CN101905165A - Preparation and application of catalyst for selective hydrodesulfurization of gasoline - Google Patents
Preparation and application of catalyst for selective hydrodesulfurization of gasoline Download PDFInfo
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- CN101905165A CN101905165A CN 201010252648 CN201010252648A CN101905165A CN 101905165 A CN101905165 A CN 101905165A CN 201010252648 CN201010252648 CN 201010252648 CN 201010252648 A CN201010252648 A CN 201010252648A CN 101905165 A CN101905165 A CN 101905165A
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Abstract
The invention relates to preparation and application of a catalyst for selective hydrodesulfurization of gasoline. The catalyst comprises the following components in percentage by weight: 6 to 20 percent of CoO+MoO, 0.1 to 5 percent of K2O, 0.1 to 5 percent of MgO, 0.1 to 5 percent of P2O5, and the balance of ZrO2-Al2O3 composite carrier, wherein the ZrO2 accounts for 0.1 to 20 percent of the weight of the composite carrier. The preparation of the catalyst comprises the following steps of: preparing the composite carrier by adopting a complex precipitation method; adding sylvite, sesbania powder and de-ionized water into the composite carrier, uniformly mixing and kneading, extruding and drying the mixture at the temperature of between 100 and 150 DEG C and roasting the mixture at the temperature of between 450 and 550 DEG C to prepare a catalyst carrier; adding ammonia, EDTA (Ethylene Diamine Tetraacetic Acid) complexing agent to prepare stable Co-Mo co-immersion liquid which contains phosphorus and magnesium; and preparing the catalyst by using an isometric spraying immersion method. The catalyst has high selectivity and stability, and can reduce saturation of olefin to the utmost extent, and has a good desulfurization effect.
Description
Technical field
The present invention relates to a kind of preparation and application of catalyst for selective hydrodesulfurizationof of gasoline.
Background technology
USP 4,140, and 626 to disclose a class be the catalyst of carrier with aluminium oxide and magnesia, wherein put down in writing and contained 3w%CoO, 16w%MoO in a kind of catalyst
3, 70w%MgO and 11w%Al
2O
3, its desulfurization degree is that 96% o'clock alkene saturation factor is 64%, the more traditional Hydrobon catalyst of desulfuration selectivity has a greater degree of improvement, but owing to contain a large amount of MgO in this carrier, makes the catalyst bad mechanical strength, is difficult to satisfy the industrial requirements of hydrogenation reaction.
USP 5,441, and 630 disclose a kind of class-hydrotalcite (HRIC) of using adds Al as carrier component
2O
3In, having high surface area, alkalescence through the HRIC of roasting, the catalyst behind the carrier impregnation Co-Mo demonstrate the characteristics that the HDS activity is high, the alkene saturation factor is low, but the octane number of gasoline still has loss to a certain degree.USP5,459,118 on above-mentioned catalytic component basis, propose to increase the alkali-metal raw catelyst of IA family, it is selected catalyst surface hydrogenation lattice degree of intoxication greater than the desulfurization lattice, though it is active but it stops the saturated characteristic of alkene even more important to reduce partial desulfurization, the subject matter of this patent is the poor stability of catalyst, selectivity with prolong the duration of runs descend very fast.
USP 5,525, and 211 disclose a kind of catalyst, and its carrier is the magnesium aluminate spinel through the potash modification, and potash is to load on the carrier by infusion process, and active component is cobalt, molybdenum, and active component loads on the carrier by twice infusion process respectively.Method for preparing catalyst is comparatively complicated, and the loss easily in the catalyst use of the potash on the catalyst, thereby causes the decline of catalyst activity and activity stability.
CN 1488721A has introduced a kind of gasoline selective hydrodesulfurizationmodification combination catalyst, oil product is carried out the two-period form hydrodesulfurization handle, and has adopted two kinds of catalyst by low Co/Mo content and high Co/Mo content respectively.To be higher than 90 ℃ high olefin FCC heavy distillate is raw material, and the desulfurization degree of this combination catalyst is 92%, and the alkene saturation factor is 35%, but product research method octane number (RON) loss is bigger, reaches 6.5 units.
