoline stocks oil after finishing, and the hydrogen dividing potential drop is 1.3MPa, and volume space velocity is 4.0h
-1, hydrogen to oil volume ratio is 500: 1, in 270 ℃ of following steady runnings sampling analysis in 100 hours.
Table 2 has been listed raw material FCC gasoline and the character of handling back clean gasoline product.
Comparative example
Experimental raw is with example 3.
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 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 8 hours in temperature, 280 ℃ of following constant temperature 8 hours.
Sulfuration is changed FCC gasoline stocks oil after finishing, and the hydrogen dividing potential drop is 1.8MPa, and volume space velocity is 3.0h
-1, hydrogen to oil volume ratio is 300: 1, in 280 ℃ of following steady runnings sampling analysis in 100 hours.
Table 2 has been listed raw material FCC gasoline and the character of handling back clean gasoline product.
Fig. 1 has listed the contrast to desulfurization degree and the influence of alkene saturation exponent of curing temperature in example 3～example 5.
The raw material of table 2 example 3,4 and comparative example and the character of product
As can be seen from Table 2: the sulphur content of FCC gasoline is reduced to ≯ 50 μ g/g (HDS leads about 90.0%) by 428 μ g/g, compared with prior art, adopts the inventive method can significantly reduce the loss of product octane value.
Claims (8)
1. method that reduces octane number loss of gasoline deep hydrodesulphurization, at first catalyzer being carried out prevulcanized handles, carrying out the hydrogenating desulfurization of bad gasoline then under the gasoline hydrodesulfurizationmethod condition handles, it is characterized in that catalyzer carries out prevulcanized and handles the following process of employing: in the catalyst-assembly reactor, vulcanized 6～12 hours down at 220 ℃～240 ℃, at (＞240 ℃) to 260 ℃ of down sulfurations 6～12 hours, curing temperature ≯ 260 ℃.
2. in accordance with the method for claim 1, it is characterized in that described gasoline hydrodesulfurizationmethod 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.
3. in accordance with the method for claim 1, it is characterized in that described gasoline hydrodesulfurizationmethod 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.
4. in accordance with the method for claim 1, it is characterized in that gasoline deep hydrodesulphurization uses single a kind of Hydrobon catalyst.
5. in accordance with the method for claim 1, it is characterized in that gasoline deep hydrodesulphurization is used two or more Hydrobon catalyst, gasoline stocks and hydrogen pass through at least two Hydrobon catalyst beds successively under hydrodesulfurizationconditions conditions, 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, by the low Hydrobon catalyst of active metallic content, differ 5.0wt%～18.0wt% then in active metallic content in the active metal oxide catalyzer.
6. in accordance with the method for claim 1, it is characterized in that described presulfiding of catalyst processing employing vulcanizing agent and under the processing condition of prevulcanized, carry out sulfuration of employing wet method or dry method sulfuration.
7. in accordance with the method for claim 6, it is characterized in that described vulcanizing agent is for easily decomposing and energy and H
2Form H
2The sulfide of S.
8. in accordance with the method for claim 1, it is characterized in that described bad gasoline is one or more in fluid catalytic cracking gasoline, catalytic cracking gasoline, coker gasoline and the pressure gasoline.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102641749A (en) * | 2011-02-17 | 2012-08-22 | 中国石油化工股份有限公司 | Prevulcanization method of hydrotreatment catalyst |
| CN103773435A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vulcanization method of selective hydrodesulfurization catalyst of FCC (Fluid Catalytic Cracking) gasoline |
| CN103773439A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Start method for gasoline selective hydro-desulfurization technology |
| CN114160168A (en) * | 2020-09-11 | 2022-03-11 | 中国石油化工股份有限公司 | Sulfurizing method of gasoline selective hydrogenation catalyst |
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|---|---|---|---|---|
| US4943547A (en) * | 1988-09-13 | 1990-07-24 | Seamans James D | Method of presulfiding a hydrotreating catalyst |
| CN1168538C (en) * | 2000-04-11 | 2004-09-29 | 阿克佐诺贝尔股份有限公司 | Process for sulphiding and additive-containing catalyst |
| CN1200081C (en) * | 2001-10-30 | 2005-05-04 | 中国石油化工股份有限公司 | Pre-sulfurizing process of hydrogenating catalyst |
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| CN102641749A (en) * | 2011-02-17 | 2012-08-22 | 中国石油化工股份有限公司 | Prevulcanization method of hydrotreatment catalyst |
| CN102641749B (en) * | 2011-02-17 | 2014-04-30 | 中国石油化工股份有限公司 | Prevulcanization method of hydrotreatment catalyst |
| CN103773435A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Vulcanization method of selective hydrodesulfurization catalyst of FCC (Fluid Catalytic Cracking) gasoline |
| CN103773439A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Start method for gasoline selective hydro-desulfurization technology |
| CN103773439B (en) * | 2012-10-24 | 2015-09-30 | 中国石油化工股份有限公司 | A kind of start-up method of gasoline selective hydrodesulfurizationmodification technique |
| CN103773435B (en) * | 2012-10-24 | 2015-12-16 | 中国石油化工股份有限公司 | A kind of vulcanization process of FCC gasoline catalyst for selectively hydrodesulfurizing |
| CN114160168A (en) * | 2020-09-11 | 2022-03-11 | 中国石油化工股份有限公司 | Sulfurizing method of gasoline selective hydrogenation catalyst |
| CN114160168B (en) * | 2020-09-11 | 2023-09-01 | 中国石油化工股份有限公司 | Sulfuration method of gasoline selective hydrogenation catalyst |
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