CN102049269B - Selective hydrogenation catalyst for gasoline and preparation method thereof - Google Patents
Selective hydrogenation catalyst for gasoline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a selective hydrogenation catalyst for gasoline and a preparation method thereof. A carrier of the catalyst consists of alumina modified by titanium oxide and/or zirconium oxide, carbon and silicone oxide in a specific ratio, wherein a proper amount of titanium oxide and/or zirconium oxide is introduced in the pulping process after the alumina is gelled; and in the kneading process, a proper amount of carbon and silicon oxide are added. The alumina is modified by the method, the total acids of the carrier are properly improved, particularly the L acid is greatly improved, and the carbon is added to inhibit the hydrogenation activity of olefin through selective interaction with an olefin hydrogenation activity center, so that the selective hydrodesulfurization capacity of the catalyst is improved, the effect of the carrier on an aid of potassium is enhanced, the carrier is coordinate with an aid of phosphorus, the loss of the potassium is prevented and the stability of the catalyst is improved. The catalyst is mainly used for selective hydrodesulfurization of the gasoline, particularly hydrodesulfurization of catalytically cracked gasoline.
Description
Technical field
The present invention relates to a kind of catalyst for selective hydrodesulfurizationof of gasoline and preparation method thereof, especially for two sections selective hydrogenation desulfurization process of catalytically cracked gasoline.
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; But the acidity of carrier is also bigger to the influence of catalyst selectivity hydrodesulfurization, and alumina support is the faintly acid carrier, is that the catalyst hydrodesulfurization active of carrier is lower with it; Introduce auxiliary agent P and K again; Inhibitory action to the alkene saturated activity is limited, and therefore, the hydrodesulfurization selectivity of this catalyst awaits further to improve.
Summary of the invention
To the deficiency of prior art, the present invention provides high selectivity that a kind of activity and selectivity all improve and catalyst for selective hydrodesulfurizationof of gasoline of high stability and preparation method thereof.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention; With Co and Mo is active metal component, is auxiliary agent with potassium and phosphorus, and carrier is made up of the aluminium oxide of silica, carbon and titanium oxide and/or zirconia modification; Carrier meleic acid total acid content is 0.34～0.72mmol/g; L acid acid amount is 0.32～0.70mmol/g, is benchmark with the weight of catalyst, MoO
3Content is 1.0%～18.0%, is preferably 1.0%～16.0%, and CoO content is 0.1%～6.0%, is preferably 0.1%～5.0%, and Co/Mo atomic ratio 0.1～1.0 is preferably 0.2～0.8, K
2O content is 0.2%～10.2%, is preferably 0.5%～5.0%, and P/K atomic ratio 0.1～10.0 is preferably 0.8～5.0, is preferably 1.0～2.0, and surplus is a carrier; Weight with carrier is benchmark, and carbon content is 1.0%～30.0%, is preferably 3.0%～15.0%, and silica content is 1.0%～30.0%, is preferably 3.0%～15.0%, TiO
2And/or ZrO
2Content be 5%～30%, be preferably 11%～19%, alumina content is 50%～90%, is preferably 50%～83%, the atomic ratio of carbon and silicon is 1.0～10.0, is preferably 2.0～8.0.
The pore volume of catalyst according to the invention is 0.3～1.2ml/g, and specific area is 150～400m
2/ g.
Preparation of catalysts method of the present invention comprises following content:
(1) 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;
(2) aluminum oxide dry glue powder, carbon black powder, Ludox and peptizing agent and the extrusion aid with titanium oxide and/or zirconia modification mixes, and mixes back extruded moulding on the extruded moulding machine, after dry and roasting, obtains catalyst carrier;
(3) adopt infusion process load auxiliary agent potassium and phosphorus, after dry and roasting, obtain containing the catalyst carrier of potassium and phosphorus again;
(4) adopt infusion process supported active metal Co and Mo,, obtain catalyst of the present invention through drying and roasting.
The present invention is in the process of Preparation of Catalyst, and extrusion aid commonly used can be: one or more in sesbania powder, citric acid, oxalic acid, cellulose, starch, the high molecular surfactant etc., and consumption accounts for 0.1%～20% of step (2) article shaped weight; Used peptizing agent can be: one or more in aluminum sulfate, citric acid, nitric acid, acetic acid, the oxalic acid etc., consumption accounts for 0.1%～20% of step (2) article shaped weight.
The described zirconium-containing compound of step (1) 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.
