CN103468312B - A kind of production method of low-sulphur oil - Google Patents
A kind of production method of low-sulphur oil Download PDFInfo
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Abstract
Produce a method for low-sulphur oil, comprise the following steps: that gasoline stocks is cut into light gasoline fraction, heavy naphtha by (1), wherein, the cut point of light gasoline fraction and heavy naphtha is 50 DEG C ~ 100 DEG C; (2) light gasoline fraction is carried out caustic wash desulfuration, obtain the light gasoline fraction after desulfurization; (3) under hydrogen and catalyst A exist, heavy naphtha is carried out once desulfurization reaction, be isolated to the oil of the heavy naphtha after hydrogenating desulfurization; (4) under rare gas element and catalyst B exist, the heavy naphtha after hydrogenating desulfurization is carried out secondary desulfuration reaction, is isolated to low-sulfur heavy naphtha; (5) heavy naphtha that light gasoline fraction step (2) obtained and step (4) obtain is mixed to get gasoline products.Wherein, described catalyst A and catalyst B are selected from load hydrogenation catalyst for refining, and in catalyst A and catalyst B, the carrier of at least one is the forming composition containing hydrated aluminum oxide.Compared with prior art, the content of sulfur in gasoline of the inventive method production is low, olefin saturated rate is low, has good desulfuration selectivity.
Description
Technical field
The present invention relates to a kind of method of producing low-sulphur oil.
Background technology
Atmospheric pollution is a serious environmental problem, and a large amount of engine discharges causes one of air-polluting major reason.In recent years, be protection of the environment, the composition of countries in the world to motor spirit proposes stricter restriction, to reduce the discharge of objectionable impurities.
At present, the sulphur of China's gasoline product has 90% ~ 99% from catalytically cracked gasoline, and therefore, reducing sulfur content of catalytic cracking gasoline is the key point reducing finished product content of sulfur in gasoline.
Employing catalytically cracked material weighted BMO spaces (front-end hydrogenation) or catalytic gasoline hydrogenation desulfurization (back end hydrogenation) are two kinds of technical schemes of the sulphur content of alternative reduction catalytically cracked gasoline.Wherein, catalytically cracked material pre-treatment significantly can reduce the sulphur content of catalytically cracked gasoline, but needs to operate under temperature and pressure all very exacting terms, simultaneously because unit capacity is large, cause hydrogen to consume also larger, these all will improve investment or the running cost of device.However, due to the heaviness of world's crude oil, increasing catalytic cracking unit starts to process the inferior raw material containing normal, vacuum residuum etc., and therefore catalytically cracked material hydrogenation unit amount is also increasing year by year.
Compare front-end hydrogenation, catalytic gasoline hydrogenation desulfurization in plant investment, production cost and hydrogen consumption all lower than catalytically cracked material weighted BMO spaces.But traditional catalyzer and technique are while hydrogenating desulfurization, and alkene significantly hydrotreated lube base oil can cause product loss of octane number very large.One of effective way solved the problem is exactly adopt selective hydrodesulfurization technology to process catalytically cracked gasoline.Selective hydrodesulfurization technology is removing sulfide in petrol simultaneously, and gasoline olefin is saturated few, can farthest reduce product loss of octane number.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of production method of new low-sulphur oil.
The present inventor finds under study for action, and in gasoline hydrodesulfurizationmethod process, alkene wherein and hydrogenation reaction generate H
2s can generate new mercaptan (being called regeneration mercaptan) and retain in the product.For the gasoline fraction oil being rich in alkene, after hydrogenation, gasoline fraction sulphur content is lower, wherein regenerates mercaptan proportion larger, therefore in order to produce low-sulfur and super low-sulfur oil, must remove the regeneration mercaptan in gasoline fraction after hydrogenation.
The content that the present invention relates to comprises:
1, produce a method for low-sulphur oil, comprise the following steps:
(1) gasoline stocks is cut into light gasoline fraction, heavy naphtha, wherein, the cut point of light gasoline fraction and heavy naphtha is 50 DEG C ~ 100 DEG C;
(2) light gasoline fraction is carried out caustic wash desulfuration, obtain the light gasoline fraction after desulfurization;
(3) under hydrogen and catalyst A exist, heavy naphtha is carried out once desulfurization reaction, be isolated to the oil of the heavy naphtha after hydrogenating desulfurization;
(4) under rare gas element and catalyst B exist, the heavy naphtha after hydrogenating desulfurization is carried out secondary desulfuration reaction, is isolated to low-sulfur heavy naphtha;
(5) heavy naphtha that light gasoline fraction step (2) obtained and step (4) obtain is mixed to get gasoline products;
Wherein, described catalyst A and catalyst B are selected from load hydrogenation catalyst for refining, and in catalyst A and catalyst B, the carrier of at least one is the forming composition containing hydrated aluminum oxide.
2, the method according to 1, is characterized in that, the condition of described once desulfurization reaction comprises: reaction pressure 0.8-3.2MPa, temperature of reaction 200-320 DEG C, feeding liquid time volume space velocity 3-8h
-1, hydrogen to oil volume ratio is 200-600; The condition of described secondary desulfuration reaction comprises: temperature of reaction is 100-350 DEG C, and pressure is 0.2-6MPa, and during feeding liquid, mass space velocity is 1-12h
-1, rare gas element and stock oil volume ratio are 2-200.
3, the method according to 2, is characterized in that, the reaction conditions of described once desulfurization reaction comprises: reaction pressure 1-2.4MPa, temperature of reaction 220-270 DEG C, gasoline fraction fluid time volume space velocity 3-6h
-1, hydrogen to oil volume ratio 300-500; The reaction conditions of described secondary desulfuration reaction comprises: pressure is 0.4-2.5MPa, and temperature of reaction is 140-240 DEG C, and during feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-120.
4, the method according to 1, is characterized in that, the forming composition of described alumina hydrate-containing contains hydrated aluminum oxide and ether of cellulose, and the radial crushing strength of described forming composition is more than or equal to 12N/mm, and water-intake rate is that 0.4-1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of forming composition, and Q2 is that forming composition is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
5, the method according to 4, is characterized in that, the radial crushing strength of described forming composition is 15-30N/mm, and water-intake rate is that 0.6-1, δ are less than or equal to 5%.
