CN103834438B - A kind of processing method of hydrogenating desulfurization - Google Patents
A kind of processing method of hydrogenating desulfurization Download PDFInfo
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- CN103834438B CN103834438B CN201310567188.3A CN201310567188A CN103834438B CN 103834438 B CN103834438 B CN 103834438B CN 201310567188 A CN201310567188 A CN 201310567188A CN 103834438 B CN103834438 B CN 103834438B
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Abstract
The invention provides a kind of processing method of hydrogenating desulfurization, the method comprises: (1) is in hydrogenator, facing under hydroformylation reaction condition, full distillation gasoline is contacted with selective hydrogenation catalyst with hydrogen, obtain facing hydroformylation reaction product, wherein, facing hydroformylation reaction condition described in control makes the saturation exponent of alkene below 10 % by weight, and the methyl isophthalic acid-butenc of more than 50 % by weight is methyl-2-butene in full distillation gasoline, and faces diene content in hydroformylation reaction product described in making and be down to ≯ 0.8gI/100g; (2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with catalyst for selectively hydrodesulfurizing with hydrogen, obtains hydrodesulfurization reaction product.Method of the present invention can obtain has ultra-low sulfur, low thioalcohol content, gasoline products that loss of octane value is less, and the yield of product is high, is very suitable for industrial application.
Description
Technical field
The present invention relates to a kind of processing method of hydrogenating desulfurization.
Background technology
At present, the sulphur more than 90% in gasoline is from catalytically cracked gasoline.Therefore, the sulphur content in reduction catalytically cracked gasoline and mercaptans content are the keys of producing low-sulphur oil, meeting current and following specification gasoline.
Traditional hydrogenating desulfurization (HDS) technique effectively can reduce sulphur in catalytically cracked gasoline and mercaptans content.But while gasoline hydrodesulfurizationmethod, gasoline octane rating (RON value) loss is larger.In order to reduce the loss of gasoline octane rating in sweetening process, develop the technique of many catalytic gasoline selective hydrodesulfurizationmodifications (SHDS) both at home and abroad, basic based on following principle: namely optionally hydrogenating desulfurization to be carried out to gasoline, sulfur compound is changed into H2S, thus reaches the gasoline octane rating damage control in acceptable level.
At present, the catalytic gasoline selective hydrodesulfurizationmodification technique of domestic industry application mainly contains the CDHydr/CDHDS technique of CDTECH company of the U.S., the Prime-G of French AXNES
+, Fushun Petrochemical Research Institute OCT-M technique, the CDOS-HCN technique of Beijing Haishunde Titanium Catalyst Co., Ltd..The feature of these techniques be catalytically cracked gasoline fractionation is cut into light, weigh two cuts or light, in, weigh three cuts, and process respectively for the characteristic of different fractions, wherein last running gasoline adopts special catalyzer to carry out selective hydrodesulfurization, and then each cut after process is obtained by mixing low-sulphur oil.But these techniques all need to arrange special fractionation plant, and have that investment is comparatively large, flow process is more complicated and the problem such as energy consumption is larger.
CN101173184A discloses a kind of method of selectively hydrogenating and desulfurizing inferior gasoline, the method comprises: bad gasoline, depriving hydrogen sulphide agent are contacted with catalyst for selectively hydrodesulfurizing with hydrogen, under hydrodesulfurization reaction condition, carry out selective hydrodesulfurization reaction, described depriving hydrogen sulphide agent is basic solvent.Although the method can process full distillation gasoline raw material, and the sulphur content of product is not more than 50 μ g/g, and mercaptan sulfur content is not more than 10 μ g/g, needs to consume a large amount of depriving hydrogen sulphide agent.
Summary of the invention
For above prior art, the technical problem to be solved in the present invention is to provide a kind of can acquisition and has ultra-low sulfur, low thioalcohol content, gasoline products that loss of octane value is less, and the processing method of the high hydrogenating desulfurization of the yield of product.
For achieving the above object, the invention provides a kind of processing method of hydrogenating desulfurization, the method comprises:
(1) in hydrogenator, facing under hydroformylation reaction condition, full distillation gasoline is contacted with selective hydrogenation catalyst with hydrogen, obtain facing hydroformylation reaction product, wherein, facing hydroformylation reaction condition described in control makes the saturation exponent of alkene below 10 % by weight, and in full distillation gasoline, the methyl isophthalic acid-butenc of more than 50 % by weight is methyl-2-butene, and faces diene content in hydroformylation reaction product described in making and be down to ≯ 0.8gI/100g;
(2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with catalyst for selectively hydrodesulfurizing with hydrogen, obtains hydrodesulfurization reaction product.
Method of the present invention can obtain has ultra-low sulfur, low thioalcohol content, gasoline products that loss of octane value is less, and the yield of product is high, is very suitable for industrial application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Accompanying drawing 1 is the schema of the processing method according to a kind of hydrogenating desulfurization preferred embodiment of the present invention.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of processing method of hydrogenating desulfurization, the method comprises:
(1) in hydrogenator, facing under hydroformylation reaction condition, full distillation gasoline is contacted with selective hydrogenation catalyst with hydrogen, obtain facing hydroformylation reaction product, wherein, facing hydroformylation reaction condition described in control makes the saturation exponent of alkene below 10 % by weight, and in full distillation gasoline, the methyl isophthalic acid-butenc of more than 50 % by weight is methyl-2-butene, and faces diene content in hydroformylation reaction product described in making and be down to ≯ 0.8gI/100g;
(2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with catalyst for selectively hydrodesulfurizing with hydrogen, obtains hydrodesulfurization reaction product.
