CN102049271B - Gasoline selective hydrogenation catalyst and preparation method and application thereof - Google Patents
Gasoline selective hydrogenation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a gasoline selective hydrogenation catalyst, a preparation method thereof and application thereof in gasoline two-stage selective hydrogenation-desulfurization. In the catalyst, titanium oxide and/or zirconium oxide-modified alumina is adopted as a carrier, wherein a proper amount of titanium oxide and/or zirconium oxide is introduced in the pulping process after alumina is gelatinized; the total acid amount of the carrier is improved, and the L acid amount is greatly improved particularly; the selective hydrogenation-desulfurization capacity of the catalyst is improved, and the effect of the carrier on a potassium aid is enhanced; and under the coordination of a phosphorus aid, the potassium is prevented from being lost and the stability of the catalyst is improved. Two catalysts with high selectivity and stability and different activities are combined, so that the hydrogenation-desulfurization activity and selectivity are high, and stable operation time is long in a gasoline two-stage selective hydrogenation-desulfurization process, and the economic efficiency of a device is improved.
Description
Technical field
The present invention relates to a kind of catalyst for selective hydrodesulfurizationof of gasoline and preparation method thereof, and use this catalyst to carry out the two-stage hydrogenation sulfur removal technology, especially for catalyst and two sections selective hydrogenation desulfurization process of catalytic gasoline selective desulfurization.
Background technology
In recent years, in order to protect environment, countries in the world government makes great efforts to reduce emission of harmful substances in the exhaust gases of internal combustion engines, and the specification of quality of automotive fuel is strict day by day, and special demands reduce the sulfur content in the motor petrol.The combustion product SO of sulfur-containing compound in the gasoline
XBe vehicle exhaust mainly contain one of harmful substances, also be one of vehicle exhaust reforming unit catalyst poison.Therefore, make laws one after another in countries in the world, and the sulfur content in the gasoline has been proposed more and more strict restriction.
As everyone knows, the direct steaming gasoline sulfur content is main relevant with sulfur content in crude oil, even sulfur content is higher, but because of its olefin(e) centent seldom, when adopting the processing of conventional H DS method, do not have tangible loss of octane number.And FCC gasoline sulfur and olefin(e) centent are all higher; Though adopt traditional HDS method can effectively remove sulfur-containing compound wherein; But because the lower alkene of the collateralization degree low-octane alkane of the saturated generation of hydrogenation very easily in the FCC gasoline, so, adopt traditional HDS method; Along with the reduction of FCC content of sulfur in gasoline, must follow the rapid decline of octane number.
US 5441630 discloses a kind of class-water talcite (Hydrotalcite-like HTIC) of using and has added γ-Al as carrier component
2O
3In, having high surface area, alkalescence through the HTIC of roasting, the catalyst behind the carrier impregnation Co-Mo demonstrate the characteristics that the HDS activity is high, the alkene saturation percentage is low, but the loss of octane number of gasoline is still bigger.US 5459118 is on the basis of above-mentioned catalytic component; Propose to increase the alkali-metal raw catelyst of IA family; It is selected catalyst surface hydrogenation lattice degree of intoxication much larger than the desulfurization lattice, though this catalyst HDS activity is lower than the HDS catalyst that those do not add this denaturant slightly, it stops the saturated characteristic of alkene is prior; The subject matter of this patent is that the poor stability of catalyst, particularly selection of catalysts property descend with the increase of the duration of runs fast.It is carrier that US 5423976, US 5538930 propose with the active carbon; Think that activated carbon surface is long-pending big; Help supporting of metal component, often contain K in addition in the active carbon, help selection of catalysts property; When the C carrier that uses does not contain above-mentioned metal, can add at the Preparation of Catalyst arbitrary steps.The shortcoming of absorbent charcoal carrier is that the metal component of load and auxiliary agent are easy to run off.
CN1488721A discloses a kind of catalyst for selective hydrodesulfurizationof of gasoline and two sections selective hydrogenation desulfurization process.This catalyst adopts alumina support, and P and K are adjuvant component, and Co and Mo are active metal component; Although the gasoline hydrodesulfurizationmethod selectivity has had raising to a certain degree, the acidity of carrier is also bigger to the influence of catalyst selectivity hydrodesulfurization, and alumina support is the faintly acid carrier; With it is that the catalyst hydrogenation activity of carrier is lower, introduces auxiliary agent P and K again, limited to the inhibitory action of alkene saturated activity; Therefore, the hydrodesulfurization selectivity of this catalyst awaits further to improve.
