CN103468303B - Method for selective hydrodesulfurization of gasoline - Google Patents
Method for selective hydrodesulfurization of gasoline Download PDFInfo
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- CN103468303B CN103468303B CN201210185216.0A CN201210185216A CN103468303B CN 103468303 B CN103468303 B CN 103468303B CN 201210185216 A CN201210185216 A CN 201210185216A CN 103468303 B CN103468303 B CN 103468303B
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Abstract
The invention discloses a method for selective hydrodesulfurization of gasoline. The method comprises that a gasoline distillate oil raw material contacts with a catalyst under gasoline hydrodesulfurization reaction conditions, wherein the catalyst comprises a forming carrier containing hydrated alumina, at least one non noble metal component loaded on the forming carrier and selected from the group VIII, and at least one metal component selected from the group VIB; the catalyst is taken as a reference, the content of the group VIII metal component is 0.1-6wt% by oxide, the content of the group VIB metal component is 1-25wt% by oxide, and the content of the carrier is 69-98wt%. Compared with the prior art, the method obviously improves gasoline hydrodesulfurization activity and has good hydrodesulfurization selectivity.
Description
Technical field
The present invention relates to a kind of hydrodesulfurizationprocess process, more specifically to a kind of method of gasoline selective hydrodesulfurizationmodification.
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.
The sulphur content reducing catalytically cracked gasoline can adopt catalytically cracked material weighted BMO spaces (front-end hydrogenation) or catalytic gasoline hydrogenation desulfurization (back end hydrogenation) two kinds of technical schemes usually.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.Meanwhile, along with the innovation of catalytic cracking technology, the application gradually of catalytic cracking desulfurization auxiliary and/or reeducation olefin assistant, the sulfur content of catalytic cracking gasoline of China's Some Enterprises can reach 500 below μ g/g, or even 150 below μ g/g.But if the sulphur content of catalytically cracked gasoline will be reduced further, make it to be less than 50 μ g/g (meeting Europe IV emission standard to the restriction of content of sulfur in gasoline), even be less than 10 μ g/g (meeting Europe V emission standard to the restriction of content of sulfur in gasoline), just still need to set up gasoline hydrogenation device again.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 adopt traditional catalyzer and technique, while hydrogenating desulfurization, 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.
Summary of the invention
The technical problem to be solved in the present invention be to provide a kind of newly, the method for the good gasoline hydrodesulfurizationmethod of selectivity.
The content that the present invention relates to comprises:
1, a kind of method for selective hydrodesulfurizationof of gasoline, under being included in gasoline hydrodesulfurizationmethod reaction conditions, gasoline fraction oil raw material and catalyst exposure are reacted, wherein, described catalyzer contains the forming composition carrier of alumina hydrate-containing, load at least one is on this carrier selected from the non-noble metal components of group VIII, at least one is selected from the metal component of 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.
2, the method according to 1, it is characterized in that, take catalyzer as benchmark, in described Hydrobon catalyst 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.
3, the method according to 1, it is characterized in that, the forming composition carrier of the described alumina hydrate-containing in described Hydrobon catalyst contains hydrated aluminum oxide and ether of cellulose, the radial crushing strength of described forming composition is 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.
4, the method according to 3, 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, the method according to 3, is characterized in that, with described forming composition for benchmark, the massfraction of described ether of cellulose is 0.5-8%.
6, the method according to 5, is characterized in that, with described forming composition for benchmark, the massfraction of described ether of cellulose is 1-6%.
7, the method according to 6, is characterized in that, with described forming composition for benchmark, the massfraction of described ether of cellulose is 2-5%.
8, the method according to 3, is characterized in that, described ether of cellulose is selected from one or more in methylcellulose gum, hydroxyethylmethyl-cellulose, Vltra tears.
9, the method according to 8, is characterized in that, described ether of cellulose is methylcellulose gum, hydroxyethylmethyl-cellulose and their mixture.
10, the method according to 1 or 3, 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, the method according to 10, is characterized in that, described hydrated aluminum oxide is pseudo-boehmite.
12, the method according to 1, 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 metal component of group VIII is 0.5-2.5.
13, the method according to 12, is characterized in that, the mol ratio of described organism and metal component of group VIII is 1-2.