EP 0,755, and 995 have introduced a kind of FCC catalyst for selective hydrodesulfurizationof of gasoline.This catalyst is at conventional Co-Mo/Al
2O
3Done 2 improvement on the basis of catalyst, purpose be to suppress alkene saturated, reduce loss of octane number.Its one of improve be on the catalyst load K of 0.2～3.0wt%, saturated to reduce alkene, suppress carbon distribution; Two of improvement is to adopt the way of area carbon that catalyst is carried out modification, avoids fresh dose of generation that causes phenomenons such as alkene is saturated, a large amount of heat releases because of hyperactivity after the presulfurization; Point out that carbon deposition quantity of catalyst should be between 3～10wt%, C/H in the coke (atomic ratio)＜0.7.Behind an amount of carbon distribution of catalyst surface, its desulphurizing activated and hydrogenation of olefins saturated activity all can descend, but by contrast, the hydrogenation activity of catalyst descends more remarkable.Therefore, under certain desulfurization degree, the olefin hydrogenation of a large amount of heat releases is suppressed, but the selectivity of hydrodesulfurization is improved relatively.The weak point of this catalyst is that its complexity, harsh carbon distribution modification require to have increased the difficulty of industrial operation, have limited its commercial Application.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of catalyst for selective hydrodesulfurizationof of gasoline, be used to produce the hydrotreatment of low-sulphur oil, used catalyst is applicable to total sulfur and the higher FCC gasoline heavy fractioning hydrogenation desulfurating and reducing olefinic hydrocarbon of olefin(e) centent, after heavy petrol behind the hydrogenation and the light gasoline fraction mixing desulfurization, can produce the clean gasoline that satisfies Europe IV sulphur index request.
The present invention is with ZrO
2Weight content is 0.1～20% ZrO
2-Al
2O
3Complex carrier prepares catalyst, and this complex carrier is taked the preparation of complex-precipitation method, and its specific area is 150～350m
2/ g, pore volume are 0.3～0.8ml/g.ZrO
2Content is preferably 10～15%.With respect to conventional carriers Al
2O
3, ZrO
2-Al
2O
3The complex carrier surface acidity strengthens, and the acid amount increases,
Increase in the acid site.Therefore, as the carrier of sulphided state CoMo catalyst, ZrO
2-Al
2O
3The catalyst of load is than traditional CoMo/Al
2O
3Catalyst has higher HDS activity.
ZrO
2-Al
2O
3Complex carrier can pass through chemical precipitation method, complexing sedimentation and traditional immersion process for preparing, and the present invention takes the ZrO of complexing sedimentation preparation
2-Al
2O
3In the complex carrier, amorphous state ZrO
2Be dispersed in Al with particle less than 10nm
2O
3The surface forms the finishing structure.Make it to have concurrently ZrO
2Surface characteristic and Al
2O
3Two kinds of advantages of texture characteristic.
Catalyst for selective hydrodesulfurizationof of gasoline of the present invention is introduced alkali metal in carrier and alkaline-earth metal is made auxiliary agent, and purpose is that minimizing alkene is saturated, suppresses carbon distribution.Selection adds with the form of mineral structure, can reduce auxiliary agent loss in use, keeps the stability of catalyst.Yet, when the phosphorous Co-Mo metallic solution of preparation, also to introduce part solubility auxiliary agent, surface acidity with further modulation carrier surface, though along with the reaction time prolongs this part auxiliary agent and runs off easily, but in initial reaction stage, the initial activity height of catalyst, the initial activity that the present invention utilizes the auxiliary agent of this part phase commute loss to come catalyst deactivation just, the alkene that reduces during this is saturated, suppresses catalyst carbon deposition.
The present invention introduces P when preparation activity component impregnation liquid, purpose is the acid strength distribution that changes carrier by the introducing of P, influences MoO
3In the distribution of carrier surface and make MoO
3Decentralization at carrier surface increases.In addition, the adding of an amount of phosphorus can reduce the Al ion of complex carrier surface tetrahedral coordination, weakens especially Al of carrier
2O
3With the strong interaction between the CoMo active component.
The adding of auxiliary agent P can add when the carrier moulding, also can phosphorous Co-Mo co-impregnated solution is disposable to load on the carrier by preparing, and the preferred latter of the present invention.Reason is if introduce P when preparing carriers, by dry, roasting, must cause significantly reducing of carrier pore volume again, under go on foot incipient impregnation reactive metal solution and caused difficulty.Because under liquor capacity very condition of limited, be difficult to prepare stable high tenor Co-Mo solution.