Summary of the invention
To the deficiency of prior art, two sections gasoline selective hydrodesulfurizationmodification methods that the present invention provides a kind of activity and selectivity all to improve.Another object of the present invention is catalyst for selective hydrodesulfurizationof of gasoline that provides employed high selectivity of gasoline two-stage hydrogenation sulfur removal technology and high stability and preparation method thereof.
Catalyst for selective hydrodesulfurizationof of gasoline provided by the invention is an active metal component with Co and Mo, is adjuvant component with potassium and phosphorus, is carrier with the aluminium oxide of titanium oxide and/or zirconia modification, TiO in the carrier
2And/or ZrO
2Weight content be 5%～30%, be preferably 11%～19%, carrier meleic acid total acid content is 0.30～0.70mmol/g, L acid acid amount is 0.28～0.68mmol/g; Weight with catalyst is benchmark, MoO
3Content be 1.0%～18.0%, the content of CoO is 0.1%～6.0%, Co/Mo atomic ratio 0.1～1.0, the content of potassium are 0.5%～10.0%, P/K atomic ratio 0.1～10.0, surplus is a carrier; The pore volume of said catalyst is 0.3～1.0ml/g, and specific area is 150～400m
2/ g.
The preparation method of catalyst for selective hydrodesulfurizationof of gasoline of the present invention; Comprise alumina support load potassium and phosphorus with titanium oxide and/or zirconia modification, after dry and roasting, supported active metal component Co and Mo again; Through drying and roasting, obtain catalyst for selective hydrodesulfurizationof of gasoline; Wherein the preparation method of the aluminium oxide of titanium oxide and/or zirconia modification is following:
The aluminum sulfate aqueous solution and the sodium metaaluminate aqueous solution carry out neutralization reaction 0.4～1.5h under 50～90 ℃ of conditions; The pH value of control neutralization reaction is 7.0～9.5; Aging then 0.2～1.0h after washing 2～5 times, adds zirconium-containing compound and/or titanium-containing compound is pulled an oar then; The filter cake that obtains after the filtration is 90～130 ℃ of dryings 5～34 hours, through grinding the aluminum oxide dry glue powder that promptly obtains titanium oxide and/or zirconia modification; This dry glue powder descended dry 1～5 hour at 100～120 ℃ through extruded moulding then, promptly obtained the alumina support of titanium oxide and/or zirconia modification in 1～5 hour 400～600 ℃ of roastings.
Described zirconium-containing compound is one or more in zirconium dioxide, basic zirconium chloride, zirconium sulfate and the zirconium carbonate, and described titanium-containing compound is one or more in metatitanic acid, titanium white powder, titanium chloride and the titanium sulfate.
Two sections gasoline selective hydrodesulfurizationmodification methods of the present invention are following: the beds that feedstock oil increases through active metallic content under the hydrodesulfurization condition successively gradually, one of them or an above beds use catalyst for selective hydrodesulfurizationof of gasoline of the present invention.Generally speaking, can adopt two beds, every section is adopted a beds, has at least a bed to use catalyst for selective hydrodesulfurizationof of gasoline of the present invention in two beds, and another bed uses conventional catalyst.Preferably among the present invention adopt two beds, and all use catalyst for selective hydrodesulfurizationof of gasoline of the present invention, wherein first bed uses the catalyst of low-metal content, is carrier with the aluminium oxide of titanium oxide and/or zirconia modification, MoO
3Weight content be more than 1.0% and less than 10.0%, the weight content of CoO is 0.1%～5.0%, Co/Mo atomic ratio 0.1～1.0; Second bed uses the catalyst of high tenor, is carrier with the aluminium oxide of titanium oxide and/or zirconia modification, MoO
3Weight content be 10.0%～18.0%, the weight content of CoO is 1.0%～6.0%, Co/Mo atomic ratio 0.1～1.0.First bed is 2/8～8/2 with the second bed catalyst admission space ratio.