6, the method according to 4, is characterized in that, with described forming composition for benchmark, the content of described ether of cellulose is 0.5-8 % by weight.
7, the method according to 6, is characterized in that, with described forming composition for benchmark, the content of described ether of cellulose is 1-6 % by weight.
8, the method according to 7, is characterized in that, with described forming composition for benchmark, the content of described ether of cellulose is 2-5 % by weight.
9, the method according to 4, is characterized in that, described ether of cellulose is selected from one or more in methylcellulose gum, hydroxyethylmethyl-cellulose, Vltra tears.
10, the catalyzer according to 9, is characterized in that, described ether of cellulose is methylcellulose gum, hydroxyethylmethyl-cellulose and their mixture.
11, the method according to 1, is characterized in that, described hydrated aluminum oxide is selected from one or more in pseudo-boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
12, the catalyzer according to 11, is characterized in that, described hydrated aluminum oxide is pseudo-boehmite.
13, the method according to 1, it is characterized in that, described load hydrogenation catalyst for refining contains the metal component that carrier, load at least one is on this carrier selected from the non-noble metal components of group VIII, at least one is selected from group vib, take catalyzer as benchmark, with the content of the group VIII metal component of oxide basis for 0.1-6 % by weight, with the content of the group vib metal component of oxide basis for 1-25 % by weight, vector contg is 69-98 % by weight.
14, the method according to 13, it is characterized in that, take catalyzer as benchmark, with the content of the group VIII metal component of oxide basis for 1-5 % by weight, with the content of the group vib metal component of oxide basis for 5-20 % by weight, vector contg is 75-94 % by weight.
15, the method according to 1 or 13, is characterized in that, containing being selected from alcohol, organic acid and organic amine one or more organism in described catalyzer, the mol ratio of described organism and group VIII metal component is 0.5-2.5.
16, the method according to 15, is characterized in that, the mol ratio of described organism and group VIII metal component is 1-2.
17, the method according to 1, is characterized in that, described catalyst A carries out prevulcanized before use.
18, the method according to 1, is characterized in that, the reactor of described secondary desulfuration reaction is countercurrent reactor.
19, the method according to 1, is characterized in that, described hydrogen-containing gas be hydrogen with arbitrary under secondary desulfuration reaction conditions with hydrogenating desulfurization after gasoline fraction be the gas of inert reaction.
20, the method according to 17, is characterized in that, described rare gas element is selected from the mixture of one or more of nitrogen, carbonic acid gas, carbon monoxide, hydro carbons, water vapour.
21, the method according to 1, is characterized in that, one or more in described gasoline fraction grease separation catalytic cracking gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.
22, the method according to 21, is characterized in that, the boiling range of described gasoline fraction oil is 30-220 DEG C.
According to method provided by the invention, the reaction of described once desulfurization is hydrogenating desulfurization (comprise hydrogenation takes off carbonylsulfide, hydro-sweetening, hydrogenation take off thiophene-type sulfide, hydrogenating desulfurization ether) reaction, and preferred reaction conditions comprises: volume space velocity 3h when reaction pressure 1MPa-2.4MPa, temperature of reaction 220 DEG C-270 DEG C, gasoline fraction fluid
-1-6h
-1, hydrogen to oil volume ratio 300-500.
The reaction of described secondary desulfuration, to remove regeneration mercaptan for main purpose, is a kind of decomposition under containing the catalyst action with hydrogenation-dehydrogenation active metal component by mercaptan and the desulphurization reaction that realizes.Preferred reaction conditions comprises: temperature of reaction is 140-240 DEG C, and pressure is 0.4-2.5MPa, and during feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-120.
Wherein, described catalyst A and catalyst B can be the same or different.Under guaranteeing that the carrier of at least one catalyzer in catalyst A and catalyst B is the prerequisite of forming composition containing hydrated aluminum oxide, the present invention is not that the selection of the Hydrobon catalyst prepared by the described forming composition carrier containing hydrated aluminum oxide does not limit, and namely can be the combination that any one that prior art provides can be used for hydrorefined catalyzer or catalyzer.
According to method provided by the invention, in a preferred embodiment, described catalyst A preferably carries out prevulcanized before use, is converted into sulfide to make wherein have hydrogenation-dehydrogenation active metal component; Catalyst B does not then need to carry out prevulcanized in use, and namely preferably having hydrogenation-dehydrogenation active metal component is oxide compound.
Described moisture and preparation method that is aluminum oxide forming composition comprises hydrated aluminum oxide and ether of cellulose mixing, shaping and dry, wherein, the consumption of each component and shaping and drying conditions make the radial crushing strength of described forming composition be more than or equal to 12N/mm, water-intake rate is that 0.4-1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of forming composition, and Q2 is that forming composition is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.The size of δ value represents hydrated alumina forming matter through the change (or be called loss of strength rate) of water soaking anteroposterior diameter to crushing strength.
Preferably, the consumption of each component and shaping and drying conditions make the radial crushing strength of described forming composition be 15N/mm-30N/mm, and water-intake rate is that 0.6-1, δ are less than or equal to 5%.With described forming composition for benchmark, the content of described ether of cellulose is 0.5-8 % by weight, and more preferably 1%-6 % by weight, is more preferably 2%-5 % by weight; Described drying conditions comprises: temperature 60 C is to being less than 350 DEG C, and more preferably 80-150 DEG C, is more preferably 100-130 DEG C; Time of drying 1-48 hour, more preferably 2-14 hour, is more preferably 3-10 hour.Described ether of cellulose is selected from one or more in methylcellulose gum, hydroxyethylmethyl-cellulose, Vltra tears, more preferably methylcellulose gum, hydroxyethylmethyl-cellulose and their mixture.
The forming composition of wherein said alumina hydrate-containing, the radial crushing strength of preferred described forming composition is 15-30N/mm, and water-intake rate is that 0.6-1, δ are less than or equal to 5%.Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of hydrated alumina forming matter, and Q2 is hydrated alumina forming matter through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.The size of δ value represents hydrated alumina forming matter through the change (or be called loss of strength rate) of water soaking anteroposterior diameter to crushing strength.
