CN101089132A - Fraction oil hydrodesulfurizing catalyst and its prepn process - Google Patents
Fraction oil hydrodesulfurizing catalyst and its prepn process Download PDFInfo
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Abstract
The present invention discloses one kind of fraction oil hydrodesulfurizing catalyst and its preparation process. The catalyst has alumina or silicon-containing alumina as carrier, W, Mo, Ni and Co as active components, and phosphorus assistant. It is prepared through saturation co-soaking process, and has active metal components possessing synergistic effect high dispersed, and high activity, especially high hydrodesulfurizing activity. It is used in the hydrodesulfurizing process, especially deep hydrodesulfurizing process, of various kinds of fraction oil.
Description
Technical field
The present invention relates to a kind of catalyst for hydrodesulfurizationfraction fraction oil and preparation method thereof, particularly the deeply desulfurizing fractional oil Catalysts and its preparation method.
Background technology
Typical Hydrobon catalyst, being carrier with aluminum oxide or siliceous aluminum oxide often, is active ingredient with VIII family and group vib metallic element, in order to improve activity of such catalysts and stability, normal adopt multiple improving one's methods, as to support modification, optimize the preparation method, add auxiliary agent etc.Auxiliary agent commonly used has P, F, B, Ti, Zr etc.
For hydrodesulfurization reaction, the active order of different metal combination of components is Co-Mo＞Ni-Mo ≈ Ni-W＞Co-W; And for hydrogenation activity, the active order of metal component combination is Ni-W＞Ni-Mo＞Co-Mo＞Co-W.Thiophene-based is not during the HDS of presence bit inhibition effect sulfide, the Co-Mo catalyzer is better than the Ni-Mo catalyzer, and for ultra-deep hydrodesulfuration, when desulfurization degree＞99%, need remove 4,6-dimethyl Dibenzothiophene class sulfide, this class sulfide is because the influence of steric effect, desulphurization reaction speed is much larger than the speed of reaction of direct hydrogenating desulfurization behind elder generation's hydrogenation, and in such cases, the Ni-Mo catalyzer is better than the Co-Mo catalyzer.
When the low-sulfur diesel-oil of production sulphur content＜500 μ g/g, its hydrodesulfurization reaction of the sulfide that need remove is mainly followed the direct desulfurization approach, generally suit under the processing condition of high-speed, low hydrogen/gasoline ratio, to operate, adopt Mo-Co type catalyzer just can realize usually.In order to reach the purpose of ultra-deep desulfurization, then require catalyzer to have the active and stronger hydrogenation performance of higher direct desulfurization simultaneously.Companies such as external many companies such as IFP, Tops φ e and ART then adopt Mo-Ni and Mo-Co catalyst combination technology.But the combination of this different activities component catalyst can not make the active and effectively collaborative simultaneously performance of suitable hydrogenation performance of the needed good direct desulfurization of deep desulfuration, can not satisfy the needs of distillate oil deep hydrogenating desulfurization.
Relevant is that the technology of preparing of Hydrobon catalyst of active ingredient is more with Mo-Ni or Mo-Co, or is not inventive point with the reactive metal cooperation, only points out generally that active ingredient is one or more in group vib metal and the group VIII metal.Disclose a kind of preparation method of catalyst for hydrodesulfurizationfraction fraction oil as Chinese patent ZL94116957.X, but catalyzer is active ingredient with Mo-Co, the deep desulfuration activity is undesirable.
Chinese patent ZL99113281.5 has made the W-Mo-Ni-P co-impregnated solution, and adopts gradation to soak legal system altogether to be equipped with catalyzer, but graded impregnation preparation flow complexity, the production cycle is long, and in addition, W-Mo-Ni-P makes up the needs that can not satisfy deep desulfuration well.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of highly active catalyst for hydrodesulfurizationfraction fraction oil and preparation method thereof, particularly highly active distillate oil deep Hydrobon catalyst and preparation method thereof.