The preparation method of catalyst for selective hydrodesulfurizationof of gasoline of the present invention, by following steps:
Press the weight percent meter of catalyst, CoO+MoO:6～20%; K
2O:0.1～5%; MgO:0.1～5%; P
2O
5: 0.1～5%; Surplus is ZrO
2-Al
2O
3Complex carrier; ZrO
2Be 0.1～20% of complex carrier weight;
1) take the complex-precipitation legal system to be equipped with ZrO
2-Al
2O
3Complex carrier:
(1) taking by weighing zirconium oxychloride is dissolved in the ethanol water;
(2) add the acetylacetone,2,4-pentanedione complexing agent in (1) solution, zirconium oxychloride and acetylacetone,2,4-pentanedione mol ratio 1: 4 are regulated the pH value with ammoniacal liquor and are about 9.0;
(3) add aluminium oxide in (2) solution, aluminium oxide adds weight and presses ZrO
2Account for complex carrier weight 0.1～20%, at room temperature stir 3 hours after, water-bath is heated to 90 ℃, system is solidified rapidly, suction filtration, Cl is removed in washing
-
(4) solid sample dries successively naturally, 3 hours, 550 ℃ roastings of 120 ℃ of dryings got final product in 4 hours;
2) carrier moulding: the ZrO that step 1) is made
2-Al
2O
3Powder grinds and is screened to below 100 orders adding sylvite, sesbania powder, deionized water, mix and pinch evenly, on single-screw extruder,, place 1～4h with Φ 2.0mm clover orifice plate extrusion, dry 3～8h for 100～150 ℃ then, 450～550 ℃ of roasting 3～8h make catalyst carrier;
3) adding ammoniacal liquor, EDTA complexing agent are prepared the Co-Mo co-impregnated solution of stable phosphorous and magnesium;
4) adopt equal-volume spray infusion process, with the solution impregnation step 2 of step 3) preparation) catalyst carrier that makes, dip time is 4～8 hours; Dry 3～8h, 400～500 ℃ of roasting 3～8h for 100～150 ℃ then.
The catalyst of preparation method's preparation of catalyst for selective hydrodesulfurizationof of gasoline of the present invention is used for selective hydrogenation desulfuration catalyst for catalytically cracking gasoline, the use procatalyst must be through vulcanizing treatment, curing temperature is 230～320 ℃, cure time is 12～36 hours, and hydrogen to oil volume ratio is 100～400; Adopt the fixed bed hydrogenation device, reaction pressure is 1～3MPa, and reaction temperature is 220～300 ℃, and volume space velocity is 1～5h
-1, hydrogen to oil volume ratio 100～400.
Catalyst of the present invention adopts the complex-precipitation method to prepare ZrO
2-Al
2O
3Complex carrier, and determined best ZrO
2Content is so that it fully has ZrO concurrently
2Surface characteristic and Al
2O
3Two kinds of advantages of texture characteristic, the catalyst desulfurizing activity is good.The present invention takes mineral structure sylvite and general water soluble magnesium salt pair carrier to carry out the substep modification in addition.The auxiliary agent of mineral structure is difficult for running off, and it is saturated to reduce alkene, suppresses catalyst carbon deposition; And the water-soluble additive that adds mainly is at the catalyst runs initial stage it to be played certain passivation, and is saturated to reduce alkene, suppresses catalyst carbon deposition.Along with prolong the duration of runs, the slow carbon distribution inactivation of catalyst meeting, but because the slow loss of above-mentioned auxiliary agent has remedied loss of activity.Therefore both comprehensively make catalyst have good activity stability.Catalyst of the present invention strengthens for the adaptability of raw material, and the moisture impurity level that waits of feedstock oil is had stronger adaptability.
The predecessor of described mineral structure sylvite comprises kaliophilite, potassic feldspar, preferred kaliophilite.
The predecessor of described magnesium comprises magnesium nitrate, magnesium chloride, magnesium acetate, magnesium phosphate, preferred magnesium nitrate.
The predecessor preferably phosphoric acid ammonium dihydrogen of described phosphorus.
Preferred cobalt nitrate of the predecessor of described Co-Mo and ammonium molybdate.
The invention effect
Characteristics of the present invention are to adopt novel ZrO
2-Al
2O
3Complex carrier prepares catalyst for selective hydrodesulfurizationof of gasoline, and in carrier, introduce alkali metal, alkaline-earth metal and phosphorus, alkali metal and alkaline-earth metal add step by step with the form of mineral structure and water soluble salt, phosphorus and active component are made into the disposable load of stabilizing solution.Catalyst of the present invention under the hydroconversion condition that relaxes, is handled the catalytically cracked gasoline of sulfur-bearing, alkene after presulfurization, show good selectivity and stability, and it is saturated to reduce alkene to greatest extent, and desulfurized effect is good.