It is carrier that catalyst of the present invention adopts the aluminium oxide of titanium oxide and/or zirconia modification; Wherein, introduces in aluminium oxide an amount of titanium oxide and/or zirconia after becoming glue in the pulping process; In this way aluminium oxide is carried out modification; Improve the total acid content of carrier, the acid of adjustment carrier distributes, and particularly increases substantially L acid acid amount.The acidity of carrier is bigger to the selective hydrodesulfurization influence; The content of thiophene-type sulfide sulphur accounts for more than 60% of total sulfur-containing compound; Thiophenes is a L alkali; Be easy on the L acid site, adsorb, thereby the close sulfur materials of selecting to form the L acid site can improve the desulphurizing ability of catalyst as carrier.Simultaneously, in carrier, introduce potassium and phosphorus component, and confirmed best potassium content and phosphorus potassium atom ratio; Two kinds of auxiliary agent coordinative roles of potassium and phosphorus, carrier and auxiliary agent coordinative role have improved alkali-metal constraint effect; Reach the effect that prevents that alkali metal runs off; And alkali metal to the inhibitory action of alkene saturated activity greater than inhibitory action to hydrodesulfurization activity, resulting catalyst has better choice property, better stability.
Selectivity are good, stability is strong, the different activities catalyst makes up owing to use two kinds for technology of the present invention, make this technology not only the steady running time long, and keep high hydrodesulfurization activity and selectivity, the economy of raising device always.
The specific embodiment
Among the present invention, specific area and pore volume employing low temperature liquid nitrogen determination of adsorption method, it is the infrared absorption spectrographic determination of employing pyridine that meleic acid total acid content, B acid amount and L acid are measured.Wt% representes mass percent among the present invention.
Gasoline hydrodesulfurizationmethod catalyst of the present invention can be confirmed best tenor according to the diverse location at reactor.The present invention preferably adopts two beds, and all uses catalyst for selective hydrodesulfurizationof of gasoline of the present invention, and wherein first beds uses the lower catalyst of tenor, MoO
3Content be that 1.0wt% is above and less than 10.0wt%, be preferably 2.0wt%～8.0wt%, the content of CoO is 0.1wt%～5.0wt%, is preferably 0.5wt%～4.0wt%, Co/Mo atomic ratio 0.1～1.0.Use the higher catalyst of tenor at second beds, contain MoO
310.0wt%～18.0wt% is preferably 10.0wt%～16.0wt%, and CoO1.0wt%～6.0wt% is preferably 2.0wt%～5.0wt%, Co/Mo atomic ratio 0.1～1.0.First beds and the second beds catalyst system therefor are to be active metal component with Co and Mo, are adjuvant component with potassium and phosphorus, are carrier with the aluminium oxide of titanium oxide and/or zirconia modification, TiO in the carrier
2And/or ZrO
2Weight content be 5%～30%, be preferably 11%～19%, carrier meleic acid total acid content is 0.30～0.70mmol/g; L acid acid amount is 0.28～0.68mmol/g, is benchmark with the weight of catalyst, and the content of potassium is 0.5%～10.0%; Be preferably 0.5%～5.0%; P/K atomic ratio 0.1～10.0 is preferably 0.8～5.0, and surplus is a carrier; The pore volume of said catalyst is 0.3～1.0ml/g, and specific area is 150～400m
2/ g.
The concrete preparation process of catalyst of the present invention is following:
The alumina support that takes by weighing a certain amount of titanium oxide and/or zirconia modification places to spray and rolls pot; Under the rotation condition, the alumina support in rolling pot sprays into the phosphorous potassium salt soln of carrier saturated water adsorptive value with atomizing type, after solution has sprayed; In rolling pot, be rotated further 10～60 minutes; Placed then 1～24 hour, 100～120 ℃ dry 1～5 hour down, rise to 400～600 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot; Spray into Mo, the Co ammonia solution of saturated water adsorptive value, after solution has sprayed, in rolling pot, be rotated further 10～60 minutes; Placed then 1～24 hour; 100～120 ℃ dry 1～5 hour down, rise to 400～650 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again, make finished catalyst.
In above-mentioned preparation method, the concentration of maceration extract is formed (content) by water absorption rate and desired catalyst and is confirmed.