All object of the present invention can be realized according to the aforesaid method of the present invention, for the present invention, in order to reduce loss of octane number further and improve desulfurization degree, simultaneously in order to ensure the cycle of operation of follow-up catalyst for selectively hydrodesulfurizing or catalyst for selectively hydrodesulfurizing and Hydrobon catalyst, facing hydroformylation reaction condition described in preferred rate-determining steps (1) makes the saturation exponent of alkene below 5 % by weight, and in full distillation gasoline more than 70 % by weight methyl isophthalic acid-butylene (
) be converted into methyl-2-butene (
), and face diene content in hydroformylation reaction product described in making and be down to ≯ 0.5gI/100g, be more preferably down to ≯ 0.2gI/100g(the present invention in symbol ≯ refer to the meaning be less than or equal to).
According to the processing method of hydrogenating desulfurization of the present invention, wherein, can realize facing hydroformylation reaction condition described in rate-determining steps (1) makes the saturation exponent of alkene below 5 % by weight, and the methyl isophthalic acid-butenc of more than 70 % by weight is methyl-2-butene in full distillation gasoline, and face diene content in hydroformylation reaction product described in making and be down to ≯ 0.5gI/100g, more preferably be down to ≯ selective hydrogenation catalyst of 0.2gI/100g all can be used for the present invention, the selective hydrogenation catalyst used in a particular embodiment of the present invention is the selective hydrogenation catalyst of commercial grades HDDO-100.
According to the processing method of hydrogenating desulfurization of the present invention, the range of choices facing hydroformylation reaction condition described in step (1) is wider, as long as guarantee to realize aforementioned object, for the present invention, face hydroformylation reaction condition preferably to comprise: temperature is 80-250 DEG C, be preferably 100-220 DEG C; Pressure is 1-5MPa, is preferably 1-3MPa; Liquid hourly space velocity is 1-20h
-1, be preferably 2-6h
-1; Hydrogen to oil volume ratio is 5-100:1, is preferably 10-50:1.Aforementioned face hydroformylation reaction condition under, object of the present invention can be realized comparatively fully, and the loss of octane number of product is less.
All can realize object of the present invention according to the aforesaid processing method of the present invention, for the present invention, preferably control described hydrodesulfurization reaction condition and make the organic sulfur conversion of in full distillation gasoline more than 80 % by weight be hydrogen sulfide.
The present inventor finds in research process, makes the organic sulfur conversion of in full distillation gasoline more than 80 % by weight be hydrogen sulfide to realize controlling described hydrodesulfurization reaction condition.Described catalyst for selectively hydrodesulfurizing can prepare according to method disclosed in CN1218021C, also can be commercially available, the catalyst for selectively hydrodesulfurizing used in a particular embodiment of the present invention is the catalyst for selectively hydrodesulfurizing of commercial grades HDOS-200.
According to the processing method of hydrogenating desulfurization of the present invention, described in step (2), the range of choices of hydrodesulfurization reaction condition is wider, and for the present invention, preferred described hydrodesulfurization reaction condition comprises: temperature is 200-400 DEG C, is preferably 220-350 DEG C; Pressure is 1-5MPa, is preferably 1-3MPa; Liquid hourly space velocity is 1-20h
-1, be preferably 2-6h
-1; Hydrogen to oil volume ratio is 100-1000:1, is preferably 300-800:1.
According to the processing method of hydrogenating desulfurization of the present invention, preferred processing method of the present invention also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
In the present invention, the method of the described gas sweetening hydrogen containing hydrogen sulfide can be carried out with reference to prior art, alcohol amine absorption process is such as generally adopted to remove hydrogen sulfide, be generally particularly adopt in absorption tower basic solvent as ethylene glycol amine as absorption agent and as described in carry out the absorption of hydrogen sulfide containing gas counter current contact in absorption tower of hydrogen sulfide, then substantially remove H
2the gas of S is discharged from absorption tower tower top, thus reaches the object of depriving hydrogen sulphide.To this, those skilled in the art all can know, do not repeat them here.
In the present invention, the described gas substantially removing hydrogen sulfide is substantially all hydrogen, so obtain basic be all that the described gas substantially removing hydrogen sulfide of hydrogen can circulate as recycle hydrogen, and owing to recycle in process H in recycle hydrogen
2s concentration is lower more favourable to raising gasoline hydrodesulfurizationmethod selectivity, and therefore, for the present invention, preferably the described concentration of hydrogen sulfide that substantially to remove in the gas of hydrogen sulfide is at 100 below μ L/L, more preferably at 50 below μ L/L.The gas substantially removing hydrogen sulfide so obtained can well use as recycle hydrogen, and it can by entering each reactive system after the boosting of recycle hydrogen press.Namely method of the present invention can also comprise: the described gas circulation substantially removing hydrogen sulfide is returned step (1) and/or step (2) uses as recycle hydrogen.