Described drying of step (2) and roasting condition are following: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
Described drying of step (3) and roasting condition are following: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
Described drying of step (4) and roasting condition are following: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
Catalyst carrier of the present invention is made up of aluminium oxide, carbon and the silica 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; When mixed pinching, add an amount of carbon and silica; Through the said method modified aluminas, can suitably improve the total acid content of carrier, particularly increase substantially L acid acid amount.The acidity of carrier is bigger to the selective hydrodesulfurization influence; The content of sulphur accounts for more than 60% of total sulfur-containing compound in the thiophene-type sulfide; 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; But the alkene saturability also can improve simultaneously; Carbon through adding proper proportion suppresses the hydrogenation activity of alkene through optionally interacting with the hydrogenation of olefins activated centre, and the amplitude of this inhibition is greater than the amplitude that desulphurizing activated center is suppressed, thereby has improved selection of catalysts property.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 selectivity, better stability.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention can be used in the gasoline selective hydrodesulfurizationmodification technology; Especially in two sections gasoline selective hydrodesulfurizationmodification technology; General process is following: 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; Wherein the active metallic content in the catalyst system therefor increases along the liquid phase stream direction gradually increases successively, and one of them or an above beds use catalyst for selective hydrodesulfurizationof of gasoline of the present invention.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention adopts the different activities catalyst to make up, can 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.
The concrete preparation process of catalyst of the present invention is following:
Aluminum oxide dry glue powder, carbon black powder, Ludox and peptizing agent and the extrusion aid of titanium oxide and/or zirconia modification are mixed; Mix back extruded moulding on the extruded moulding machine; Following dry 1～5 hour at 100～120 ℃ then; Rise to 200～550 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again, obtain catalyst carrier.Place afterwards and roll 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, drying is 1～5 hour under 100～120 ℃; Rise to 400～550 ℃ of roastings 1～5 hour with 150～250 ℃/hour programming rate again, obtain phosphorous and catalyst carrier potassium.Again phosphorous placing with catalyst carrier potassium rolled 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 400～550 ℃ 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.
Below specify catalyst used in the present invention with embodiment.
Used carbon black powder is to be produced by the Fushun safe chemical industry of gold Co., Ltd in the embodiment of the invention.
Embodiment 1
The 600ml aluminum sulfate aqueous solution and the 200ml sodium metaaluminate aqueous solution are carried out neutralization reaction 1.0h under 80 ℃ 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; Dry glue powder, 54g Ludox (SiO with the modification of 222g zirconia
2Weight content is 30%), 14g carbon black powder and 136ml water, 23ml nitric acid mixes; Extruded moulding on the extruded moulding machine was placed 18 hours, and drying is 3 hours under 110 ℃; Rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, obtain catalyst carrier A.Take by weighing to place again after the weight and roll pot; Under the rotation condition, the alumina support A 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% (weight) ammoniacal liquor again, add the 29.4g ammonium molybdate in above-mentioned solution to 170ml; The dissolving back transfers to 200ml with liquor capacity, airtight preservation with 25% (weight) ammoniacal liquor.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 A.
Embodiment 2
The 600ml aluminum sulfate aqueous solution and the 200ml sodium metaaluminate aqueous solution are carried out neutralization reaction 1.0h under 70 ℃ of conditions; The pH value of control neutralization reaction is 8.8～9.0; Aging then 0.5h after washing 3 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; Aluminum oxide dry glue powder, 61g Ludox (SiO with the modification of 222g titanium oxide
2Weight content is 30%), 24g carbon black powder and 136ml water, 23ml nitric acid mixes; Extruded moulding on the extruded moulding machine; Placed 18 hours, 110 ℃ dry 3 hours down, rise to 3 hours catalyst carrier B of 500 ℃ of roastings with 200 ℃/hour programming rate again.Take by weighing to place again after the weight and roll pot; Under the rotation condition, the alumina support B 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 B.
Embodiment 3
Change basic zirconium chloride amount among the embodiment 1 into 173g, the potassium dihydrogen phosphate amount changes 17.6g into, 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 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 80 ℃ 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; Aluminum oxide dry glue powder, 54g Ludox (SiO with 222g zirconia and titanium oxide modification
2Weight content is 30%), 16g carbon black powder and 136ml water, 23ml nitric acid mixes; Extruded moulding on the extruded moulding machine was placed 18 hours, and drying is 3 hours under 110 ℃; Rise to 500 ℃ of roastings 3 hours with 200 ℃/hour programming rate again, obtain catalyst carrier D.Take by weighing to place again after the weight and roll pot; Under the rotation condition, the alumina support D in rolling pot sprays into 154ml with atomizing type and contains the phosphoric acid mixed aqueous solution that 9.3g 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 25wt% ammoniacal liquor again to 170ml, add the 8.4g ammonium molybdate in above-mentioned solution, the dissolving back transfers to 200ml with 25wt% 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 F.