Gasoline selective hydrodesulfurizationmodification technical process of the present invention is: under hydrodesulfurizationconditions conditions, raw material at first contacts with one section catalyst with hydrogen, gets into two sections through one section reactor product, contacts with two sections catalyst.One, the filling ratio of two sections catalyst in reactor is 2/8～8/2, is preferably 3/7～8/2, is preferably 4/6～8/2.Operating condition is following: reaction temperature is 230～320 ℃, better is 250～300 ℃; Reaction pressure is 1.0～4.0MPa, better is 1.6～3.2MPa; Hydrogen to oil volume ratio is 100～1000Nm
3/ m
3, better be 200～800Nm
3/ m
3Volume space velocity is 1.0～10.0h during liquid
-1, better be 2.0～6.0h
-1
According to the inventive method; In order further to improve the overall performance of reaction system; Can be along the Flow of Goods and Materials direction; According to the two or more Hydrobon catalyst that uses in order that catalyst activity (active metallic content) increases gradually, like the catalyst of 3～5 kinds of different activities, other composition of catalyst preferably provides by the present invention program.
Below specify with embodiment and to adopt two sections selective hydrodesulfurization processes of catalyst of the present invention and employed catalyst.
Embodiment 1
The 600ml aluminum sulfate aqueous solution and the 200ml sodium metaaluminate aqueous solution are carried out neutralization reaction 1.0h under 50～90 ℃ of conditions; The pH value of control neutralization reaction is 8.8～9.0; Aging then 0.5h after washing 2 times, adds the 130g basic zirconium chloride then and pulls an oar; The filter cake that obtains after the filtration is 110 ℃ of dryings 24 hours, through grinding the aluminum oxide dry glue powder that promptly obtains the zirconia modification; This dry glue powder descended dry 3 hours at 110 ℃ through extruded moulding then, promptly obtained the alumina support of zirconia modification in 3 hours 600 ℃ of roastings.The alumina support of 200g zirconia modification placed to spray roll pot; Under the rotation condition, the alumina support in rolling pot sprays into the aqueous solution that 158ml contains the 16.6g potassium dihydrogen phosphate with atomizing type, after solution has sprayed; In rolling pot, be rotated further 30 minutes; Placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 9.6g citric acid is dissolved in the 134ml water purification, adds the 6.6g cobalt carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 14.6g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes; Placed then 18 hours; 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst A.
Embodiment 2
The 600ml aluminum sulfate aqueous solution and the 200ml sodium metaaluminate aqueous solution are carried out neutralization reaction 1.0h under 50～90 ℃ of conditions; The pH value of control neutralization reaction is 8.8～9.0; Aging then 0.5h after washing 2 times, adds the 21g titanium white powder then and pulls an oar; The filter cake that obtains after the filtration is 110 ℃ of dryings 24 hours, through grinding the aluminum oxide dry glue powder that promptly obtains the titanium oxide modification; This dry glue powder descended dry 3 hours at 110 ℃ through extruded moulding then, promptly obtained the alumina support of titanium oxide modification in 3 hours 600 ℃ of roastings.The alumina support of 200g titanium oxide modification placed to spray roll pot; Under the rotation condition, the alumina support in rolling pot sprays into the aqueous solution that 158ml contains the 16.6g potassium dihydrogen phosphate with atomizing type, after solution has sprayed; In rolling pot, be rotated further 30 minutes; Placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 21.1g citric acid is dissolved in the 122ml water purification, adds the 14.6g cobalt carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 29.4g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 153ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes; Placed then 18 hours; 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst B.
Embodiment 3
The 600ml aluminum sulfate aqueous solution and the 200ml sodium metaaluminate aqueous solution are carried out neutralization reaction 1.0h under 50～90 ℃ of conditions; The pH value of control neutralization reaction is 8.8～9.0; Aging then 0.5h after washing 2 times, adds the 173g basic zirconium chloride then and pulls an oar; The filter cake that obtains after the filtration is 110 ℃ of dryings 24 hours, through grinding the aluminum oxide dry glue powder that promptly obtains the zirconia modification; This dry glue powder descended dry 3 hours at 110 ℃ through extruded moulding then, promptly obtained the alumina support of zirconia modification in 3 hours 600 ℃ of roastings.The alumina support of 200g zirconia modification placed to spray roll pot; Under the rotation condition, the alumina support in rolling pot sprays into 154ml with atomizing type and contains the phosphoric acid mixed aqueous solution that 2.3g potassium nitrate and 24.0g contain 53wt%, after solution has sprayed; In rolling pot, be rotated further 30 minutes; Placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 7.8g citric acid is dissolved in the 172ml water purification, adds the 5.4g cobalt carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 8.4g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes; Placed then 18 hours; 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst C.