In the present invention, the measuring method of the radial crushing strength of described forming composition is carried out according to RIPP25-90 catalyzer compressive strength assay method, and the concrete steps measured about the radial crushing strength of forming composition have detailed introduction at RIPP25-90, do not repeat here.
Described water-intake rate adopts following concrete grammar to measure: first dried 4 hours by testing sample 120 DEG C.Take out sample, be positioned in exsiccator and be cooled to room temperature, with 40 mesh standard sieve screenings, take screen overflow 20g (numbering: w1) testing sample, add 50g deionized water, soak 30min, filter, solid phase drains 5min, weigh solid phase weight (numbering: w2), solid phase be transferred in baking oven, 120 DEG C of heating, dryings 4 hours, are positioned in exsiccator and are cooled to room temperature.Water-intake rate=(w2-w1)/w1
In the present invention, can containing the adjuvant component not affecting or be of value to radial crushing strength, water-intake rate and the δ value of improving described forming composition in described alumina hydrate-containing forming composition.Such as, containing starch addO-on therapy, described starch can be the powder obtained through pulverizing by plant seed arbitrarily, as sesbania powder.
Described hydrated aluminum oxide is selected from the hydrated aluminum oxide that any one can be used as sorbent material and support of the catalyst precursor, such as, can be pseudo-boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides, preferred pseudo-boehmite.
In the present invention, the preparation method of described hydrated alumina forming matter can be arbitrary prior art.Such as, described forming method can be the forming method of extrusion, round as a ball, compressing tablet and their combination.For ensureing shaping carrying out smoothly, auxiliary agent and water etc. can be introduced herein in material (being the mixture of hydrated aluminum oxide and ether of cellulose) when shaping, such as, when adopting extrusion method shaping, comprise by described hydrated aluminum oxide and ether of cellulose and water, containing or do not mix containing extrusion aid, then extrusion moulding, obtains wet bar, then drying obtains forming composition of the present invention.Described auxiliary agent is selected from starch, and described starch can be the powder obtained through pulverizing by plant seed arbitrarily, as sesbania powder.Preferred forming method is the method for extruded moulding.
On shaping water and alumina supporter, load at least one is selected from the metal component that the non-noble metal metal component of VIII and at least one are selected from group vib, and in the catalyst containing when being selected from alcohol, organic acid and organic amine, the method that the method that load is selected from alcohol, organic acid and organic amine on shaping water and alumina supporter is preferably flooded, described dipping method is ordinary method, such as hole saturation method dipping, excessive immersion stain and spray impregnating.Wherein, comprise preparation dipping solution, such as, described in containing, be selected from the compound of the metal component of at least one group vib, prepare dipping solution (when containing organism) respectively containing the compound of the metal component of at least one group VIII or described organism, and by the method for these dipping solution impregnated carriers; Or be selected from described in containing at least one group vib metal component, prepare hybrid infusion solution containing in two kinds or three in the compound of the metal component of at least one group VIII and described organism (when containing organism), and by the method for these dipping solution impregnated carriers.When described dipping is step impregnation, the order of described dipping solution impregnated carrier is not limited.Although optional, after each dipping, preferably include dry step.Described drying conditions comprises: drying temperature 100-210 DEG C, preferred 150-190 DEG C, and time of drying, 1-6 hour, was preferably 2-4 hour.
The compound of the described non-noble metal components containing VIII is selected from one or more in their soluble salt and complex compound, such as, one or more in the nitrate of group VIII metal, muriate, acetate, subcarbonate, are selected from one or more in the solubility of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Cobaltous diacetate, cobaltous dihydroxycarbonate, cobalt chloride and cobalt for cobalt salt.The described compound containing group vib metal component is selected from one or more in their soluble compound, such as, molybdenum oxide, molybdate are (such as, ammonium molybdate, ammonium paramolybdate, ammonium phosphomolybdate), one or more in tungstate (such as, ammonium tungstate, ammonium metawolframate, ammonium paratungstate, ethyl metatungstate).
Described alcohol can be selected from one or more in ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, described acid is selected from acetic acid, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartrate, oxysuccinic acid, described organic amine is selected from quadrol or EDTA and ammonium salt thereof.Wherein, the mol ratio that the introduction volume being selected from alcohol, organic acid and organic amine described in meets described organism and group VIII metal component is preferably 0.5-2.5, more preferably 1-2.
According to method provided by the invention, wherein said catalyzer maybe can improve the material of the catalytic performance of catalyzer provided by the invention containing any material not affecting the catalytic performance that the invention provides catalyzer.As contained phosphorus, be benchmark in element and with catalyzer, the content of above-mentioned auxiliary agent is no more than 10 % by weight, is preferably 0.5-5 % by weight.
When in described catalyzer also containing when being selected from the components such as phosphorus, the described introducing method being selected from the components such as phosphorus can be arbitrary method, as can be by containing as described in auxiliary agent compound be selected from VIII non-noble metal metal-salt and be selected from group vib metal-salt be mixed with mixing solutions after flood as described in the method for carrier introduce.
When being with the catalyzer that is carrier of the forming composition containing hydrated aluminum oxide one of in catalyst A and catalyst B, another kind of catalyzer can be selected from the Hydrobon catalyst that arbitrary prior art provides.Such as, described catalyst A with aluminum oxide or silica-alumina for carrier, to be selected from the metal component of at least one group vib and at least one VIII for hydrogenation active metals component, be benchmark with oxide basis and with catalyzer, the content being selected from vib metal component is 5 ~ 30 heavy %, the content of VIII metal component is 0.5 ~ 5 heavy %, and optionally described catalyzer can also contain adjuvant component, such as, containing a small amount of auxiliary agent being selected from IA main group, IIA main group or VA subgroup; Described catalyst B take aluminum oxide as carrier, to be selected from the metal component of at least one group vib and at least one VIII for hydrogenation active metals component, be benchmark with oxide basis and with catalyzer, the content being selected from vib metal component is 4 ~ 15 heavy %, and the content of VIII metal component is 1 ~ 5 heavy %.About this type of catalyzer example as, at 200710099304.8,200710099302.9,200710099834.2 respectively disclosed catalyzer, they can be used for the present invention as catalyzer.