14, the method according to 1, it is characterized in that, when described gasoline fraction oil raw material is contacted with Hydrobon catalyst together with hydrogen, also comprise and introduce a kind of heavy distillate and catalyst exposure, the initial boiling point of described heavy distillate is greater than described gasoline fraction oil final boiling point, in volume space velocity during liquid, the introduction volume of heavy distillate is 0.2h
-1-2h
-1,
15, the method according to 14, it is characterized in that, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 1 DEG C, in volume space velocity during liquid, the introduction volume of heavy distillate is 0.4h
-1-1.8h
-1.
16, the method according to 15, is characterized in that, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 10 DEG C, and in volume space velocity during liquid, the introduction volume of heavy distillate is 0.6h
-1-1.8h
-1.
17, the method according to 15 or 16, is characterized in that, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 20 DEG C.
18, the method according to 17, is characterized in that, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 40 DEG C.
19, the method according to 15 or 16, is characterized in that, described heavy distillate is derived from one or more in oil, synthetic oil.
20, the method according to 19, is characterized in that, described synthetic oil is selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil.
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.
23, the method according to 1, is characterized in that, described gasoline hydrodesulfurizationmethod reaction conditions comprises: volume space velocity 3h when pressure 0.8MPa ~ 3.2MPa, temperature 200 DEG C ~ 320 DEG C, gasoline fraction fluid
-1~ 8h
-1, hydrogen-oil ratio 200Nm
3/ m
3~ 600Nm
3/ m
3.
24 methods according to 23, it is characterized in that, described gasoline hydrodesulfurizationmethod reaction conditions comprises: volume space velocity 3h when reaction pressure 1MPa-2.8MPa, temperature of reaction 220 DEG C-270 DEG C, gasoline fraction fluid
-1-6h
-1, hydrogen-oil ratio 300Nm
3/ m
3-500Nm
3/ m
3.
25, the method according to 1 or 14, is characterized in that, after gasoline fraction oil raw material and catalyst exposure being reacted, also comprises the described step generating oil and be separated under described gasoline hydrodesulfurizationmethod reaction conditions.
26, the method according to 24, is characterized in that, described separation comprises the step of stripping and fractionation.
Wherein, 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 massfraction of described ether of cellulose is 0.5-8%, more preferably 1%-6%, is more preferably 2%-5%; 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.
In the present invention, the measuring method of the radial crushing strength of described forming composition is carried out according to RIPP 25-90 catalyzer compressive strength assay method, and the concrete steps measured about the radial crushing strength of forming composition have detailed introduction at RIPP 25-90, 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
According to hydrated alumina forming matter provided by the invention, wherein 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.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 the VIIIth race 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 the VIIIth race 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 metal component of group VIII 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.
Catalyzer provided by the invention before the use, usually preferably in presence of hydrogen, at the temperature of 140-370 DEG C, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out outside device also can be In-situ sulphiding in device, is translated into sulfide type.
Described gasoline hydrodesulfurizationmethod reaction conditions is usual gasoline selective hydrodesulfurizationmodification reaction conditions, and preferred operational condition comprises: volume space velocity 3h when reaction pressure 0.8MPa-3.2MPa, temperature of reaction 200 DEG C-320 DEG C, gasoline fraction fluid
-1-8h
-1, hydrogen-oil ratio 200Nm
3/ m
3-600Nm
3/ m
3, preferred reaction conditions comprises further: 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-oil ratio 300Nm
3/ m
3-500Nm
3/ m
3.
According to method provided by the present invention, described in treat that the gasoline stocks of hydrogenation can be one or more in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and pressure gasoline.Describedly treat that the gasoline stocks of hydrogenation is full distillation gasoline raw material, boiling range is the usual boiling range of gasoline fraction oil, such as: be 30-220 DEG C.
In the present invention, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, and the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 1 DEG C, is preferably not less than 10 DEG C, preferably be not less than 20 DEG C further, be more preferably not less than 40 DEG C.The introduction volume of heavy distillate is preferably 0.4h
-1-1.8h
-1, more preferably 0.6h
-1-1.8h
-1.
Described heavy distillate is derived from one or more in oil, synthetic oil (such as: be selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil).Under reaction conditions of the present invention, wherein said heavy distillate exists at least partly in fluid form.
Be enough to described heavy distillate to be introduced and with under the condition of catalyst exposure, the introducing method of the present invention to described heavy distillate does not limit in guarantee.Such as, described heavy distillate can first with gasoline fraction oil mix, afterwards introducing reactor under gasoline hydrodesulfurizationmethod reaction conditions with catalyst exposure; Also can be by described heavy distillate and gasoline fraction oil raw material introduce reactor respectively, afterwards under gasoline selective hydrodesulfurizationmodification reaction conditions with catalyst exposure.To this, the present invention is not particularly limited.Described reactor can be the reactor that in prior art, any one is suitable for gasoline fraction oil hydrogenation, such as fixed bed hydrogenation reactor.