The composition and the character of catalyst for hydrodesulfurizationfraction fraction oil of the present invention are as follows:
With aluminum oxide or siliceous aluminum oxide is carrier, is active ingredient with W, Mo, Ni, Co, and for helping catalyst component, in catalyst weight, each component concentration is respectively WO with P
35%～25%, MoO
35%～25%, NiO1%～5%, CoO1%～5%, P
2O
50.5%～9%; WO preferably
3Be 6～16%, MoO
38～22%, NiO1～3%, CoO1～4%, P
2O
51～3%.0.20～0.40 milliliter/gram of catalyzer pore volume, 110～270 meters of specific surface areas
2/ gram.Described active ingredient and to help catalyst component be to load on the support of the catalyst by saturated mode of soaking is altogether once promptly carried out single-steeping with load active component with help catalyst component with the co-impregnated solution that contains W, Mo, Ni, Co, P to support of the catalyst.
Preparation of catalysts method of the present invention comprises following process:
Catalyzer of the present invention is a carrier with aluminum oxide or siliceous aluminum oxide, is active ingredient with W-Mo-Ni-Co, adds the P auxiliary agent, makes the W-Mo-Ni-Co-P co-impregnated solution, makes stable co-impregnated solution through 70～120 ℃ of heating.With the mode impregnated carrier of saturated dipping once, moist catalysis was through 80～150 ℃ of dryings 2～8 hours with above-mentioned co-impregnated solution, and 350～550 ℃ of roastings made in 2～5 hours.
The preparation of described aluminum oxide or siliceous alumina supporter can be that aluminum oxide is added peptizing agent and extrusion aid or silicon sol, mixes and pinches the back extruded moulding or drip ball forming, makes in 2～5 hours through 2～8 hours, 500～650 ℃ roastings of 80～150 ℃ of dryings.Described aluminum oxide can be to adopt various existing method preparations, makes as aluminum chloride ammoniacal liquor method, Tai-Ace S 150-sodium metaaluminate method, carborization and alkyl aluminum hydrolysis method etc.
The compound method of W-Mo-Ni-Co-P co-impregnated solution can be: tungsten compound, nickel compound, cobalt compound, molybdenum compound, phosphorus compound and deionized water are mixed simultaneously, stir after 70～120 ℃ of heating make stable co-impregnated solution.
Above-mentioned tungsten compound can be one or more in ammonium metawolframate, wolframic acid or other tungstate, preferably ammonium metawolframate; Molybdenum compound can be one or more in molybdic oxide or the ammonium molybdate, preferably molybdic oxide; Nickel compound can be a kind of in nickelous carbonate, nickelous nitrate and the nickel acetate, preferably nickelous carbonate; Cobalt compound can be a kind of in cobaltous carbonate, Xiao Suangu and the Cobaltous diacetate, preferably cobaltous carbonate; Phosphorus compound can be a kind of in phosphoric acid or the phosphorous acid, preferably phosphoric acid.
Each component concentrations is in the described co-impregnated solution:
WO
3:/100 milliliters of 10～40 grams, NiO:2～10 restrain/100 milliliters, and CoO:2～10 restrain/100 milliliters, MoO
3:/100 milliliters of 5～40 grams, P
2O
5:/100 milliliters of 2～8 grams.The temperature of solution preparation is 70～120 ℃.
The condition of dipping: saturated dipping under the room temperature.Saturated dipping refers to that the consumption of dipping solution equals the water-intake rate of support of the catalyst.
Above-mentioned extrusion aid is: one or more in sesbania powder, citric acid, the acetic acid etc.
Above-mentioned peptizing agent is: one or more in nitric acid, hydrochloric acid and the deionized water etc.