According to method provided by the present invention, wherein said separation, its method and be the method and apparatus that this area usually adopts for realizing device needed for the method.Such as, the usual apparatus and method in this area are adopted to carry out air lift, distillation etc. to generation oil, to remove the hydrogen sulfide and other non-gasoline components that generate and contain in oil.
Be enough to make described charging under the cited reaction conditions with under the prerequisite of described catalyst exposure, the present invention is not particularly limited described reactor.Such as, described in carry out once desulfurization reaction reactor can be the reactor that in prior art, any one is suitable for gasoline fraction oil hydrodesulfurization reaction, such as fixed bed hydrogenation reactor.The described reactor carrying out secondary desulfuration reaction can be comprise the various forms of reactors such as fixed-bed reactor, fluidized-bed reactor, distillation column reactor or ebullated bed reactor.In a preferred embodiment, described in carry out secondary desulfuration reaction reactor be preferably counter-current reactor, the gasoline fraction namely after described hydrogenating desulfurization flows in the reactor from top to bottom, described rare gas element flows from bottom to top and contacts with catalyst B.In counter-current reactor, the gasoline fraction after hydrogenating desulfurization and rare gas element are reverse in the presence of a catalyst to be contacted, by the H that reaction produces
2s shifts out beds in time, and rare gas element medium takes reactor out of.Described counter-current reactor can be various forms, such as, can be fixed bed, fluidized-bed, distillation tower or ebullated bed reactor etc., also can carry out in the stripping tower being filled with catalyst B or stabilizer tower.In the gasoline hydrogenation technique of routine, general have stripping tower or stabilizer tower in order to remove lighter hydrocarbons and the hydrogen sulfide such as methane, ethane after hydrogenation in gasoline, utilize the stripping tower in existing hydrogenation unit or stabilizer tower, while removing reacted regeneration mercaptan and lighter hydrocarbons and hydrogen sulfide, can simplification of flowsheet, save facility investment.When the reactor that described secondary desulfuration reacts selects counter-current reactor, described rare gas element and stock oil volume ratio more preferably 5-40.
Described hydrogen can be pure hydrogen gas also can be the refinery gas being rich in hydrogen, and such as hydrogen volume percentage composition is the refinery gas of more than 70%, and preferred hydrogen volume percentage composition is the refinery gas (comprising circulating hydrogen) of more than 80%
Described rare gas element, for arbitrary under secondary desulfuration reaction conditions with hydrogenating desulfurization after gasoline fraction be the gas of inert reaction, such as, they can be the mixtures of one or more being selected from nitrogen, carbonic acid gas, carbon monoxide, hydro carbons, water vapour, preferred hydro carbons.
According to method provided by the invention, described gasoline stocks oil can be catalytically cracked gasoline distillate, catalytic cracking gasoline distillate, Straight run naphthas oil, coker naphtha is oily, pyrolysis gasoline cut fraction is oily and one or more in pressure gasoline distillate.The boiling range of described gasoline stocks oil is the usual boiling range of gasoline fraction oil, such as: can be 30-220 DEG C.
The cut point of described light gasoline fraction and heavy naphtha is preferably 50-75 DEG C.In a preferred embodiment, the yield by cutting described light gasoline fraction and heavy naphtha is respectively the 30 heavy % in heavy % ~ 60 and the heavy % in 40 heavy % ~ 70 of gasoline stocks.
According to method provided by the present invention, wherein, the method for described caustic wash desulfuration and operational condition are this area conventional process and condition.Such as, the method for alkali cleaning extracting, the operational condition of described alkali cleaning extracting comprises: oily alkali volume ratio 15: 1-1: 1, and extraction temperature is less than 40 DEG C, extraction pressure 0.1MPa-0.8MPa.About these methods " petroleum refining engineering " (volume two) (petroleum industry press, Lin Shixiong work, version in 1988) 350 pages carried out description, quote as a reference here.
According to method provided by the invention, described gasoline stocks oil can be catalytically cracked gasoline distillate, catalytic cracking gasoline distillate, Straight run naphthas oil, coker naphtha is oily, pyrolysis gasoline cut fraction is oily and one or more in pressure gasoline distillate.The boiling range of described gasoline stocks oil is the usual boiling range of gasoline fraction oil, such as: can be 30-220 DEG C.
Compared with prior art, the sulphur content of the inventive method production gasoline is low, olefin saturated rate is low, has good desulfuration selectivity.Particularly, when described secondary desulfuration reaction is carried out in counter-current reactor, hydrogen sulfide in fluid, lighter hydrocarbons shift out reaction zone with on rare gas element, and the stripping fluid of sulfide hydrogen and lighter hydrocarbons is discharged on counter-current reactor top, and reactor bottom obtains the gasoline products being stripped of mercaptan.Therefore, can realization response product separation while completing reaction.
Accompanying drawing explanation
Figure-1 is for the invention provides a kind of schematic flow sheet of method.
Embodiment
The invention provides a kind of of method preferred embodiment to realize by the flow process shown in Fig. 1.
According to the flow process shown in Fig. 1, gasoline stocks enters separation column 2 through pipeline 3 and is cut into light gasoline fraction, heavy naphtha, wherein light gasoline fraction enters soda-wash tower 26 through pipeline 4 and removes mercaptan removal, heavy naphtha enters pump 6 through pipeline 5 and mixes with the hydrogen from pipeline 17, process furnace 8 is entered through pipeline 7, material after heating enters through pipeline 9 the once desulfurization reactor 10 being filled with catalyst A and carries out desulphurization reaction, hydrogenated oil enters high-pressure separator 13 through pipeline 11, from high-pressure separator 13 top, hydrogen-rich gas out enters compressor 15 through pipeline 14, hydrogen-rich gas after compression mixes through pipeline 16 or with the supplementary fresh hydrogen from pipeline 1, mixing hydrogen is through pipeline 17, dereaction is mixed with the gasoline stocks and heavy distillate raw material that carry out self-pumping 6.Bottom separator 13, liquid stream out enters the secondary desulfuration reactor 18 being filled with catalyst B through pipeline 12, and secondary desulfuration reactor 18 is a kind of stripping tower of routine, be filler is wherein catalyst B with conventional gas stripping column difference.Hydrogen sulfide in charging, lighter hydrocarbons are separated with gasoline fraction in stripping tower.Gasoline flows downward and the rare gas element risen counter current contact on mercaptan-eliminating catalyst in secondary desulfuration reactor, at the bottom of tower after mercaptan removal, liquid flows out from pipeline 23, a part obtains the heavy naphtha after mercaptan removal through pipeline 25, mix with the light gasoline fraction after the mercaptan removal of pipeline 27, obtain gasoline products and go out device through pipeline 28.Another part returns in tower through pipeline 24 after entering reboiler vaporization.Part hydrocarbon ils steam, hydrogen sulfide and lighter hydrocarbons distillate from tower top, enter condenser through pipeline 19 and carry out condensation, separator 20 is entered after condensation, from separator 20 top, lighter hydrocarbons such as hydrogen sulfide and methane, ethane, propane are out emptying through pipeline 21 as non-condensable gas, and bottom separator 20, liquid product is out back in stripping tower through pipeline 22.