The specific embodiment
Embodiment 1
ZrO
2-Al
2O
3The preparation of complex carrier powder
Complexing sedimentation: with ZrO in the carrier
2Relative Al
2O
3For 10wt% is an example: take by weighing 32gZrOCl
28H
2It is in 1: 1 the ethanol water that O is dissolved in the 500ml volume ratio, adds the 45ml acetylacetone,2,4-pentanedione, and dropping ammonia transfers system pH to be about 9.0, obtains bright yellow solution.In this solution, add the Al of 100g after through 120 ℃ of oven dry
2O
3, at room temperature stir 4h after, water-bath is heated to 90 ℃, system is solidified rapidly.After filtration, be washed to no Cl
-After, dry 12h, 120 ℃ of oven dry 4h naturally, make support powder.
Other different ZrO
2The complex carrier of content can be by changing ZrOCl pari passu
28H
2O, acetylacetone,2,4-pentanedione consumption are by preparing with quadrat method.
Embodiment 2
The preparation of catalyst carrier
The ZrO that embodiment 1 is made
2-Al
2O
3Powder grinds and is screened to below 100 orders, takes by weighing 50g then, adds 10g kaliophilite, 1.25g sesbania powder, 30ml deionized water, mix and pinch evenly, on single-screw extruder,, place 1～4h with Φ 2.0mm clover orifice plate extrusion, dry 4h, 550 ℃ of roasting 4h for 120 ℃ then.Make preformed catalyst carrier.
Embodiment 3
The preparation of Co-Mo co-impregnated solution
The catalyst carrier that makes with 100g embodiment 2 is an example: at first the water absorption rate with conventional method measurement catalyst carrier is the 65ml/100g carrier, the solution preparation steps is: weighing 13g EDTA, add the stirring of 40ml weak aqua ammonia and make its dissolving, add 13g cobalt nitrate, 15g ammonium molybdate stirring and dissolving then successively, add 10g ammonium dihydrogen phosphate (ADP) and 15g magnesium nitrate stirring and dissolving again.Being settled to 65ml with ammoniacal liquor at last gets final product.
Embodiment 4
Preparation of catalysts
The catalyst carrier that makes with 100g embodiment 2 is an example, concrete steps are: load weighted catalyst carrier is slowly put into the spray impregnating autoclave, it is at the uniform velocity slowly rotated, the solution that embodiment 3 is prepared evenly is sprayed onto the catalyst carrier surface, the solution that the full and uniform absorption of catalyst carrier is joined continues after having sprayed to rotate half an hour again, catalyst is poured out and the static placement of room temperature 4h again, place 120 ℃ of oven dry of baking oven 4h then, 450 ℃ of roasting 4h.Make catalyst sample Cat-1.
Embodiment 5
Preparation of catalysts
The preparation process of present embodiment catalyst Cat-2 is identical with Cat-1, and that different is ZrO
2-Al
2O
3ZrO in the complex carrier
2Relative Al
2O
3Content is 15wt%.
Comparative Examples 1
The preparation process of this Comparative Examples catalyst Cat-3 is identical with Cat-1, and different is without ZrO
2-Al
2O
3Complex carrier, and all use Al
2O
3Make carrier.Need add the nitric acid that accounts for alumina dry basic weight amount 2wt% during extruded moulding and make peptizing agent.
Comparative Examples 2
The preparation process of this Comparative Examples catalyst Cat-4 is identical with Cat-1, and that different is ZrO
2-Al
2O
3Complex carrier uses the chemical precipitation method preparation.Concrete preparation process is:
Boehmite and the proper amount of deionized water 30min that pulls an oar under high speed machine stirs slowly adds a certain amount of ZrOCl again
28H
2The O aqueous solution.After continue stirring 10min, slowly add concentration and be 12.5% ammoniacal liquor, solidify up to liquid mixed system moment.After filtration, be washed to no Cl
-After, dry 12h, 120 ℃ of oven dry 4h naturally, make support powder.