In the present invention, described liquid phase substance being carried out air lift is generally carry out in stripping unit, obtains the gasoline of described low sulfur content after air lift at the bottom of described stripping stabilizer tower tower.
For the present invention, in order to reduce the olefin(e) centent of the raw material of the entrance of described hydrogenator and/or described hydrodesulphurisatioreactors reactors, preferred method of the present invention also comprises: described low sulfur content gasoline circulation is returned step (1) and/or step (2), wherein, the amount returned in step (1) is the 0.1-4 times of weight of the described full distillation gasoline of raw material as step (1), is preferably 0.2-1 times of weight; The amount in step (2) of returning, for facing the 0.1-4 times of weight of hydroformylation reaction product described in the raw material as step (2), is preferably 0.2-1 times of weight.The present inventor finds, under the condition of the internal circulating load of the gasoline of aforementioned low sulfur content, the olefin(e) centent of the raw material in corresponding reactor can be reduced, can reduce thus according to the octane value in the hydrodesulfurization process of the method for hydrogenating desulfurization of the present invention loss and improve the selectivity of the hydrogenating desulfurization in hydrodesulfurization process.In specific implementation process, the gasoline of described low sulfur content can be recycled to any one position of the entrance of described hydrogenator and/or the beds of described hydrogenator; Or any one position be recycled to by the gasoline of described low sulfur content in the entrance of described hydrodesulphurisatioreactors reactors and/or the beds of described hydrodesulphurisatioreactors reactors, can realize the corresponding olefin(e) centent reduced in corresponding reactor inlet raw material thus.In industrial implementation process, usually the gasoline of low sulfur content can be squeezed into any one position of the entrance of described hydrogenator and/or the beds of described hydrogenator by pump, or squeeze into any one position in the entrance of described hydrodesulphurisatioreactors reactors and/or the beds of hydrodesulphurisatioreactors reactors by pump.The recirculation of the gasoline of low sulfur content is carried out according to preceding method, then by controlling the recirculation volume of gasoline in each reactor of low sulfur content, can make olefin(e) centent in each corresponding reactor Raw below 40 % by weight, preferably below 35 % by weight, can improve when using the higher full distillation gasoline of olefin(e) centent as raw material thus, according to the selectivity of the hydrogenating desulfurization of the method for hydrogenating desulfurization of the present invention.
According to the method for aforementioned hydrogenation desulfurization of the present invention, the low sulfur content sulfur content in gasoline obtained and mercaptans content are all lower, and the gasoline octane rating loss that the method for hydrogenating desulfurization of the present invention obtains is less, particularly, the sulfur content in gasoline of described low sulfur content is generally at 10 below μ g/g, and mercaptans content is not more than 10 μ g/g.Full distillation gasoline fresh feed compared by described low sulfur content gasoline (full cut), and its RON loss is generally less than 2 units, and MON loss is generally less than 1 unit.
According to the method for hydrogenating desulfurization of the present invention, according to needing, preferred method of the present invention also comprises: before the product after described hydrogenating desulfurization is carried out gas-liquid separation, product after described hydrogenating desulfurization and hydrodesulfurization reaction product are sent in hydrofining reactor, under hydrofining reaction condition, contact with Hydrobon catalyst with hydrogen.In the present invention, carrying out hydrorefined main purpose is supplementing aforementioned hydrogenation desulphurization reaction, is mainly used to decompose sulfide, particularly mercaptan contained in hydrogenating desulfurization product.According to method of the present invention, the range of choices of described hydrorefined condition is wider, specifically can adjust according to actual needs, and for the present invention, preferred described Hydrofinishing conditions comprises: temperature is 250-450 DEG C, preferred 300-380 DEG C; Pressure is 1-5MPa, is preferably 1-3MPa; Liquid hourly space velocity is 1-30h
-1, be preferably 2-10h
-1; Hydrogen to oil volume ratio is 100-1000:1, is preferably 300-800:1.
All can realize object of the present invention according to the aforesaid method of the present invention, for the present invention, preferably control described hydrofining reaction condition and make more than 90 % by weight in full distillation gasoline, more preferably the organic sulfur conversion of more than 95 % by weight is hydrogen sulfide.
The present inventor finds in research process, more than 90 % by weight in full distillation gasoline is made in order to realize controlling described hydrofining reaction condition, more preferably the organic sulfur conversion of more than 95 % by weight is hydrogen sulfide, and the Hydrobon catalyst used in a particular embodiment of the present invention is the Hydrobon catalyst of commercial grades HDMS-100.
As previously mentioned, when method of the present invention comprises described hydrorefined step, according to needing, can the gasoline of described low sulfur content be recycled in described hydrofining reactor, such as, described low sulfur content gasoline can be recycled to any one position in the entrance of described hydrofining reactor and/or the beds of described hydrofining reactor.