Though the component that the present invention selects is comparatively conventional component, in the prior art not directly with all these components as the necessary component in the product.Though generally point out in some patents, active ingredient is one or more in group vib metal and the group VIII metal, and inreal indication adopts different components to cooperate to produce what technique effect.The present invention is unexpected to be found, adopts the W-Mo-Ni-Co-P cooperation of specified proportion to be the catalyst component of desulfurization catalyst, and the suitable preparation method by specific makes catalyzer of the present invention have beyond thought catalytic activity in the deeply desulfurizing fractional oil process.Compared with prior art, catalyzer of the present invention has not only overcome the defective of prior art deep hydrodesulfurizationof, and the catalyzer that adopts the inventive method to prepare, when handling high sulfur diesel, its deep hydrodesulfurizationof specific activity Mo-Co type catalyzer improves more than 30%, be better than Mo-Ni or W-Ni type catalyzer, and direct desulfurization specific activity Mo-Ni or W-Ni type catalyzer improve more than 50%, can satisfy the needs of different desulfurization depth.This catalyzer has very high hydrodesulfurization activity to distillate, is specially adapted to 80～380 ℃ straight run oil, the hydrodenitrification and the hydrogenating desulfurization of secondary processing oil, is particularly suitable for the deep hydrodesulfurizationof of diesel oil.The hydrodesulfurization activity of this catalyzer is higher more than 35% than W-Mo-Ni-P catalyst activity.Preparation of catalysts method of the present invention is simple, can finish by single-steeping, has simplified Production Flow Chart, can reduce production costs.Experiment finds that single-steeping not only process is simple, and than repeatedly flooding the cooperation effect that more helps different components, highly beneficial to the comprehensive use properties that improves catalyzer.
Embodiment
Further set forth feature of the present invention and effect below in conjunction with specific examples.Wherein content is weight content.
The preparation of carrier T-1
Use aluminium hydrate powder 1000g, add 20 milliliters in nitric acid, 700 milliliters of deionized waters and extrusion aid mixing and roll, become trifolium-shaped through extrusion, 3 hours, 550 ℃ roastings of 110 ℃ of dryings made carrier T-1 in 3 hours.
The preparation of carrier T-2
Use aluminium hydrate powder 900g, add 18 milliliters in nitric acid, 600 milliliters of deionized waters, silicon sol 450g and extrusion aid mixing and roll, become trifolium-shaped through extrusion, 3 hours, 550 ℃ roastings of 110 ℃ of dryings made carrier T-2 in 3 hours.
Comparative example 1
Use ammonium metawolframate 140g, nickelous nitrate 70g adds 120 milliliters of deionized waters, stirring and dissolving gets 200 milliliters of the W-Ni aqueous solution, adopts saturated this solution of pickling process single-steeping with above-mentioned carrier T-1 150g, and wet bar was through 110 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours make catalyst A.
Comparative example 2
Molybdenum oxide 100 grams, nickelous carbonate 40 grams, phosphoric acid 20 grams and 120 ml deionized water are mixed, be warming up to 95 ℃ of dissolvings 2 hours then, obtain the Mo-Ni-P co-impregnated solution, be diluted to 200 milliliters with deionized water, carrier T-1 after the 200 gram roastings floods under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours obtained catalyst B.
Comparative example 3
Molybdenum oxide 100 grams, cobaltous carbonate 40 grams, phosphoric acid 20 grams and 120 ml deionized water are mixed, be warming up to 95 ℃ of dissolvings 2 hours then, obtain the Mo-Co-P co-impregnated solution, be diluted to 200 milliliters with deionized water, carrier T-1 after the 200 gram roastings floods under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours made catalyzer C.
Comparative example 4
Ammonium metawolframate 95 grams, nickelous carbonate 41 grams, molybdenum oxide 38 grams, phosphoric acid 20 grams and 130 ml deionized water are mixed, and are warming up to 95 ℃ of dissolvings 3 hours then, obtain 200 milliliters of W-Mo-Ni-P co-impregnated solutions, carrier T-1 after the 200 gram roastings floods under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours made catalyzer D.
Embodiment 1
Ammonium metawolframate 60 grams, nickelous carbonate 21 grams, cobaltous carbonate 20 grams, molybdenum oxide 45 grams, phosphoric acid 20 grams and 130 ml deionized water are mixed, in 95 ℃ of dissolvings 3 hours, obtain 200 milliliters of W-Mo-Ni-Co-P co-impregnated solutions, the 200 carrier T-1s of gram after the roastings flooded under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours make catalyzer E.