Comparative Examples 3
The preparation process of this Comparative Examples catalyst Cat-5 is identical with Cat-1, and that different is ZrO
2-Al
2O
3Complex carrier uses immersion process for preparing.Concrete preparation process is:
According to γ-Al
2O
3Water absorption rate and made complex carrier in ZrO
2Content, prepare certain density ZrOCl
28H
2The O aqueous solution.With a certain amount of Al
2O
3Be immersed in excessive ZrOCl
28H
2In the O aqueous solution, stir 4h under the room temperature after, suction filtration is removed unnecessary liquid, with filter cake dry naturally successively, 120 ℃ of oven dry 4h, make support powder.
Comparative Examples 4
The preparation process of this Comparative Examples catalyst Cat-6 is identical with Cat-1, and different is not add kaliophilite when the carrier moulding.
Comparative Examples 5
The preparation process of this Comparative Examples catalyst Cat-7 is identical with Cat-1, and different is not introduce magnesium and phosphorus when preparation Co-Mo co-impregnated solution.
Application examples
Present embodiment explanation adopts above-mentioned catalyst in the application that improves aspect the FCC quality of gasoline.The Main physical chemical property of each catalysis sees Table 1.
The evaluating catalyst process is as follows: catalyst Cat-1～Cat-7 is respectively charged in the small stationary bed bioreactor, and charge weight is 10ml, airtight qualified after, at first carry out presulfiding of catalyst.Sulfurized oil is a direct steaming gasoline, and vulcanizing agent is CS
2, its concentration is 3.0wt%, and sulfide stress is 2.0Mpa, and hydrogen to oil volume ratio is 300, and the sulfurized oil volume space velocity is 4.0h
-1, the sulfuration program is 150 ℃ of vulcanizing treatment 1 hour, 230 ℃, 290 ℃, 320 ℃ about 6 hours of vulcanizing treatment respectively.After sulfuration finishes, feed the catalytically cracked gasoline heavy distillat (cut point is 90 ℃) of 90～210 ℃ of boiling ranges under probe temperature, reaction condition is: 250 ℃, pressure 2.0Mpa, hydrogen-oil ratio (volume) is 300: 1, air speed 2h
-1Sample analysis behind the reaction 72h.Reaction result sees Table 2.
The main physico-chemical property of table 1 catalyst Cat-1～Cat-7
| Project | Cat-1 | Cat-2 | Cat-3 | Cat-4 | Cat-5 | Cat-6 | Cat-7 |
| MoO 3，w％ | 10.3 | 9.6 | 10.5 | 10.3 | 9.5 | 10.8 | 11.5 |
| CoO，w％ | 2.9 | 2.7 | 2.9 | 3.0 | 2.7 | 3.2 | 3.6 |
| The Co/Mo atomic ratio | 0.54 | 0.54 | 0.53 | 0.56 | 0.55 | 0.57 | 0.60 |
| ZrO 2，w％ | 7.4 | 11.5 | - | 7.8 | 8.3 | 8.0 | 8.2 |
| P 2O 5，w％ | 3.4 | 3.5 | 3.5 | 3.3 | 3.2 | 3.4 | - |
| K 2O，w％ | 1.8 | 1.5 | 1.3 | 2.0 | 1.7 | - | 1.7 |
| MgO，w％ | 2.0 | 1.8 | 1.9 | 1.8 | 1.7 | 2.2 | - |
| Pore volume, ml/g | 0.46 | 0.42 | 0.54 | 0.42 | 0.32 | 0.47 | 0.48 |
| Specific area, m 2/g | 240 | 226 | 263 | 233 | 205 | 250 | 254 |
| Bulk density, g/ml | 0.72 | 0.75 | 0.70 | 0.74 | 0.73 | 0.71 | 0.76 |
| Intensity, N/cm | 135 | 132 | 130 | 135 | 131 | 133 | 129 |
The FCC gasoline selective hydrodesulfurizationmodification reaction result of table 2 catalyst Cat-1～Cat-7
| Project | Feedstock oil | Cat-1 | Cat-2 | Cat-3 | Cat-4 | Cat-5 | Cat-6 | Cat-7 |
| Sulphur/μ gg -1 | 450 | 61 | 73 | 125 | 67 | 194 | 70 | 68 |
| Alkene/v% | 49.5 | 37.9 | 35.5 | 34.6 | 35.1 | 42.3 | 35.2 | 31.2 |
| RON | 90.5 | 87.2 | 86.5 | 86.2 | 86.4 | 88.5 | 86.4 | 85.5 |
| The RON loss | - | 3.3 | 4.0 | 4.3 | 4.1 | 2.0 | 4.1 | 5.0 |
| Desulfurization degree/% | - | 86.4 | 83.8 | 72.2 | 85.1 | 56.9 | 84.4 | 84.9 |
| Alkene saturation factor/% | - | 23 | 28 | 30 | 29 | 15 | 29 | 37 |
Table 1,2 results show that the present invention is with the ZrO of complex-precipitation method preparation
2-Al
2O
3Complex carrier prepares catalyst for selective hydrodesulfurizationof of gasoline, more common Al
2O
3The ZrO that carrier and other modes prepare
2-Al
2O
3Complex carrier is desulphurizing activated wants high; Introduce potassium, magnesium and phosphate builder in catalyst, under the situation of equal desulfurization degree, loss of octane number is little.With catalyst Cat-1 is research object, investigates its stability to the hydrodesulfurization of FCC heavy petrol, the results are shown in Table 3.As seen from table, at the 300h run duration, this catalyst activity, selectivity are good, and every reactivity worth index is stable and with early stage the result consistent, indicate its selective hydrodesulfurization good stability, have industrial application value.