According to method of the present invention, the range of choices of the described full distillation gasoline as raw material is wider, conventional full distillation gasoline all can carry out hydrogenating desulfurization according to the method for hydrogenating desulfurization of the present invention, described full distillation gasoline is generally from catalytic cracking unit or from other cracking unit, for the present invention, preferred described full distillation gasoline be selected from catalytically cracked gasoline, coker gasoline, catalytic cracking gasoline and pressure gasoline one or more, more preferably described full distillation gasoline is catalytically cracked gasoline (FCC); In further preferred described full distillation gasoline, sulphur content is at 1200 below μ g/g, preferably at 800 below μ g/g, particularly preferably in 600 below μ g/g; Olefin(e) centent at 50 below volume %, preferably at 40 below volume %, particularly preferably in 35 below volume %.More preferably, described full distillation gasoline do below 250 DEG C, preferably below 220 DEG C, particularly preferably in less than 205 DEG C.
According to the processing method of hydrogenating desulfurization of the present invention, as long as carry out can well realizing object of the present invention according to preceding method, described step (1) and step (2) can complete in same reactor, and (namely hydrogenator of the present invention and hydrodesulphurisatioreactors reactors refer to is the reactor realizing respective function, can select to carry out in their each comfortable reactors according to practical situation in specific implementation process, still may be incorporated in same reactor and carry out), also can complete in respective reactor, as long as can ensure to realize aforementioned condition of the present invention.As previously mentioned, hydrofining of the present invention can be carried out in reactor alone, also can carry out in same reactor with the hydrogenating desulfurization of step (2), when described hydrofining and hydrogenating desulfurization are carried out in same reactor, generally Hydrobon catalyst can be seated in the top of reactor, Hydrobon catalyst is seated in the bottom of reactor, when loading Hydrobon catalyst and Hydrobon catalyst in this manner, the top charging of hydroformylation reaction product from reactor can be faced by described, face hydroformylation reaction product described in realizing thus and carry out hydrogenating desulfurization and hydrorefined process successively.
According to one of the present invention preferred embodiment, the processing method of hydrogenating desulfurization of the present invention is carried out as follows:
(1) in hydrogenator, facing under hydroformylation reaction condition, full distillation gasoline being contacted with selective hydrogenation catalyst with hydrogen, obtaining facing hydroformylation reaction product;
(2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with catalyst for selectively hydrodesulfurizing with hydrogen, obtains hydrodesulfurization reaction product;
(3) laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide;
Selectable, before step (3), carry out hydrofining, carry out as follows particularly: in hydrofining reactor, under hydrofining reaction condition, described hydrodesulfurization reaction product is contacted with Hydrobon catalyst with hydrogen;
(4) circulation of the gasoline of described low sulfur content is returned step (1) and/or step (2) and/or hydrofining step, the described gas circulation substantially removing hydrogen sulfide is returned step (1) and/or step (2) and/or hydrofining step and use as recycle hydrogen.
The processing method technical process of hydrogenating desulfurization of the present invention is simple, and can obtain and have ultra-low sulfur, low thioalcohol content, gasoline products that loss of octane value is less, and the yield of product is high, is very suitable for industrial application.
Be described below in conjunction with the processing method of accompanying drawing 1 to hydrogenating desulfurization of the present invention.
Full distillation gasoline 1 is introduced by the road, mixes, then heat in interchanger 14 with the hydrogen from pipeline 2, enters in hydrogenator 15 carry out facing H-H reaction and obtain facing hydroformylation reaction product after being heated to the temperature and pressure required for hydrogenation reaction through pipeline 3;
Face hydroformylation reaction product and 4 to flow out from hydrogenator 15 by the road, after then mix with hydrogen, after interchanger 16 heating, enter in hydrodesulphurisatioreactors reactors 17 and carry out hydrodesulfurization reaction and obtain hydrodesulfurization reaction product;
Hydrodesulfurization reaction product 5 to flow out by the road from hydrodesulphurisatioreactors reactors 17, then enters in hydrofining reactor 19 after interchanger 18 heats and carries out hydrofining reaction and obtain hydrofining reaction product;
Hydrofining reaction product 6 to flow out by the road from hydrofining reactor 19, enters in knockout drum 21 and carry out gas-liquid separation and obtain containing H after interchanger 20 is lowered the temperature
2the gas of S and liquid phase substance, what separation obtained contains H
2the gas of S 7 enters de-H by the road
2de-H is carried out in S tower 22
2s process obtains de-H
2gas after S, wherein, de-H
2gas after S 9 enters in recycle hydrogen press 23 and re-uses by the road, and be separated the liquid phase substance that obtains and 8 enter in stripping stabilizer tower 24 and carry out air lift by the road, wherein, after air lift, the overhead gas of stabilizer tower 24 10 is recovered by the road, the low sulfur content gasoline fraction obtained at the bottom of tower 11 reclaims (being such as sent to gasoline pool) by the road, another part low sulfur content gasoline can circulate through circulation line 12 and return hydrogenator 15, hydrodesulphurisatioreactors reactors 17, (such as hydrogenator 15 can be delivered in hydrofining reactor 19, hydrodesulphurisatioreactors reactors 17, the entrance recirculation point of hydrofining reactor 19 and hydrogenator 15, hydrodesulphurisatioreactors reactors 17, recirculation point between the beds of hydrofining reactor 19).