Embodiment 7
On 200ml fixed bed small hydrogenation device, adopt A, B, C, D, E, F catalyst respectively, volume space velocity 3.0h when reaction pressure 1.6MPa, liquid
-1, hydrogen to oil volume ratio is 300Nm
3/ m
3, reaction temperature is respectively under 270,310,260,310,260,250 ℃ of conditions, is that 770 μ g/g, RON are that 92.6 raw material carries out selective hydrodesulfurization to sulfur content.
Comparative example 1
The preparation method does not add basic zirconium chloride with embodiment 3 in the aluminum oxide dry glue powder, do not add carbon black powder and Ludox in the carrier, obtains catalyst carrier G.
Comparative example 2
The preparation method does not just introduce phosphorus and potassium component on the carrier with embodiment 3, obtains catalyst H.
Comparative example 3
The preparation method does not just introduce carbon on the carrier with embodiment 3, obtains catalyst I.
Comparative example 4
The preparation method does not just introduce zirconium and silicon on the carrier with embodiment 3, obtains catalyst J.
Comparative example 5
Difference evaluate catalysts G, H, I, J, evaluation method is with embodiment 7.
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 1,2.
Table 1 catalyst main character
| The catalyst numbering | A | B | C | D | E | F | G | II | I | J |
| Carrier is formed | ||||||||||
| ZrO 2，wt％ | 13.89 | - | 18.52 | 17.55 | - | 8.34 | - | 18.52 | 18.52 | - |
| TiO 2，wt％ | - | 11.03 | - | - | 12.98 | 9.19 | - | - | - | - |
| C，wt％ | 6.11 | 9.89 | 6.04 | 5.68 | 11.76 | 6.94 | - | 6.04 | - | 6.04 |
| SiO 2，wt％ | 6.99 | 9.13 | 6.89 | 6.50 | 8.85 | 6.88 | - | 6.89 | 6.89 | - |
| Aluminium oxide, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | 100 | Surplus | Surplus | Surplus |
| Carrier character | ||||||||||
| Infrared total acid content, mmol/g | 0.583 | 0.409 | 0.488 | 0.488 | 0.409 | 0.591 | 0.226 | 0.488 | 0.490 | 0.216 |
| B acid acid amount, mmol/g | 0.091 | 0.081 | 0.069 | 0.069 | 0.081 | 0.099 | 0.023 | 0.069 | 0.070 | 0.021 |
| L acid acid amount, mmol/g | 0.492 | 0.328 | 0.419 | 0.419 | 0.328 | 0.492 | 0.203 | 0.419 | 0.420 | 0.195 |
| Catalyst is formed | ||||||||||
| MoO 3，wt％ | 8.1 | 4.2 | 11.9 | 4.3 | 11.9 | 15.8 | 11.8 | 12.1 | 11.9 | 11.8 |
| CoO，wt％ | 2.5 | 1.4 | 3.2 | 1.4 | 3.2 | 4.0 | 3.2 | 3.4 | 3.2 | 3.2 |
| The Co/Mo atomic ratio | 0.59 | 0.64 | 0.52 | 0.63 | 0.52 | 0.49 | 0.52 | 0.53 | 0.52 | 0.52 |
| P，wt％ | 1.7 | 1.9 | 1.6 | 0.8 | 1.6 | 1.8 | 1.6 | - | 1.6 | 1.6 |
| K 2O，wt％ | 2.6 | 2.7 | 2.5 | 7.5 | 2.5 | 2.0 | 2.5 | - | 2.5 | 2.5 |
| The P/K atomic ratio | 1.0 | 1.1 | 1.0 | 0.2 | 1.0 | 1.0 | 1.0 | - | 1.0 | 1.0 |
| Catalyst property | ||||||||||
| Pore volume, ml/g | 0.40 | 0.47 | 0.39 | 0.40 | 0.39 | 0.37 | 0.45 | 0.40 | 0.38 | 0.42 |
| Specific area, m 2/g | 205 | 209 | 194 | 188 | 189 | 192 | 221 | 213 | 196 | 220 |
| Bulk density, g/ml | 0.80 | 0.78 | 0.82 | 0.81 | 0.83 | 0.85 | 0.74 | 0.80 | 0.83 | 0.72 |
| Intensity, N/ unit | 135 | 150 | 130 | 135 | 133 | 142 | 124 | 133 | 131 | 123 |
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, catalyst of the present invention has better hydrodesulfurization selectivity, and under the situation of equal desulfurization degree, loss of octane number is less.Through after certain duration of runs, selection of catalysts property hydrodesulfurization performance of the present invention is stable than the comparative catalyst.