Embodiment 4
Change the potassium nitrate amount among the embodiment 3 into 37.4g, phosphoric acid amount changes 11.1g into, after solution has sprayed, in rolling pot, is rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 9.6g citric acid is dissolved in the 134ml water purification, adds the 6.6g cobalt carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 14.6g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes; Placed then 18 hours; 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst D.
Embodiment 5
Change potassium dihydrogen phosphate amount among the embodiment 2 into 17.6g, after solution has sprayed, in rolling pot, be rotated further 30 minutes, placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 26.7g citric acid is dissolved in the 94ml water purification, adds the 18.3g cobalt carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 46.5g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 156ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes; Placed then 18 hours; 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst E.
Embodiment 6
The 600ml aluminum sulfate aqueous solution and the 200ml sodium metaaluminate aqueous solution are carried out neutralization reaction 1.0h under 50～90 ℃ of conditions; The pH value of control neutralization reaction is 8.8～9.0; Aging then 0.5h after washing 2 times, adds the 65g basic zirconium chloride, the 10.5g titanium white powder is pulled an oar then; The filter cake that obtains after the filtration is 110 ℃ of dryings 24 hours, through grinding the aluminum oxide dry glue powder that promptly obtains zirconia and titanium oxide modification; This dry glue powder descended dry 3 hours at 110 ℃ through extruded moulding then, promptly obtained the alumina support of zirconia and titanium oxide modification in 3 hours 600 ℃ of roastings.The alumina support of 200g zirconia and titanium oxide modification placed to spray roll pot; Under the rotation condition, the alumina support in rolling pot sprays into atomizing type that the potassium dihydrogen phosphate amount changes 18.5g among the embodiment 2, after solution has sprayed; In rolling pot, be rotated further 30 minutes; Placed then 18 hours, 110 ℃ dry 3 hours down, rise to 450 ℃ of roastings 2 hours with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot.The 37.4g citric acid is dissolved in the 40ml water purification, adds the 25.6g cobalt carbonate, boil dissolving, after the cooling, add 25% ammoniacal liquor again to 170ml, add the 61.0g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25% ammoniacal liquor with liquor capacity, airtight preservation.Spray with molybdenum that 155ml joins, cobalt ammonia solution, after solution has sprayed, in rolling pot, be rotated further 30 minutes; Placed then 18 hours; 110 ℃ dry 3 hours down, rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, make finished catalyst F.
Comparative example 1
Preparation catalyst G, the preparation method does not just add Zr with embodiment 1.
Comparative example 2
Preparation catalyst H, the preparation method does not just add Ti with embodiment 5.
Comparative example 3
The preparation catalyst I, the preparation method does not just add auxiliary agent phosphorus and potassium with embodiment 1.
Comparative example 4
Preparation catalyst J, the preparation method does not just add auxiliary agent phosphorus and potassium with embodiment 5.
Embodiment 7
On 200ml fixed bed small hydrogenation device; One section is adopted A, B, C, D catalyst respectively; Two sections are adopted catalyst E, E, F, E respectively, and the filling ratio of one, two section catalyst is respectively 5/5,7/3,3/7,5/5, volume space velocity 3.0h when reaction pressure 1.6MPa, liquid
-1, hydrogen to oil volume ratio is 300Nm
3/ m
3, under 270 ℃ of conditions of reaction temperature, be that 664 μ g/g, RON are that 93.0 raw material carries out selective hydrodesulfurization to sulfur content.
Comparative example 5
Evaluation method adopts catalyst G for 7, one sections with embodiment, and two sections are adopted catalyst H.One, the filling ratio of two sections catalyst is 5/5.
Comparative example 6
Evaluation method adopts catalyst I for 7, one sections with embodiment, and two sections are adopted catalyst J.One, the filling ratio of two sections catalyst is 5/5.
Embodiment 8
This example is that the comparing result that above each routine institute controlling catalyst physico-chemical property and above each example turned round 600 hours on small hydrogenation device is seen table 1 and table 2.