Below by specific embodiment, the present invention will be described in detail, but the present invention is not limited to this.
In the present invention, boiling range is according to GB/T6536(ASTM D86) regulation measure, sulfur content (or claim sulphur content) is according to SH/T0689(ASTM D5453) regulation measure, mercaptan sulfur content is according to GB/T1792(ASTM D3227) regulation measure.
In the present invention, FIA(alkene, aromatic hydrocarbons and saturated alkane) according to GB/T11132(ASTM D1319) regulation measure.
In the present invention, diene content is according to QJ/FSH.YX.128-97(UOP-326-82) regulation of Maleic Anhydride Method measures.
In the present invention, methyl isophthalic acid-butylene and methyl-2-butene adopt Agilent6890N type chromatographic instrument to measure, wherein, with N
2for carrier, HP-PONA chromatographic column is adopted to measure.
In the present invention, research octane number (RON) (RON), motor-method octane number (MON) are respectively according to GB/T5487(ASTM D2669), GB/T503(ASTM D2700) regulation measure.
In the present invention, olefin saturated rate refers to the amount that alkene is converted into (comprising the alkene such as monoolefine and diolefin) stable hydrocarbon in hydrodesulfurization process, specifically refer to the per-cent of the difference of olefin(e) centent and the olefin(e) centent of stock oil in the product after the olefin(e) centent of stock oil and respective reaction, such as, olefin saturated rate after step (1) refers to the per-cent of the difference of the olefin(e) centent facing hydroformylation reaction product and stock oil and the olefin(e) centent of stock oil.
Embodiment 1
According to flow process shown in Fig. 1 (wherein, do not comprise unifining process) carry out hydrogenating desulfurization, there iing the small-sized hydrogenation evaluating apparatus of the 200ml of two reactors of connecting (wherein, do not comprise hydrofining reactor) in be respectively charged into this reactor of selective hydrogenation catalyst HDDO-100(that Beijing Haishunde Titanium Catalyst Co., Ltd. produces and be hydrogenator), this reactor of catalyst for selectively hydrodesulfurizing HDOS-200(is hydrodesulphurisatioreactors reactors), to stock oil A(character in table 1) carry out hydrogenating desulfurization in accordance with the following steps:
(1) in hydrogenator, facing under hydroformylation reaction condition, stock oil A being contacted with selective hydrogenation catalyst with hydrogen, obtaining facing hydroformylation reaction product (character is in table 1);
Face hydroformylation reaction condition as follows:
Temperature=135 DEG C
Pressure=2.2MPa
Liquid hourly space velocity=3h
-1
Hydrogen to oil volume ratio=10:1
(2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with catalyst for selectively hydrodesulfurizing with hydrogen, obtain hydrodesulfurization reaction product (also claim hydrogenating desulfurization product, all the other embodiments are also like this);
Hydrodesulfurization reaction condition is as follows:
Temperature=250 DEG C
Pressure=2.0MPa
Liquid hourly space velocity=3h
-1
Hydrogen to oil volume ratio=400:1
(3) laggard row gas-liquid separation of being lowered the temperature by the product after described hydrogenating desulfurization obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out the gasoline (character is in table 1) that air lift obtains low sulfur content, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
Table 1
* desulfurization degree %=100% × (sulphur content of raw material C sulphur content-corresponding product)/raw material C sulphur content
* the RON value of the RON value-stock oil A of the corresponding product of △ RON=;
As can be seen from the data of table 1, through step (1), the diene content in stock oil A is down to 0.13gI/100g by 1.8gI/100g, and olefin saturated rate is 3%, and wherein, the methyl isophthalic acid-butenc of 74.1 quality % is methyl-2-butene;
Through step (2), desulfurization degree is 95.7%, the level more than 90%;
Further, as can be seen from the data of table 1, for the stock oil A compared with low sulfur content and olefin(e) centent, hydrogenating desulfurization is carried out according to method of the present invention, when not carrying out hydrofining reaction, the gasoline products of gained low sulfur content contains the sulphur of 10 μ g/g, wherein, mercaptan sulfur is 7 μ g/g, and the RON loss comparing raw material A is 1.3 units.