The following examples will be further described method provided by the invention, but not thereby limiting the invention.
Embodiment 1-6 illustrates shaping carrier and the preparation thereof of alumina hydrate-containing.
Embodiment 1
Get the pseudo-boehmite powder 100g that catalyzer Chang Ling branch office produces, add 4.0g methylcellulose gum, 3.0g sesbania powder and 95mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains the wet forming composition of aluminium hydroxide.Wet hydrogen aluminum oxide forming composition to be positioned in baking oven 150 DEG C of dryings 12 hours.Obtain shaping carrier Z1, measure the radial crushing strength of Z1, water-intake rate and δ value (loss of strength rate), the results are shown in table 1.
Embodiment 2
Get the pseudo-boehmite powder 50g that catalyzer Chang Ling branch office produces, self-control unformed aluminium hydroxide powder 50g, add 2.0g methylcellulose gum, 3.0g hydroxyethylmethyl-cellulose and 95mL deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains the wet forming composition of aluminium hydroxide.Wet hydrogen aluminum oxide forming composition to be positioned in baking oven 220 DEG C of dryings 6 hours.Obtain shaping carrier Z2, measure the radial crushing strength of Z2, water-intake rate and δ value, the results are shown in table 1.
Embodiment 3
Get the pseudo-boehmite powder 60g that catalyzer Chang Ling branch office produces, three water-aluminum hydroxide 40g, add 1.0g methylcellulose gum, 2.0g Vltra tears, 3.0g sesbania powder and 95mL deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains the wet forming composition of aluminium hydroxide.Wet hydrogen aluminum oxide forming composition to be positioned in baking oven 80 DEG C of dryings 12 hours.Obtain shaping carrier Z3, measure the radial crushing strength of Z3, water-intake rate and δ value, the results are shown in table 1.
Embodiment 4
Get the pseudo-boehmite SB powder 100g that Sasol company produces, add 3.0g hydroxyethylmethyl-cellulose and 90mL deionized water, be fully uniformly mixed, after even by banded extruder kneading, extruded moulding obtains shaping bar.The shaping bar of aluminium hydroxide to be positioned in baking oven 150 DEG C of dryings 12 hours.Obtain shaping carrier Z4, measure the radial crushing strength of Z4, water-intake rate and δ value, the results are shown in table 1.
Embodiment 5
Get the pseudo-boehmite SB powder 100g that Sasol company produces, add 3.0g hydroxyethylmethyl-cellulose, 2g Vltra tears, 3.0g sesbania powder and 90mL deionized water, fully be uniformly mixed, after even by banded extruder kneading, extruded moulding obtains shaping bar.The shaping bar of aluminium hydroxide to be positioned in baking oven 250 DEG C of dryings 4 hours.Obtain shaping carrier Z5, measure the radial crushing strength of Z5, water-intake rate and δ value, the results are shown in table 1.
Embodiment 6
Get the pseudo-boehmite powder 100g that Yantai, Shandong Heng Hui Chemical Co., Ltd. produces, add 5.0g Vltra tears, 3.0g sesbania powder and 90mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 120 DEG C of dryings 4 hours.Obtain shaping carrier Z6, measure the radial crushing strength of Z6, water-intake rate and δ value, the results are shown in table 1.
Comparative example 1-4 illustrates reference shaping carrier and preparation thereof.
Comparative example 1
Get the pseudo-boehmite powder 100g that catalyzer Chang Ling branch office produces, add concentrated nitric acid 2.5mL, 3.0g sesbania powder and 95mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 80 DEG C of dryings 4 hours.Obtain shaping carrier DZ1, measure the radial crushing strength of DZ1, water-intake rate and δ value, the results are shown in table 1.
Comparative example 2
Get the pseudo-boehmite SB powder 100g that Condea company produces, add 20ml Alumina gel, 3.0g sesbania powder and 90mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 150 DEG C of dryings 4 hours.Obtain shaping carrier DZ2, measure the radial crushing strength of DZ2, water-intake rate and δ value, the results are shown in table 1.
Comparative example 3
Get the pseudo-boehmite powder 100g that Yantai, Shandong Heng Hui Chemical Co., Ltd. produces, add 5.0mL acetic acid, 3.0g sesbania powder and 90mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 180 DEG C of dryings 4 hours.Obtain shaping carrier DZ3, measure the radial crushing strength of DZ3, water-intake rate and δ value, the results are shown in table 1.
Comparative example 4
Get the pseudo-boehmite powder 100g that catalyzer Chang Ling branch office produces, add concentrated nitric acid 2.5mL, 3.0g sesbania powder and 95mL deionized water, be fully uniformly mixed, and after even by banded extruder kneading, extruded moulding obtains shaping bar.Shaping bar to be positioned in baking oven 80 DEG C of dryings 4 hours.Dried strip 600 DEG C of roastings 4 hours.Obtain shaping carrier DZ4, measure the radial crushing strength of DZ4, water-intake rate and δ value, the results are shown in table 1.
Table 1
Embodiment 7-11 and comparative example 5-6 illustrates the catalyzer adopting the shaping carrier Kaolinite Preparation of Catalyst of alumina hydrate-containing He have comparative example carrier to prepare respectively.