Table 1 catalyst main character
| Project | A | B | C | D | E | F | G | H | I | J |
| Carrier character | ||||||||||
| ZrO 2，wt％ | 15.0 | - | 18.9 | 19.0 | - | 9.0 | - | - | 15.0 | - |
| TiO 2，wt％ | - | 15.1 | - | - | 14.9 | 9.8 | - | - | - | 14.9 |
| Infrared total acid content, mmol/g | 0.517 | 0.350 | 0.595 | 0.595 | 0.350 | 0.366 | 0.226 | 0.226 | 0.517 | 0.350 |
| B acid acid amount, mmol/g | 0.041 | 0.046 | 0.049 | 0.049 | 0.046 | 0.044 | 0.023 | 0.023 | 0.041 | 0.046 |
| L acid acid amount, mmol/g | 0.476 | 0.304 | 0.546 | 0.546 | 0.304 | 0.322 | 0.203 | 0.203 | 0.476 | 0.304 |
| Catalyst property | ||||||||||
| MoO 3，wt％ | 4.2 | 8.1 | 2.5 | 4.3 | 11.9 | 15.8 | 4.1 | 11.8 | 4.5 | 12.9 |
| CoO，wt％ | 1.4 | 2.5 | 1.0 | 1.4 | 3.2 | 4.0 | 1.3 | 3.2 | 1.5 | 3.5 |
| The Co/Mo atomic ratio | 0.64 | 0.59 | 0.77 | 0.63 | 0.52 | 0.49 | 0.61 | 0.52 | 0.64 | 0.52 |
| P，wt％ | 1.9 | 1.7 | 1.9 | 0.8 | 1.6 | 1.8 | 1.9 | 1.6 | - | - |
| K 2O，wt％ | 2.7 | 2.6 | 0.5 | 7.5 | 2.5 | 2.7 | 2.7 | 2.5 | - | - |
| The P/K atomic ratio | 1.1 | 1.0 | 5.8 | 0.2 | 1.0 | 1.0 | 1.1 | 1.0 | - | - |
| Pore volume, ml/g | 0.50 | 0.45 | 0.51 | 0.54 | 0.47 | 0.45 | 0.48 | 0.45 | 0.57 | 0.50 |
| Specific area, m 2/g | 249 | 235 | 246 | 228 | 222 | 218 | 225 | 223 | 238 | 232 |
| Bulk density, g/ml | 0.70 | 0.72 | 0.68 | 0.67 | 0.76 | 0.78 | 0.66 | 0.73 | 0.65 | 0.73 |
| Intensity, N/cm | 150 | 135 | 141 | 121 | 130 | 125 | 121 | 125 | 131 | 145 |
Table 2 catalyst activity and selectivity
Reaction condition: P=1.6MPa; LHSV=3.0h
-1H
2/ Oil=300Nm
3/ m
3
Table 2 is the result show, the present invention adopts two sections selective hydrodesulfurization processes, and one section and two sections is adopted catalyst for selectively hydrodesulfurizing of the present invention, and under the situation of equal desulfurization degree, loss of octane number is little.Through after certain duration of runs, activity of such catalysts of the present invention and selectivity are good, and the selective hydrodesulfurization performance is stable than the comparative catalyst.
Claims (13)
1. catalyst for selective hydrodesulfurizationof of gasoline is a carrier with the aluminium oxide of titanium oxide and/or zirconia modification, TiO in the carrier
2And/or ZrO
2Weight content be 5%～30%, carrier meleic acid total acid content is 0.30～0.70mmol/g, L acid acid amount is 0.28～0.68mmol/g, is active metal component with Co and Mo, is adjuvant component with potassium and phosphorus, is benchmark with the weight of catalyst, MoO
3Content be 1.0%～18.0%, the content of CoO is 0.1%～6.0%, Co/Mo atomic ratio 0.1～1.0, the content of potassium are 0.5%～10.0%, P/K atomic ratio 0.1～10.0, surplus is a carrier; The pore volume of said catalyst is 0.3～1.0ml/g, and specific area is 150～400m
2/ g, wherein specific area is to adopt the low temperature liquid nitrogen determination of adsorption method.
2. according to the described catalyst of claim 1, it is characterized in that in the described catalyst carrier TiO
2And/or ZrO
2Weight content be 11%～19%.
3. according to claim 1 or 2 described catalyst, it is characterized in that in the described catalyst MoO
3Weight content be more than 1.0% and less than 10.0%, the weight content of CoO is 0.1%～5.0%.
4. according to claim 1 or 2 described catalyst, it is characterized in that in the described catalyst MoO
3Weight content be 10.0%～18.0%, the weight content of CoO is 1.0%～6.0%.
5. according to the described catalyst of claim 1, it is characterized in that in the described catalyst P/K atomic ratio 0.8～5.0.