Embodiment 2
Hydrogenating desulfurization is carried out according to flow process shown in Fig. 1, be respectively charged into this reactor of selective hydrogenation catalyst HDDO-100(that Beijing Haishunde Titanium Catalyst Co., Ltd. produces and be hydrogenator having in the small-sized hydrogenation evaluating apparatus of the 200ml of three reactors of connecting), this reactor of catalyst for selectively hydrodesulfurizing HDOS-200(is hydrodesulphurisatioreactors reactors) and this reactor of Hydrobon catalyst HDMS-100(be hydrofining reactor), in accordance with the following steps hydrogenating desulfurization is carried out to stock oil B:
(1) in hydrogenator, facing under hydroformylation reaction condition, stock oil B being contacted with hydrogenation catalyst with hydrogen, obtaining facing hydroformylation reaction product (character is in table 2); Face hydroformylation reaction condition identical with embodiment 1;
(2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with Hydrobon catalyst with hydrogen, obtain hydrodesulfurization reaction product (character is in table 2); Hydrodesulfurization reaction condition is except temperature is 260 DEG C, and all the other conditions are identical with embodiment 1;
(3) in hydrofining reactor, under Hydrofinishing conditions, described hydrodesulfurization reaction product is contacted with Hydrobon catalyst with hydrogen;
Hydrofining reaction condition is as follows:
Temperature=320 DEG C
Pressure=2.0MPa
Liquid hourly space velocity=3h
-1
Hydrogen to oil volume ratio=400:1
Laggard row gas-liquid separation of being lowered the temperature by product after described hydrofining obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out the gasoline (character is in table 2) that air lift obtains low sulfur content, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
Table 2
* the RON value of the RON value-stock oil B of the corresponding product of △ RON=
As can be seen from the data of table 2, through step (1), the diene content in stock oil B is down to 0.14gI/100g by 1.7gI/100g, and olefin saturated rate is 3.1%, and wherein, the methyl isophthalic acid-butenc of 72.7 quality % is methyl-2-butene;
Through hydrogenating desulfurization and the unifining process of step (2) and step (3), desulfurization degree is 97.8%;
Further, as can be seen from the data of table 2, for the stock oil B of relatively high sulfur content and olefin(e) centent, be 10 μ g/g according to method gained low sulfur content gasoline products sulphur content of the present invention, wherein, mercaptan sulfur is 6 μ g/g, and the RON loss comparing raw material B is 1.5 units.
Embodiment 3
Hydrogenating desulfurization (wherein hydrogenating desulfurization and hydrofining are carried out in a reactor) is carried out according to flow process shown in Fig. 1, having in the small-sized hydrogenation evaluating apparatus of the 200ml of two reactors of connecting, the selective hydrogenation catalyst HDDO-100(hydrogenator that Beijing Haishunde Titanium Catalyst Co., Ltd. produces is loaded) in first reactor, the catalyst for selectively hydrodesulfurizing HDOS-200 of the said firm's production is loaded on second reactor top, the Hydrobon catalyst HDMS-100 that the said firm produces is loaded in bottom, second reactor is hydrogenating desulfurization-hydrofining reactor, as follows hydrogenating desulfurization is carried out to stock oil C:
(1) in hydrogenator, facing under hydroformylation reaction condition, stock oil C being contacted with selective hydrogenation catalyst with hydrogen, obtaining facing hydroformylation reaction product (character is in table 3); Face hydroformylation reaction condition except temperature is 150 DEG C, all the other conditions are identical with embodiment 2;
(2) in hydrodesulphurisatioreactors reactors-hydrofining reactor, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with Hydrobon catalyst with hydrogen, obtains the product after hydrogenating desulfurization; Hydrodesulfurization reaction condition is except temperature is 280 DEG C, and all the other conditions are identical with embodiment 2;
(3) in hydrodesulphurisatioreactors reactors-hydrofining reactor, under Hydrofinishing conditions, the product after described hydrogenating desulfurization is contacted with Hydrobon catalyst with hydrogen; Hydrofining reaction condition is identical with embodiment 2;
Laggard row gas-liquid separation of being lowered the temperature by product after described hydrofining obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out the gasoline (character is in table 3) that air lift obtains low sulfur content, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
Table 3
* the RON value of the RON value-stock oil C of the corresponding product of △ RON=
As can be seen from the data of table 3, through step (1), the diene content in stock oil C is down to 0.18gI/100g by 1.8gI/100g; And olefin saturated rate is 4.7%; Wherein, the methyl isophthalic acid-butenc of 72.4 % by weight is methyl-2-butene;
Through hydrogenating desulfurization and the unifining process of step (2) and step (3), desulfurization degree is 98.3%;
Further, as can be seen from the data of table 3, for the stock oil C of relatively high sulfur content and olefin(e) centent, be 10 μ g/g according to method gained low sulfur content gasoline products sulphur content of the present invention, wherein, mercaptan sulfur is 8 μ g/g, and the RON loss comparing stock oil C is 2.0 units.
Embodiment 4
Hydrogenating desulfurization is carried out according to the method for embodiment 3, unlike, the low sulfur content gasoline obtained is recycled to the opening for feed of device, namely the opening for feed of hydrogenator (wherein, recirculation volume is 0.3-2 times that pending material quantity and stock oil C measure, specifically in table 4), and the temperature (specifically in table 4) of hydrodesulfurization reaction suitably in set-up procedure (2) in hydrodesulphurisatioreactors reactors, make the gasoline products sulphur content of the low sulfur content obtained be about 10 μ g/g(specific natures in table 4).
Table 4
* the RON value of the RON value-stock oil C of the corresponding product of △ RON=
As can be seen from the data of table 4, under the condition of different recirculation ratio (recirculation volume/pending material quantity), the 40.4 volume % olefin(e) centents that the olefin(e) centent of hydrodesulphurisatioreactors reactors entrance compares raw material C have and decline in various degree, and control low sulfur content gasoline products in sulphur content under the condition of 10 μ g/g, hydrogenator is operated in the mode of the gasoline of recirculation part low sulfur content, the low sulfur content gasoline products olefin(e) centent that obtains can be made higher, thus the gasoline products loss of octane number of low sulfur content is diminished, compare embodiment 3, RON loss can reduce by 0.6 unit at most.