According to method provided by the present invention, wherein, also comprise any one for obtaining the separating step needed for object product, described separation method and device are the method and apparatus that this area usually adopts.Such as, adopt the usual apparatus and method in this area to carry out air lift to generation oil, to remove gaseous impuritieies such as generating the hydrogen sulfide that contains in oil, carry out the step of fractionation by distillation afterwards.The gasoline fraction oil be isolated to is as Product recycling, and when comprising introducing heavy distillate, after being separated, reclaim heavy distillate, this oil can partly or entirely recycle
Compared with prior art, gasoline hydrodesulfurizationmethod activity of the present invention significantly improves, and has good hydrogenating desulfurization selectivity.
Embodiment
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
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 illustrates and the invention provides method and effect thereof.
High-sulfur catalytically cracked gasoline is adopted to carry 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 18-22 illustrates and the invention provides method and effect thereof.
Embodiment 18
With C3 be catalyzer in fixed-bed reactor to a kind of catalytically cracked gasoline for stock oil A carries out hydrogenating desulfurization.
Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production through air lift, and the character of product lists in table 7.
Comparative example 9
With DB2 be catalyzer in fixed-bed reactor to a kind of catalytically cracked gasoline for stock oil A carries out hydrogenating desulfurization.
Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production through air lift, and the character of product lists in table 7.
Embodiment 19
Be that catalyzer carries out hydrogenating desulfurization to stock oil C in fixed-bed reactor with C3.Stock oil C is the mixture of stock oil A and heavy distillate B (Fischer-Tropsch synthesis oil), and in mixture, the content of B is 30 volume %.Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production and heavy distillate B through air lift, distillation, and the character of product lists in table 7.
Comparative example 10
Be that catalyzer carries out hydrogenating desulfurization to stock oil I in fixed-bed reactor with DB2.Stock oil C is the mixture of stock oil A and heavy distillate B (Fischer-Tropsch synthesis oil), and in mixture, the content of B is 30 volume %.Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production and heavy distillate B through air lift, distillation, and the character of product lists in table 7.
Embodiment 20
Be that catalyzer carries out hydrogenating desulfurization to stock oil E in fixed-bed reactor with C3.Stock oil E is the mixture of stock oil A and heavy distillate D (white oil), and in mixture, the content of D is 30 volume %.Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production and heavy distillate D through air lift, distillation, and the character of product lists in table 7.
Embodiment 21
Be that catalyzer carries out hydrogenating desulfurization to stock oil I in fixed-bed reactor with C5.Stock oil I is the mixture of stock oil A and heavy distillate H (PAO8), and in mixture, the content of H is 20 volume %.Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production and heavy distillate H through air lift, distillation, and the character of product lists in table 7.
Embodiment 22
Be that catalyzer carries out hydrogenating desulfurization to stock oil K in fixed-bed reactor with C3.Stock oil K is the mixture of stock oil A and heavy distillate J (VGO), and in mixture, the content of J is 20 volume %.Stock oil character is in table 6, and reaction conditions is in table 7.Reaction product obtains gasoline fraction oil production and heavy distillate J through air lift, distillation, and the character of product lists in table 7.
Table 6
Table 7
Claims (26)
1. a method for selective hydrodesulfurizationof of gasoline, under being included in gasoline hydrodesulfurizationmethod reaction conditions, gasoline fraction oil raw material and catalyst exposure are reacted, wherein, described catalyzer contains the forming composition carrier of alumina hydrate-containing, load at least one is on this carrier selected from the non-noble metal components of group VIII, at least one is selected from the metal component of 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.
2. method according to claim 1, it is characterized in that, take catalyzer as benchmark, in described catalyzer 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.
3. method according to claim 1, it is characterized in that, the forming composition carrier of the described alumina hydrate-containing in described catalyzer contains hydrated aluminum oxide and ether of cellulose, the radial crushing strength of described forming composition carrier is 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 carrier, and Q2 is that forming composition carrier is through water soaking 30 minutes, through the radial crushing strength of 120 DEG C of heating, dryings after 4 hours.
4. method according to claim 3, is characterized in that, the radial crushing strength of described forming composition carrier 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 3, is characterized in that, with described forming composition carrier for benchmark, the massfraction of described ether of cellulose is 0.5-8%.