Embodiment 7
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum, cobalt and organism at carrier Z1.First, take citric acid 11.5 grams, after being dissolved to clear in deionized water, continuous heating is to solution temperature 50 DEG C, slowly adds molybdic oxide 12.9 grams, cobaltous dihydroxycarbonate 7.1 grams, continues to be dissolved to total liquid 84 milliliters.Dissolution process heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C of dryings 4 hours, obtains catalyzer C1.In catalyzer C1, the molar ratio of citric acid and group VIII metal component is cobalt in 1.0, C1, molybdenum oxide content lists in table 2.
Embodiment 8
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 12.7 grams, take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 11.3 grams, citric acid 12.6 grams, dissolves ammonium paramolybdate, citric acid and Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES to total liquid 84 milliliters successively with deionized water, heating, solvent temperature remains on 50 DEG C, with this solution impregnating carrier Z1, in 170 DEG C of dryings 4 hours, obtain catalyzer C2.In catalyzer C2, the molar ratio of citric acid and group VIII metal component is cobalt in 1.6, C2, molybdenum oxide content lists in table 2.
Embodiment 9
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 18.0 grams, after being dissolved to clear with ammonia solvent to 70 ml soln that concentration is 18 % by weight, take cobaltous dihydroxycarbonate 8.4 grams, EDTA22.2 gram, add above-mentioned solution and continue to be dissolved to total liquid 84 milliliters.Dissolution process heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier Z3, in 170 DEG C of dryings 4 hours, obtains catalyzer C3.In catalyzer C3, the molar ratio of EDTA and group VIII metal component is cobalt in 1.0, C3, molybdenum oxide content lists in table 2.
Embodiment 10
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 8.9 grams, after being dissolved to clear with ammonia solvent to 90 ml soln that concentration is 18 % by weight, take cobaltous dihydroxycarbonate 3.6 grams, EDTA9.7 gram, add above-mentioned solution and continue to be dissolved to total liquid 84 milliliters.Dissolution process heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier Z1, in 170 DEG C of dryings 4 hours, obtains catalyzer C4.In catalyzer C4, the molar ratio of EDTA and group VIII metal component is cobalt in 1.2, C4, molybdenum oxide content lists in table 2.
Embodiment 11
Get 100 grams of carrier Z1.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier Z1.First, take ammonium paramolybdate 21.9 grams, take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 18.6 grams, spend after strong aqua dissolves ammonium paramolybdate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES to clear successively and mend weak ammonia to total liquid 84 milliliters, dissolution process heats, and temperature remains on 40 DEG C, with this solution impregnating carrier Z1, in 120 DEG C of dryings 4 hours, 420 DEG C of roastings 3 hours, obtained catalyzer C5.In C5, cobalt, molybdenum oxide content are listed in table 2.
Comparative example 5
Get 100 grams of carrier DZ4.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier DZ4.First, take ammonium paramolybdate 8.9 grams, after being dissolved to clear with ammonia solvent to 90 ml soln that concentration is 18 % by weight, take cobaltous dihydroxycarbonate 3.6 grams, EDTA9.7 gram, add above-mentioned solution and continue to be dissolved to total liquid 95 milliliters.Dissolution process heats, and temperature remains on 50 DEG C, with this solution impregnation 100g carrier DZ4, in 170 DEG C of dryings 4 hours, obtains catalyzer DB1.In catalyzer DB1, the molar ratio of EDTA and group VIII metal component is cobalt in 1.2, DB1, molybdenum oxide content lists in table 2.
Comparative example 6
Get 100 grams of carrier DZ4.
The method of total immersion stain is adopted to introduce molybdenum and cobalt at carrier DZ4.First, take ammonium paramolybdate 12.8 grams, after being dissolved to clear with ammonia solvent to 80 ml soln that concentration is 18 % by weight, take Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 13.6 grams, add above-mentioned solution and continue to be dissolved to total liquid 95 milliliters.The micro-heating of dissolution process, temperature remains on 30 DEG C, and with this solution impregnation 100g carrier DZ4, in 170 DEG C of dryings 4 hours, 350 DEG C of roastings 3 hours, obtain catalyzer DB2.In DB2, cobalt, molybdenum oxide content are listed in table 2.
Table 2
| Example | Catalyzer | Carrier | CoO, % by weight | MoO 3, % by weight |
| 7 | C1 | Z1 | 3.5 | 11.0 |
| 8 | C2 | Z1 | 2.5 | 9.0 |
| 9 | C3 | Z1 | 4.3 | 12.4 |
| 10 | C4 | Z1 | 1.9 | 6.5 |
| 11 | C5 | Z1 | 3.8 | 14.5 |
| Comparative example 5 | DB1 | DZ4 | 1.9 | 6.5 |
| Comparative example 6 | DB2 | DZ4 | 3.0 | 9.0 |
Remarks: on metal, amount is for catalyzer is through 550 DEG C of roastings XRF analysis result after 4 hours.
Embodiment 12-16
The model compound containing 10% thiophene, 20% n-hexylene and 70% normal heptane is adopted to carry out activity rating to catalyzer C1-C5.Evaluating apparatus is fixed bed hydrogenation microreactor, and hydrogen adopts and once passes through.First carry out prevulcanized before evaluating catalyst, vulcanized oil is for containing 6%CS
2hexanaphthene.Cure conditions is: pressure 1.6MPa, hydrogen to oil volume ratio 3600: 1, weight space velocity 6.0h
-1, temperature 320 DEG C, time 2 h.
Change model compound into after sulfuration terminates, temperature of reaction 230 ~ 320 DEG C of changes, on-line chromatograph analysis, and draw thiophene transformation efficiency-hydrotreated lube base oil rate curve, when being 80% according to response curve reading thiophene transformation efficiency afterwards, the hydrotreated lube base oil rate HYD of n-hexylene, the results are shown in Table 3.
Comparative example 7-8
Evaluate comparative catalyst DB1, DB2 according to embodiment 12-16 same procedure, the results are shown in Table 3.
Table 3
| Embodiment | Catalyzer | HYD，％ |
| 12 | C1 | 43 |
| 13 | C2 | 47 |
| 14 | C3 | 40 |
| 15 | C4 | 48 |
| 16 | C5 | 45 |
| Comparative example 7 | DB1 | 63 |
| Comparative example 8 | DB2 | 58 |
Embodiment 17
This example high-sulfur catalytically cracked gasoline carries out activity rating to catalyzer C3.Stock oil character is in table 4.