Comparative example 1
(1) gasoline selective hydrodesulfrization processing method traditionally, in hydrogenator, under hydrogenation conditions, stock oil C is contacted the product after obtaining hydrogenation reaction with hydrogen with selective hydrogenation catalyst, wherein selective hydrogenation catalyst is HDDO-100.
Hydrogenation conditions is as follows:
Temperature=150 DEG C
Pressure=2.2MPa
Liquid air speed=3h
-1
Hydrogen to oil volume ratio=10:1
(2) product after described hydrogenation reaction is cut into petroleum naphtha (LCN) and heavy petrol (HCN) according to weight constituent mass ratio 4:6 fractionation; In hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, HCN and hydrogen contacted with catalyst for selectively hydrodesulfurizing and carry out hydrodesulfurization reaction, obtain the HCN after desulfurization, wherein, catalyst for selectively hydrodesulfurizing is HDOS-200.
Hydrodesulfurization reaction condition is as follows:
Temperature=280 DEG C
Pressure=2.0MPa
Liquid air speed=3h
-1
Hydrogen to oil volume ratio=400:1
Then obtain low sulfur content gasoline products after being mixed with LCN by the HCN after hydrogenating desulfurization process, wherein, the main character of the HCN after stock oil C, petroleum naphtha (LCN), heavy petrol (HCN), desulfurization and the gasoline products of low sulfur content lists in table 5 again.
Table 5
HCN after the gasoline products=LCN+ desulfurization of * low sulfur content, the RON value of the RON value-stock oil C of △ RON=low sulfur content gasoline products.
As can be seen from the data of table 10, the gasoline products of gained low sulfur content contains the sulphur of 45 μ g/g, and wherein, mercaptan sulfur content is 8 μ g/g, and the RON loss comparing raw material C is 1.4 units.
Comparative example 2
The hydrogenating desulfurization of stock oil C is carried out according to the method for comparative example 1, unlike: cutting weight gasoline, make the mass ratio of petroleum naphtha and heavy petrol be 2:8, and the temperature of heavy petrol hydrogenating desulfurization is 290 DEG C.
Wherein, the main character of the HCN after stock oil C, petroleum naphtha (LCN), heavy petrol (HCN), desulfurization and the gasoline products of low sulfur content lists in table 6.
Table 6
HCN after the gasoline products=LCN+ desulfurization of * low sulfur content, the RON value of the RON value-stock oil C of the gasoline products of △ RON=low sulfur content.
As can be seen from the data of table 6, the gasoline products of gained low sulfur content contains the sulphur of 10 μ g/g, and wherein, mercaptan sulfur content is 6 μ g/g, and the RON loss comparing raw material C is 2.4 units.
As can be seen here, carry out hydrogenating desulfurization according to the comparative example 1 of conventional art and the method for comparative example 2 in the past, when the sulphur content of stock oil C is reduced to 45 μ g/g and 10 μ g/g from 600 μ g/g, its octane value RON loss is respectively 1.4 units and 2.4 units.And according to method of the present invention, 10 μ g/g all can be reached for the sweet gasoline sulphur content after stock oil process all in embodiment, octane value RON loss is simultaneously no more than 2.0 units, and the yield of product is greater than 99 % by weight.And method of the present invention is without the need to cutting stock oil, technical process is simple and saved a large amount of energy consumptions needed for fractionation cutting, and as can be seen here, method of the present invention is very suitable for industrial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (24)
1. a processing method for hydrogenating desulfurization, this processing method comprises:
(1) in hydrogenator, facing under hydroformylation reaction condition, full distillation gasoline is contacted with selective hydrogenation catalyst with hydrogen, obtain facing hydroformylation reaction product, wherein, facing hydroformylation reaction condition described in control makes the saturation exponent of alkene below 10 % by weight, and in full distillation gasoline, the methyl isophthalic acid-butenc of more than 50 % by weight is methyl-2-butene, and faces diene content in hydroformylation reaction product described in making and be down to ≯ 0.8gI/100g;
(2) in hydrodesulphurisatioreactors reactors, under hydrodesulfurization reaction condition, the described hydroformylation reaction product that faces is contacted with catalyst for selectively hydrodesulfurizing with hydrogen, obtains hydrodesulfurization reaction product.
2. method according to claim 1, wherein, facing hydroformylation reaction condition described in rate-determining steps (1) makes the saturation exponent of alkene below 5 % by weight, and the methyl isophthalic acid-butenc of more than 70 % by weight is methyl-2-butene in full distillation gasoline, and faces diene content in hydroformylation reaction product described in making and be down to ≯ 0.5gI/100g.
3. method according to claim 1 and 2, wherein, face hydroformylation reaction condition and comprise described in step (1): temperature is 80-250 DEG C, pressure is 1-5MPa, and liquid hourly space velocity is 1-20h
-1, hydrogen to oil volume ratio is 5-100:1; Described selective hydrogenation catalyst is HDDO-100.