6. method according to claim 5, is characterized in that, with described forming composition carrier for benchmark, the massfraction of described ether of cellulose is 1-6%.
7. method according to claim 6, is characterized in that, with described forming composition carrier for benchmark, the massfraction of described ether of cellulose is 2-5%.
8. method according to claim 3, 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. the method according to claim 1 or 3, is characterized in that, described hydrated aluminum oxide is selected from one or more in pseudo-boehmite, boehmite, 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, 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.
13. methods according to claim 12, is characterized in that, the mol ratio of described organism and group VIII metal component is 1-2.
14. methods according to claim 1, it is characterized in that, when described gasoline fraction oil raw material is contacted with Hydrobon catalyst together with hydrogen, also comprise and introduce a kind of heavy distillate and catalyst exposure, the initial boiling point of described heavy distillate is greater than described gasoline fraction oil final boiling point, in volume space velocity during liquid, the introduction volume of heavy distillate is 0.2h
-1-2h
-1.
15. methods according to claim 14, it is characterized in that, described heavy distillate is selected from diesel oil distillate oil and/or lubricating oil distillate, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 1 DEG C, in volume space velocity during liquid, the introduction volume of heavy distillate is 0.4h
-1-1.8h
-1.
16. methods according to claim 15, is characterized in that, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 10 DEG C, and in volume space velocity during liquid, the introduction volume of heavy distillate is 0.6h
-1-1.8h
-1.
17. methods according to claim 15 or 16, it is characterized in that, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 20 DEG C.
18. methods according to claim 17, is characterized in that, the temperature difference of the initial boiling point of described heavy distillate and the final boiling point of described gasoline fraction oil is not less than 40 DEG C.
19. methods according to claim 15 or 16, it is characterized in that, described heavy distillate is derived from one or more in oil, synthetic oil.
20. methods according to claim 19, is characterized in that, described synthetic oil is selected from olefin oligomerization synthetic oil, Fischer-Tropsch synthesis oil and biosynthesizing oil.
21. 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.
22. methods according to claim 21, is characterized in that, the boiling range of described gasoline fraction oil is 30-220 DEG C.
23. methods according to claim 1, is characterized in that, described gasoline hydrodesulfurizationmethod reaction conditions comprises: volume space velocity 3h when pressure 0.8MPa ~ 3.2MPa, temperature 200 DEG C ~ 320 DEG C, gasoline fraction fluid
-1~ 8h
-1, hydrogen-oil ratio 200Nm
3/ m
3~ 600Nm
3/ m
3.
24. methods according to claim 23, is characterized in that, described gasoline hydrodesulfurizationmethod reaction conditions comprises: volume space velocity 3h when reaction pressure 1MPa-2.8MPa, temperature of reaction 220 DEG C-270 DEG C, gasoline fraction fluid
-1-6h
-1, hydrogen-oil ratio 300Nm
3/ m
3-500Nm
3/ m
3.
25. methods according to claim 1 or 14, is characterized in that, after react by gasoline fraction oil raw material, also comprise the oily step be separated of generation under described gasoline hydrodesulfurizationmethod reaction conditions with catalyst exposure.
26. methods according to claim 25, is characterized in that, described separation comprises the step of stripping and fractionation.
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|---|---|---|---|---|
| US4378308A (en) * | 1980-11-26 | 1983-03-29 | Mobil Oil Corporation | Poison-resistant hydrodesulfurization catalyst |
| JP2005305418A (en) * | 2004-03-26 | 2005-11-04 | Cosmo Oil Co Ltd | Hydrotreating catalyst of hydrocarbon oil and its manufacturing method and hydrotreating method of hydrocarbon oil |
| CN1778872A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrogenation desulfurized catalyst containing molecular screen |
| 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 |
| CN101722014A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4378308A (en) * | 1980-11-26 | 1983-03-29 | Mobil Oil Corporation | Poison-resistant hydrodesulfurization catalyst |
| JP2005305418A (en) * | 2004-03-26 | 2005-11-04 | Cosmo Oil Co Ltd | Hydrotreating catalyst of hydrocarbon oil and its manufacturing method and hydrotreating method of hydrocarbon oil |
| CN1778872A (en) * | 2004-11-26 | 2006-05-31 | 中国石油天然气股份有限公司 | Hydrogenation desulfurized catalyst containing molecular screen |
| 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 |
| CN101722014A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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