6. claim 1 or 2 said Preparation of catalysts methods; Comprise alumina support load potassium and phosphorus with titanium oxide and/or zirconia modification, after dry and roasting, supported active metal component Co and Mo again; Through drying and roasting, obtain catalyst for selective hydrodesulfurizationof of gasoline; Wherein the preparation method of the aluminium oxide of titanium oxide and/or zirconia modification is following:
The aluminum sulfate aqueous solution and the sodium metaaluminate aqueous solution carry out neutralization reaction 0.4～1.5h under 50～90 ℃ of conditions; The pH value of control neutralization reaction is 7.0～9.5; Aging then 0.2～1.0h after washing 2～5 times, adds zirconium-containing compound and/or titanium-containing compound is pulled an oar then; The filter cake that obtains after the filtration is 90～130 ℃ of dryings 5～34 hours, through grinding the aluminum oxide dry glue powder that promptly obtains titanium oxide and/or zirconia modification; This dry glue powder descended dry 1～5 hour at 100～120 ℃ through extruded moulding then, promptly obtained the alumina support of titanium oxide and/or zirconia modification in 1～5 hour 400～600 ℃ of roastings.
7. according to the described method of claim 6; It is characterized in that described zirconium-containing compound is one or more in zirconium dioxide, basic zirconium chloride, zirconium sulfate and the zirconium carbonate, described titanium-containing compound is one or more in metatitanic acid, titanium white powder, titanium chloride and the titanium sulfate.
8. according to the described method of claim 6; The alumina support that it is characterized in that described titanium oxide and/or zirconia modification is to spray method load potassium and phosphorus; 100～120 ℃ dry 1～5 hour down, rise to 400～600 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again.
9. according to the described method of claim 6; It is characterized in that described supported active metal component Co and Mo adopt saturated infusion process; 100～120 ℃ dry 1～5 hour down, rise to 400～650 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again.
10. two sections gasoline selective hydrodesulfurizationmodification methods comprise: the beds that feedstock oil increases through active metallic content under the hydrodesulfurization condition successively gradually, the wherein described catalyst of at least one beds employing claim 1.
11. according to the described method of claim 10, it is characterized in that described two sections gasoline selective hydrodesulfurizationmodification methods adopt two beds, wherein first bed uses the catalyst of low-metal content, the i.e. described catalyst of claim 3; Second bed uses the catalyst of high tenor, i.e. the described catalyst of claim 4; First bed is 2/8～8/2 with the second bed catalyst admission space ratio.
12. according to claim 10 or 11 described methods; It is characterized in that described gasoline selective hydrodesulfurizationmodification technical process is: under hydrodesulfurizationconditions conditions; Raw material at first contacts with one section catalyst with hydrogen; One section product gets into two sections, contacts with two sections catalyst, obtains gasoline products; Described hydrodesulfurizationconditions conditions is following: reaction temperature is 230～320 ℃; Reaction pressure is 1.0～4.0MPa; Hydrogen to oil volume ratio is 100～1000Nm
3/ m
3Volume space velocity is 1.0～10.0h during liquid
-1
13. according to the described method of claim 12, it is characterized in that described hydrodesulfurizationconditions conditions is following: reaction temperature is 250～300 ℃; Reaction pressure is 1.6～3.2MPa; Hydrogen to oil volume ratio is 200～800Nm
3/ m
3Volume space velocity is 2.0～6.0h during liquid
-1
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| CN110935460B (en) * | 2018-09-21 | 2023-02-28 | 中国石油天然气股份有限公司 | High-selectivity hydrodesulfurization catalyst and preparation method thereof |
| CN111117693B (en) * | 2018-10-30 | 2021-08-31 | 中国石油化工股份有限公司 | Gasoline selective hydrodesulfurization method |
| CN112619632B (en) * | 2019-09-24 | 2022-07-08 | 中国石油化工股份有限公司 | Modified alumina carrier and preparation method thereof |
| CN114618511B (en) * | 2020-12-11 | 2023-07-14 | 中国石油化工股份有限公司 | Heavy oil hydrodesulfurization catalyst and heavy oil hydrotreating method |
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| CN1488721A (en) * | 2002-10-10 | 2004-04-14 | 中国石油化工股份有限公司 | Selective hydrogenation catalyst for gasoline and process |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
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| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
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