Evaluating apparatus is fixed bed hydrogenation reactor, and hydrogen adopts and once passes through.Before reaction, first catalyzer carries out prevulcanized, and vulcanized oil is for containing 2%CS
2grand celebration straight-run spirit.Cure conditions is: pressure 1.6MPa, hydrogen to oil volume ratio 400: 1, volume space velocity 2.0h
-1, temperature is 320 DEG C, 3 hours time.Charging is switched to grand celebration straight-run spirit, after stablizing 30 hours, charging is switched to the reaction of high-sulfur catalytically cracked gasoline, reaction conditions and the results are shown in Table 5.
Anti-knock index is (RON+MON)/2.Anti-knock index change refers to the anti-knock index of desulfurization product and the difference of stock oil anti-knock index.If the anti-knock index of desulfurization product is lower than stock oil anti-knock index, then anti-knock index is changed to negative value, on the contrary be on the occasion of.
Table 4
| Test number | Raw material |
| Sulphur, microgram/g | 1500 |
| Group composition, v% | |
| Stable hydrocarbon | 38.0 |
| Alkene | 22.9 |
| Aromatic hydrocarbons | 39.1 |
Table 5
| Embodiment | 17 |
| Temperature of reaction, DEG C | 280 |
| LHSV，h -1 | 4 |
| Reaction pressure, kg/cm 2 | 16 |
| Hydrogen-oil ratio, v/v | 400∶1 |
| Sulphur, microgram/g | 38 |
| Desulfurization degree, m% | 97.47 |
| Olefin saturated rate, v% | 32.26 |
Table 5 result shows, the catalyzer prepared by alumina hydrate-containing shaping carrier has high desulfurization activity and lower olefin saturated is active, is more suitable for the selective hydrodesulfurization for olefine contained gasoline distillate.
Embodiment 18-19 illustrates and the invention provides method and effect thereof.
Usedly in embodiment except by the catalyzer except alumina hydrate-containing shaping carrier Kaolinite Preparation of Catalyst be:
RSS-1, be benchmark with oxide basis and with catalyzer, it consists of: nickel content 4.5 % by weight, W content 13.6 % by weight, and surplus is alumina supporter.
Embodiment 18
Low-sulphur oil is produced according to the flow process shown in Fig. 1.
Gasoline stocks oil is catalytic cracking full distillate gasoline, and character is in table 6.Obtain light gasoline fraction and heavy naphtha through fractionation cutting, cut point is 65 DEG C.Light gasoline fraction and heavy naphtha character list in table 1.
Light gasoline fraction enters soda-wash tower mercaptan removal, and operational condition is: extraction temperature 30 DEG C, pressure 0.4MPa, concentration of lye 15%, oily alkali volume ratio 10: 1.
Heavy naphtha enters a hydrodesulphurisatioreactors reactors and carries out desulfurization, and after hydrogenating desulfurization, heavy naphtha enters secondary desulfuration reactor and carries out desulfurization.Catalyst A is C3, and catalyst B is RSS-1.
Once desulfurization reaction conditions is: temperature of reaction is 265 DEG C, and reaction pressure is 1.6MPa, and gasoline feeding volume space velocity is 4h
-1, gasoline feeding hydrogen to oil volume ratio is 400.After hydrogenating desulfurization, the character of heavy naphtha lists in table 7.
Secondary desulfuration reaction conditions is: pressure is 1.3MPa, and the following beds medial temperature of charging is 220 DEG C, feedstock quality air speed 3h
-1, steam (volatized hydrocarbon) and stock oil volume ratio are 7.After secondary desulfuration, the character of heavy naphtha lists in table 8.
After the heavy naphtha of secondary desulfuration and caustic wash desulfuration, light gasoline fraction is mixed to get gasoline products S1, and its character is in table 9.
Embodiment 19
Low-sulphur oil is produced according to the flow process shown in Fig. 1.
Gasoline stocks oil is catalytic cracking full distillate gasoline, and character is in table 6.Obtain light gasoline fraction and heavy naphtha through fractionation cutting, cut point is 65 DEG C.Light gasoline fraction and heavy naphtha character list in table 6.
Light gasoline fraction enters soda-wash tower 26 mercaptan removal, and operational condition is: extraction temperature 30 DEG C, pressure 0.4MPa, concentration of lye 15%, oily alkali volume ratio 10: 1.
Heavy naphtha enters a hydrodesulphurisatioreactors reactors 10 and carries out desulfurization, and after hydrogenating desulfurization, heavy naphtha enters secondary desulfuration reactor 18 and carries out desulfurization.Catalyst A is C3, and catalyst B is C2.
Once desulfurization reaction conditions is: temperature of reaction is 240 DEG C, and reaction pressure is 1.6MPa, and gasoline feeding volume space velocity is 3h
-1, gasoline feeding hydrogen to oil volume ratio is 400.After hydrogenating desulfurization, the character of gasoline fraction lists in table 7.
Secondary desulfuration reaction conditions is: pressure is 1.3MPa, and the following beds medial temperature of charging is 220 DEG C, feedstock quality air speed 3h
-1, steam (volatized hydrocarbon) and stock oil volume ratio are 7.The character of gasoline products S2 lists in table 9.
Comparative example 9
Gasoline products is produced according to the flow process shown in embodiment 18.Difference is, the catalyzer C3 in reactor 10 is replaced by DB1, and the catalyst B in embodiment 18 is replaced by RSS-1.Stripping tower working pressure is 1.1MPa, feedstock quality air speed 3h
-1, steam (volatized hydrocarbon) and stock oil volume ratio are 7.
After hydrogenating desulfurization, the character of gasoline fraction lists in table 7, and the character of gasoline products DB1 lists in table 9.