The stability experiment result of table 3 catalyst Cat-1
| Reaction time/h | Sulphur/μ gg -1 | Alkene/v% | RON |
| Raw material | 450 | 49.5 | 90.5 |
| 100 | 60 | 37.8 | 87.2 |
| 200 | 63 | 37.9 | 87.3 |
| 300 | 61 | 37.5 | 87.1 |
| Mean value | 61 | 37.7 | 87.2 |
Claims (2)
1. the preparation method of a catalyst for selective hydrodesulfurizationof of gasoline is characterized in that:
Press the weight percent meter of catalyst, CoO+MoO:6～20%; K
2O:0.1～5%; MgO:0.1～5%; P
2O
5: 0.1～5%; Surplus is ZrO
2-Al
2O
3Complex carrier; ZrO
2Be 0.1～20% of complex carrier weight;
1) take the complex-precipitation legal system to be equipped with ZrO
2-Al
2O
3Complex carrier:
(1) taking by weighing zirconium oxychloride is dissolved in the ethanol water;
(2) in (1) solution, add the acetylacetone,2,4-pentanedione complexing agent, zirconium oxychloride and acetylacetone,2,4-pentanedione mol ratio 1: 4, regulating the pH value with ammoniacal liquor is 9.0;
(3) add aluminium oxide in (2) solution, aluminium oxide adds weight and presses ZrO
2Account for complex carrier weight 0.1～20%, at room temperature stir 3 hours after, water-bath is heated to 90 ℃, system is solidified rapidly, suction filtration, Cl is removed in washing
-
(4) solid sample dries successively naturally, 3 hours, 550 ℃ roastings of 120 ℃ of dryings got final product in 4 hours;
2) carrier moulding: the ZrO that step 1) is made
2-Al
2O
3The complex carrier powder grinds and is screened to below 100 orders adding sylvite, sesbania powder, deionized water, mix and pinch evenly, on single-screw extruder,, place 1～4h with Φ 2.0mm clover orifice plate extrusion, dry 3～8h for 100～150 ℃ then, 450～550 ℃ of roasting 3～8h make catalyst carrier;
3) adding ammoniacal liquor, EDTA complexing agent are prepared the Co-Mo co-impregnated solution of stable phosphorous and magnesium;
4) adopt equal-volume spray infusion process, with the solution impregnation step 2 of step 3) preparation) catalyst carrier that makes, dip time is 4～8 hours; Dry 3～8h, 400～500 ℃ of roasting 3～8h for 100～150 ℃ then.
2. the preparation method of a catalyst for selectively hydrodesulfurizing according to claim 1, its feature is used for selective hydrogenation desulfuration catalyst for catalytically cracking gasoline, the use procatalyst must be through vulcanizing treatment, curing temperature is 230～320 ℃, cure time is 12～36 hours, and hydrogen to oil volume ratio is 100～400; Adopt the fixed bed hydrogenation device, reaction pressure is 1～3MPa, and reaction temperature is 220～300 ℃, and volume space velocity is 1～5h
-1, hydrogen to oil volume ratio 100～400.
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| CN106311316A (en) * | 2016-07-25 | 2017-01-11 | 中国石油大学(北京) | Selective hydrodesulfurization catalyst and desulfurization method |
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| CN101905165B (en) | 2012-07-18 |
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