Embodiment 2
Ammonium metawolframate 30 grams, nickelous carbonate 20 grams, cobaltous carbonate 20 grams, molybdenum oxide 85 grams, phosphoric acid 20 grams and 130 ml deionized water are mixed, be warming up to 95 ℃ of dissolvings 3 hours then, obtain 200 milliliters of W-Mo-Ni-Co-P co-impregnated solutions, the 200 carrier T-1s of gram after the roastings flooded under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours make catalyzer F.
Embodiment 3
Ammonium metawolframate 30 grams, nickelous carbonate 20 grams, cobaltous carbonate 20 grams, molybdenum oxide 85 grams, phosphoric acid 20 grams and 130 ml deionized water are mixed, be warming up to 95 ℃ of dissolvings 3 hours then, obtain 200 milliliters of W-Mo-Ni-Co-P co-impregnated solutions, the 200 carrier T-2s of gram after the roastings flooded under room temperature with above-mentioned steeping fluid, through 120 ℃ of dryings 3 hours, 500 ℃ of roastings 3 hours make catalyzer G.
The active facies analysis of representative electron-microscope scanning the results are shown in Table 1 behind several catalyst vulcanizations.As seen from Table 1, the active phase behind the catalyst vulcanization of the present invention increases owing to wafer is littler, has the higher active centre, edge of more activity, the reactive metal high dispersing.
With Middle East sulfur-bearing Medium diesel oil is raw material, is 6.0MPa at hydrogen pressure, hydrogen-oil ratio 350: 1, and air speed 2.5h-1, temperature of reaction is under 350 ℃ the condition, catalyzer of the present invention to be carried out activity rating, stock oil character and evaluation result see Table 2 and table 3 respectively.
Table 1 catalyst activity comparative evaluation result
| Catalyzer | A | B | C | D | E | F | G |
| The maximum length of lines, nm | 25.4 | 22.3 | 18.7 | 19.4 | 8.5 | 9.8 | 9.2 |
| The mean length of lines, nm | 15.2 | 14.5 | 12.2 | 12.4 | 3.5 | 4.8 | 4.5 |
| Maximum wafer numbers in the single buttress layer, sheet | 10 | 10 | 10 | 10 | 5 | 5 | 5 |
| Average wafer number in the single buttress layer, sheet | 4.8 | 4.6 | 4.1 | 4.3 | 1.6 | 2.3 | 2.2 |
Lines refer to: it (is WS that lines are being represented S-Mo-S or S-W-S
2Or MoS
2Wafer).
The buttress layer refers to: the buttress tile height that S-Mo-S or S-W-S wafer were piled up after the buttress layer referred to vulcanize.
Wafer refers to: wafer refers to vulcanize the shape that exists of back S-Mo-S or S-W-S.
The Iranian catalytic diesel oil character of table 2
| Density (20 ℃), g/cm 3 | 0.8597 |
| IBP/10％ | 195/246 |
| 30％/50％ | 274/295 |
| 70％/90％ | 320/352 |
| 95％/EBP | 367/369 |
| Sulphur content, m% | 1.65 |
| Nitrogen content, μ g/g | 172 |
Table 3 catalyst activity comparative evaluation result
| Catalyzer | WO 3 | MoO 3 | NiO | CoO | P 2O 5 | Specific surface area | Pore volume | The hydrogenating desulfurization relative reactivity | The product sulfur content, μ g/g |
| A | 28.2 | - | 4.1 | - | - | 230 | 0.37 | 100 | 965 |
| B | - | 24.5 | 4.2 | - | 3.5 | 235 | 0.38 | 115 | 799 |
| C | - | 24.7 | - | 4.0 | 3.0 | 238 | 0.38 | 135 | 650 |
| D | 18.5 | 10.8 | 4.6 | - | 3.2 | 221 | 0.35 | 130 | 680 |
| E | 15.8 | 12.0 | 2.8 | 3.5 | 3.3 | 217 | 0.36 | 180 | 445 |
| F | 5.8 | 19.8 | 2.7 | 3.1 | 3.2 | 213 | 0.35 | 172 | 465 |
| G | 5.9 | 19.6 | 2.8 | 2.9 | 3.1 | 215 | 0.36 | 175 | 472 |
The hydrogenating desulfurization relative reactivity is calculated as follows:
Desulphurizing activated relatively %=[1/ (S
p)
0.65-1/ (S
f)
0.65]/[1/ (S
Pr)
0.65-1/ (S
f)
0.65] * 100
Wherein: S
fBe stock oil sulphur content (percentage composition); S
PrSulphur content for reference agent hydrogenated oil; S
pSulphur content for the raw catalyst hydrogenated oil.