4. method according to claim 1 and 2, wherein, hydrodesulfurization reaction condition described in rate-determining steps (2) makes the organic sulfur conversion of in full distillation gasoline more than 80 % by weight be hydrogen sulfide.
5. method according to claim 3, wherein, hydrodesulfurization reaction condition described in rate-determining steps (2) makes the organic sulfur conversion of in full distillation gasoline more than 80 % by weight be hydrogen sulfide.
6. method according to claim 1 and 2, wherein, described in step (2), hydrodesulfurization reaction condition comprises: temperature is 200-400 DEG C, and pressure is 1-5MPa, and liquid hourly space velocity is 1-20h
-1, hydrogen to oil volume ratio is 100-1000:1; Described catalyst for selectively hydrodesulfurizing is HDOS-200.
7. method according to claim 3, wherein, described in step (2), hydrodesulfurization reaction condition comprises: temperature is 200-400 DEG C, and pressure is 1-5MPa, and liquid hourly space velocity is 1-20h
-1, hydrogen to oil volume ratio is 100-1000:1; Described catalyst for selectively hydrodesulfurizing is HDOS-200.
8. method according to claim 4, wherein, described in step (2), hydrodesulfurization reaction condition comprises: temperature is 200-400 DEG C, and pressure is 1-5MPa, and liquid hourly space velocity is 1-20h
-1, hydrogen to oil volume ratio is 100-1000:1; Described catalyst for selectively hydrodesulfurizing is HDOS-200.
9. method according to claim 5, wherein, described in step (2), hydrodesulfurization reaction condition comprises: temperature is 200-400 DEG C, and pressure is 1-5MPa, and liquid hourly space velocity is 1-20h
-1, hydrogen to oil volume ratio is 100-1000:1; Described catalyst for selectively hydrodesulfurizing is HDOS-200.
10. method according to claim 1 and 2, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
11. methods according to claim 3, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
12. methods according to claim 4, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
13. methods according to claim 5, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
14. methods according to claim 6, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
15. methods according to claim 7, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
16. methods according to claim 8, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
17. methods according to claim 9, wherein, the method also comprises: laggard row gas-liquid separation of being lowered the temperature by described hydrodesulfurization reaction product obtains gas containing hydrogen sulfide and liquid phase substance, described liquid phase substance is carried out air lift and obtains low sulfur content gasoline, the described gas sweetening hydrogen containing hydrogen sulfide is removed substantially the gas of hydrogen sulfide.
18. methods according to claim 10, wherein, the method also comprises: described low sulfur content gasoline circulation is returned step (1) and/or step (2), wherein, the amount returned in step (1) is the 0.1-4 times of weight of the described full distillation gasoline of raw material as step (1), and the amount in step (2) of returning is for facing the 0.1-4 times of weight of hydroformylation reaction product described in the raw material as step (2).
19. methods according to claim 10, wherein, the described concentration of hydrogen sulfide that substantially to remove in the gas of hydrogen sulfide is at 100 below μ L/L, and the method also comprises: the described gas circulation substantially removing hydrogen sulfide is returned step (1) and/or step (2) uses as recycle hydrogen.
20. methods according to claim 10, wherein, the method also comprises: according to needs, before described hydrodesulfurization reaction product is carried out gas-liquid separation, described hydrodesulfurization reaction product is sent in hydrofining reactor, under hydrofining reaction condition, contact with Hydrobon catalyst with hydrogen.
21. methods according to claim 20, wherein, control described hydrofining reaction condition and make the organic sulfur conversion of in full distillation gasoline more than 95 % by weight be hydrogen sulfide.
22. methods according to claim 20, wherein, described hydrofining reaction condition comprises: temperature is 250-450 DEG C, and pressure is 1-5MPa, and liquid hourly space velocity is 1-30h
-1, hydrogen to oil volume ratio is 100-1000:1; Described Hydrobon catalyst is HDMS-100.
23. methods according to claim 1 and 2, wherein, described full distillation gasoline be selected from catalytically cracked gasoline, coker gasoline, catalytic cracking gasoline and pressure gasoline one or more.
24. methods according to claim 1 and 2, wherein, in described full distillation gasoline, sulphur content is at 1200 below μ g/g, olefin(e) centent at 50 below volume %, doing below 250 DEG C of full distillation gasoline.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411658A (en) * | 1991-08-15 | 1995-05-02 | Mobil Oil Corporation | Gasoline upgrading process |
| EP1031622A1 (en) * | 1999-02-24 | 2000-08-30 | Institut Francais Du Petrole | Process for the production of low sulphur gasolines |
| CN1597865A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN1782034A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
-
2013
- 2013-11-14 CN CN201310567188.3A patent/CN103834438B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5411658A (en) * | 1991-08-15 | 1995-05-02 | Mobil Oil Corporation | Gasoline upgrading process |
| EP1031622A1 (en) * | 1999-02-24 | 2000-08-30 | Institut Francais Du Petrole | Process for the production of low sulphur gasolines |
| CN1597865A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN1782034A (en) * | 2004-11-30 | 2006-06-07 | 中国石油化工股份有限公司 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
| CN101245260A (en) * | 2008-02-20 | 2008-08-20 | 宋金文 | Method for producing ultra-low-sulfur oil |
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