Table 6
Table 7
Table 8
Table 9
| Gasoline products character | Embodiment 18 | Embodiment 19 | Comparative example 9 |
| S1 | S2 | DB1 | |
| Density (20 DEG C), g/cm 3 | 0.7320 | 0.7319 | 0.7326 |
| Sulphur content, μ g/g | 38 | 41 | 53 |
| Mercaptans content, μ g/g | 4 | 3 | 10 |
| Alkene, volume % | 35.7 | 35.1 | 34.8 |
Claims (19)
1. produce a method for low-sulphur oil, comprise the following steps:
(1) gasoline stocks is cut into light gasoline fraction, heavy naphtha, wherein, the cut point of light gasoline fraction and heavy naphtha is 50 DEG C ~ 100 DEG C;
(2) light gasoline fraction is carried out caustic wash desulfuration, obtain the light gasoline fraction after desulfurization;
(3) under hydrogen and catalyst A exist, heavy naphtha is carried out once desulfurization reaction, be isolated to the oil of the heavy naphtha after hydrogenating desulfurization;
(4) under rare gas element and catalyst B exist, the heavy naphtha after hydrogenating desulfurization is carried out secondary desulfuration reaction, is isolated to low-sulfur heavy naphtha;
(5) heavy naphtha that light gasoline fraction step (2) obtained and step (4) obtain is mixed to get gasoline products;
Wherein, described catalyst A and catalyst B are selected from load hydrogenation catalyst for refining, and in catalyst A and catalyst B, the carrier of at least one is the forming composition containing hydrated aluminum oxide, the forming composition of described alumina hydrate-containing contains hydrated aluminum oxide and ether of cellulose, the radial crushing strength of described forming composition is more than or equal to 12N/mm, and water-intake rate is that 0.4-1.5, δ value is for being less than or equal to 10%; Wherein, δ=((Q1-Q2)/Q1) × 100%, Q1 is the radial crushing strength of forming composition, and Q2 is that forming composition is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
2. method according to claim 1, is characterized in that, the condition of described once desulfurization reaction comprises: reaction pressure 0.8-3.2MPa, temperature of reaction 200-320 DEG C, feeding liquid time volume space velocity 3-8h
- 1, hydrogen to oil volume ratio is 200-600; The condition of described secondary desulfuration reaction comprises: temperature of reaction is 100-350 DEG C, and pressure is 0.2-6MPa, and during feeding liquid, mass space velocity is 1-12h
-1, rare gas element and stock oil volume ratio are 2-200.
3. method according to claim 2, is characterized in that, the reaction conditions of described once desulfurization reaction comprises: reaction pressure 1-2.4MPa, temperature of reaction 220-270 DEG C, gasoline fraction fluid time volume space velocity 3-6h
-1, hydrogen to oil volume ratio 300-500; The reaction conditions of described secondary desulfuration reaction comprises: pressure is 0.4-2.5MPa, and temperature of reaction is 140-240 DEG C, and during feeding liquid, mass space velocity is 2-10h
-1, rare gas element and stock oil volume ratio are 5-120.
4. method according to claim 1, is characterized in that, the radial crushing strength of described forming composition is 15-30N/mm, and water-intake rate is that 0.6-1, δ are less than or equal to 5%.
5. method according to claim 1, is characterized in that, with described forming composition for benchmark, the content of described ether of cellulose is 0.5-8 % by weight.
6. method according to claim 5, is characterized in that, with described forming composition for benchmark, the content of described ether of cellulose is 1-6 % by weight.
7. method according to claim 6, is characterized in that, with described forming composition for benchmark, the content of described ether of cellulose is 2-5 % by weight.
8. method according to claim 1, is characterized in that, described ether of cellulose is selected from one or more in methylcellulose gum, hydroxyethylmethyl-cellulose, Vltra tears.
9. method according to claim 8, is characterized in that, described ether of cellulose is methylcellulose gum, hydroxyethylmethyl-cellulose and their mixture.
10. method according to claim 1, is characterized in that, described hydrated aluminum oxide is selected from one or more in pseudo-boehmite, boehmite, aluminium hydroxide, three water-aluminum hydroxides.
11. methods according to claim 10, is characterized in that, described hydrated aluminum oxide is pseudo-boehmite.
12. methods according to claim 1, it is characterized in that, described load hydrogenation catalyst for refining contains the metal component that carrier, load at least one is on this carrier selected from the non-noble metal components of group VIII, at least one is selected from group vib, take catalyzer as benchmark, with the content of the group VIII metal component of oxide basis for 0.1-6 % by weight, with the content of the group vib metal component of oxide basis for 1-25 % by weight, vector contg is 69-98 % by weight.
13. methods according to claim 12, it is characterized in that, take catalyzer as benchmark, with the content of the group VIII metal component of oxide basis for 1-5 % by weight, with the content of the group vib metal component of oxide basis for 5-20 % by weight, vector contg is 75-94 % by weight.
14. methods according to claim 1 or 13, is characterized in that, containing being selected from alcohol, organic acid and organic amine one or more organism in described catalyzer, the mol ratio of described organism and group VIII metal component is 0.5-2.5.
15. methods according to claim 14, is characterized in that, the mol ratio of described organism and group VIII metal component is 1-2.
16. methods according to claim 1, is characterized in that, described catalyst A carries out prevulcanized before use.
17. methods according to claim 1, is characterized in that, the reactor of described secondary desulfuration reaction is countercurrent reactor.
18. methods according to claim 1, is characterized in that, one or more in described gasoline fraction grease separation catalytic cracking gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.
19. methods according to claim 18, is characterized in that, the boiling range of described gasoline fraction oil is 30-220 DEG C.
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| CN1995290A (en) * | 2006-01-06 | 2007-07-11 | 中国石油天然气股份有限公司 | Selective nickel series hydrogenating catalyst and its preparing process and uses |
| CN101152631A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurizing catalyzer and method of producing the same |
| CN102443432A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline by non-hydroforming sulfur and alcohol removal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1995290A (en) * | 2006-01-06 | 2007-07-11 | 中国石油天然气股份有限公司 | Selective nickel series hydrogenating catalyst and its preparing process and uses |
| CN101152631A (en) * | 2006-09-29 | 2008-04-02 | 中国石油化工股份有限公司 | Selective hydrogenation desulfurizing catalyzer and method of producing the same |
| CN102443432A (en) * | 2010-10-15 | 2012-05-09 | 中国石油化工股份有限公司 | Method for producing low-sulfur gasoline by non-hydroforming sulfur and alcohol removal |
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