By table 2～table 3 as can be seen, be the catalyzer of the present invention of active ingredient preparation with W-Mo-Ni-Co, disperse better than the catalyst activity metal that with W-Ni, Mo-Ni, Mo-Co, W-Mo-Ni is the active ingredient preparation, thereby have higher hydrodesulfurization activity.
Claims (10)
1, a kind of catalyst for hydrodesulfurizationfraction fraction oil is a carrier with aluminum oxide or siliceous aluminum oxide, it is characterized in that with w, Mo, Ni, Co be active ingredient, and for helping catalyst component, in catalyst weight, each component concentration is respectively WO with P
35%～25%, MoO
35%～25%, NiO1%～5%, CoO1%～5%, P
2O
50.5%～9%.
2, according to the described catalyzer of claim 1, it is characterized in that 0.20～0.40 milliliter/gram of pore volume of described catalyzer, specific surface area is 110～270 meters
2/ gram.
3, according to the described catalyzer of claim 1, it is characterized in that described WO
3Content is 6%～16%, MoO
3Content is 8%～22%, and NiO content is 1%～3%, and CoO content is 1%～4%, P
2O
5Content is 1%～3%.
4,, it is characterized in that described active ingredient and help catalyst component to load on the support of the catalyst by saturated mode of soaking altogether once according to the described catalyzer of claim 1.
5, the described Preparation of catalysts method of a kind of claim 1, comprise following process: with aluminum oxide or siliceous aluminum oxide is carrier, is active ingredient with W-Mo-Ni-Co, adds the P auxiliary agent, make the W-Mo-Ni-Co-P co-impregnated solution, make stable co-impregnated solution through 70～120 ℃ of heating; With the mode impregnated carrier of saturated dipping once, moist catalysis was through 80～150 ℃ of dryings 2～8 hours with above-mentioned co-impregnated solution, and 350～550 ℃ of roastings made in 2～5 hours.
6, in accordance with the method for claim 5, the preparation that it is characterized in that described aluminum oxide or siliceous alumina supporter is that aluminum oxide is added peptizing agent and extrusion aid or silicon sol, mix and pinch the back extruded moulding or drip ball forming, made in 2～5 hours through 2～8 hours, 500～650 ℃ roastings of 80～150 ℃ of dryings.
7, in accordance with the method for claim 5, the compound method that it is characterized in that described W-Mo-Ni-Co-P co-impregnated solution is: tungsten compound, nickel compound, cobalt compound, molybdenum compound, phosphorus compound and deionized water are mixed simultaneously, stir after 70～120 ℃ of heating make stable co-impregnated solution.
8, in accordance with the method for claim 7, it is characterized in that described tungsten compound is one or more in ammonium metawolframate, wolframic acid or other tungstate, molybdenum compound is one or more in molybdic oxide or the ammonium molybdate; Nickel compound is a kind of in nickelous carbonate, nickelous nitrate and the nickel acetate; Cobalt compound is a kind of in cobaltous carbonate, Xiao Suangu and the Cobaltous diacetate; Phosphorus compound can be a kind of in phosphoric acid or the phosphorous acid.
9, in accordance with the method for claim 8, it is characterized in that each component concentrations is in the described co-impregnated solution: wO
3:/100 milliliters of 10～40 grams, NiO:2～10 restrain/100 milliliters, and CoO:2～10 restrain/100 milliliters, MoO
3:/100 milliliters of 5～40 grams, P
2O
5:/100 milliliters of 2～8 grams.
10, in accordance with the method for claim 5, it is characterized in that described dipping is saturated dipping at room temperature.
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