Claims (11)
1. catalyst for selective hydrodesulfurizationof of gasoline; With Co and Mo is active metal component, is auxiliary agent with potassium and phosphorus, and carrier is made up of the aluminium oxide of silica, carbon and employing titanium oxide and/or zirconia modification; Carrier meleic acid total acid content is 0.34～0.72mmol/g; L acid acid amount is 0.32～0.70mmol/g, is benchmark with the weight of catalyst, MoO
3Content is 1.0%～18.0%, and CoO content is 0.1%～6.0%, Co/Mo atomic ratio 0.1～1.0, K
2O content is 0.2%～10.2%, P/K atomic ratio 0.1～10.0, and surplus is a carrier; Weight with carrier is benchmark, and carbon content is 1.0%～30.0%, and silica content is 1.0%～30.0%, TiO
2And/or ZrO
2Content be 5%～30%, alumina content is 50%～90%, the atomic ratio of carbon and silicon is 1.0～10.0.
2. according to the described catalyst of claim 1, it is characterized in that the weight with catalyst is benchmark MoO
3Content is 1.0%～16.0%, and CoO content is 0.1%～5.0%, and the Co/Mo atomic ratio is 0.2～0.8, K
2O content is 0.5%～5.0%, and the P/K atomic ratio is 0.8～5.0, and surplus is a carrier.
3. according to the described catalyst of claim 1, it is characterized in that the weight with carrier is benchmark, carbon content is 3.0%～15.0%, and silica content is 3.0%～15.0%, TiO
2And/or ZrO
2Weight content be 11%～19%, alumina content is 50%～83%, the atomic ratio of carbon and silicon is 2.0～8.0, carbon, silica, TiO in the carrier
2And/or ZrO
2And the weight content sum of aluminium oxide is 100%.
4. according to the described catalyst of claim 1, it is characterized in that in the said catalyst P/K atomic ratio 1.0～2.0.
5. according to the arbitrary described catalyst of claim 1, the pore volume that it is characterized in that said catalyst is 0.3～1.2mL/g, and specific area is 150～400m
2/ g.
6. the arbitrary said Preparation of catalysts method of claim 1～5 comprises following content:
(1) 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;
(2) aluminum oxide dry glue powder, carbon black powder, Ludox and peptizing agent and the extrusion aid with titanium oxide and/or zirconia modification mixes, and mixes back extruded moulding on the extruded moulding machine, after dry and roasting, obtains catalyst carrier;
(3) adopt infusion process load auxiliary agent potassium and phosphorus, after dry and roasting, obtain containing the catalyst carrier of potassium and phosphorus again;
(4) adopt infusion process supported active metal Co and Mo,, obtain the catalyst finished product through drying and roasting.
7. according to the described method of claim 6; It is characterized in that the described zirconium-containing compound of step (1) 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, it is characterized in that described drying of step (2) and roasting condition are following: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
9. according to the described method of claim 6, it is characterized in that described drying of step (3) and roasting condition are following: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
10. according to the described method of claim 6, it is characterized in that described drying of step (4) and roasting condition are following: drying was 1～5 hour under 100～120 ℃, 400～550 ℃ of roastings 1～5 hour.
11. a gasoline selective hydrodesulfurizationmodification method is characterized in that adopting the arbitrary described catalyst of claim 1～5.
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| CN108067210B (en) * | 2016-11-17 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of zirconium-containing alumina dry glue powder and its preparation method and application |
| CN109317142B (en) * | 2017-07-31 | 2021-12-21 | 中国石油化工股份有限公司 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
| CN108452806B (en) * | 2017-10-27 | 2021-01-01 | 中国石油天然气股份有限公司 | Coking naphtha dialkene saturation 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 |
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| CN1249208A (en) * | 1998-09-28 | 2000-04-05 | 中国石油化工集团公司 | Macroporous alumina carrier and preparing process thereof |
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