CN1362482A - Catalyst for hydrotreatment of petroleum hydrocarbon - Google Patents
Catalyst for hydrotreatment of petroleum hydrocarbon Download PDFInfo
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- CN1362482A CN1362482A CN 01106010 CN01106010A CN1362482A CN 1362482 A CN1362482 A CN 1362482A CN 01106010 CN01106010 CN 01106010 CN 01106010 A CN01106010 A CN 01106010A CN 1362482 A CN1362482 A CN 1362482A
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Abstract
The catalyst for hydrocarbon hydrogenation treatment (hydrogenation denitrification, hydrogenation desulfurization, hydrogenation demetalization and hydrogenation saturation) at least contains one kind of metal of family VIB, for example molybdenum or tungsten and one kind of metal of family VIII, for example nickel or cobalt as active component and contains pseudothin empholite and one kind of bifunctional compound containing metal element of family IIIB and non-metal element of family VIIB as carrier raw material. The high stability solution containing active component and carrier raw material are mixed together, kneaded and made into the form of bar, dried and roasted at high-temp. to obtain the invented hydrogenation treatment catalyst with higher activity.
Description
The present invention relates to a kind of hydrocarbon hydrogenizing treamtent catalyst and preparation method thereof.
Petroleum fractions especially contains sulphur, nitrogen, oxygen and metal impurity such as (as iron, nickel, vanadium) in the heavier petroleum fraction.The existence of these impurity not only influences its stability, in use also gives off a large amount of obnoxious flavour contaminate environment.Face hydrogen in petroleum fractions and handle in (catalytic reforming, hydrocracking, hydroisomerizing etc.) process, also may cause poisoning of catalyst.The main purpose that hydrocarbons hydrogenation is handled is the hazardous compound that removes in the raw material, for example organosulfur compound, organic nitrogen compound and organometallic compound etc.
The hydrocarbon hydrogenizing treamtent catalyst of excellent property requires to possess following condition: (1), at first reactive metal such as molybdenum (tungsten), nickel (cobalt) etc. have higher chemical individual layer dispersion amount on catalyst surface; (2), reactive metal has good dispersion state on catalyst surface; (3), " interaction between metal-carrier " intensity is wanted suitably in catalyst preparation process, make its " just right " by modulation.
In the prior art, about the preparation of hydrocarbon hydrogenizing treamtent catalyst, mainly be to adopt two-step approach.The first step is preparation carrier γ-Al earlier
2O
3Then second step, with the solution impregnating carrier that contains active ingredient, catalyzer is made in drying, roasting.Existing a large amount of patent disclosure preparation γ-Al
2O
3Method (USP4,513,097 and the clear 58-216740 of JP), then with γ-Al
2O
3Be carrier, by the immersion process for preparing hydrotreating catalyst (USP 4,317,746; 4,446,248; 4,568,449; 4,738,767).The advantage that adopts two-step approach to prepare catalyzer is: (1), prepare carrier separately and can guarantee that carrier (thereby also being catalyzer) has enough big aperture and surface properties preferably; (2), adopt the immersion process for preparing catalyzer, can be evenly dispersed on the carrier surface with fixed ratio height relatively between the active ingredient, thereby active ingredient has higher dispersity and good dispersion state on catalyst surface.But, adopt two-step approach to prepare catalyzer, each active ingredient loading is subjected to certain restriction, for example MoO
3Content only reaches 20w% usually, surpass 24w% then dispersity to descend.Except two-step approach, also has gel method (UPS 4,832,827).This method directly begins with the preparation alumina gel from aluminium salt, contains Mo-Ni-P solution, vacuum-drying again, extrusion, oven dry through aging, washing, vacuum-drying, adding, after catalyzer is made in roasting.The advantage of this method is that preparation carrier and two steps of catalyzer are integrated, and specific surface area of catalyst is bigger.The shortcoming of this method is: the loading of (1), catalyst activity component (metal) still is restricted, even is lower than the catalyzer with the two-step approach preparation; (2), prepared catalyzer aperture is too little.Hole less than 7.0nm accounts for more than 80% of whole pore volume, even surpasses 90%, is unfavorable for the diffusion and the reaction of macromolecule hydrocarbon compound (as heavy distillate) molecule.
The objective of the invention is: even kneading method of one step of (1), employing, directly prepare hydrocarbon hydrogenizing treamtent catalyst by intending thin water aluminum oxide, thereby simplify the Catalyst Production process, reduce production costs; (2), increase the catalyst activity component concentration with further raising catalyst activity; (3), in catalyst preparation process, contain the dual-function compound of IIIB family metal and VIIB family non-metallic element by interpolation, improve the carrier surface character step of going forward side by side and become interaction between metal-carrier, thereby further improve catalyst activity.
The present invention adopts even kneading method of a step, is about to prepare the preparation method of the hydrocarbon hydrogenizing treamtent catalyst that carrier and two steps of preparation catalyzer integrate.To intend thin water aluminum oxide and to contain IIIB family metallic element and the dual-function compound of VIIB family non-metallic element is a raw material, with metallic solution, through mixing, kneading, extruded moulding, drying, roasting then, thus " a step ground " finishes the method for whole hydrotreating catalyst preparation process.
To achieve these goals, the present invention includes two aspects: Mo-Ni (the Co)-P solution of (1), preparation high stability, high density; (2), with this solution with intend thin water aluminum oxide and contain IIIB family metal (boron or gallium) and VIIB family non-metallic element (fluorine) the dual-function compound thorough mixing, be kneaded into plastic shape, be extruded into the trifolium strip, adopt " three sections constant temperature calcinings " program then, control suitable heat-up rate and each section maturing temperature to guarantee that active ingredient has higher dispersity and good dispersion state on catalyst surface, guarantee that simultaneously catalyzer has enough big specific surface area, suitable aperture and good pore structure.
The dual-function compound of the said IIIB of containing family's metallic element and VIIB family non-metallic element is BF
3, or HBF
4GaF
3Or GaF
33H
2O.
The solution of the said high metal concentration of the present invention is Mo-Ni (Co)-P solution, and its preparation process is as follows:
(1), phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and is heated to molybdenum oxide all dissolving or basic dissolving.
(2), above-mentioned solution is cooled to 60 ℃～70 ℃ after, slowly add basic nickel carbonate or nickelous nitrate (and/or Xiao Suangu), place and be warming up to little boiling again after 15 minutes, be heated to the basic dissolving of precipitation.Reduce to the room temperature after-filtration to remove insoluble impurity.
(3), with above-mentioned solution concentration to needed concentration.
Prepared Mo-Ni (Co)-P solution according to the present invention has following character:
(1), every 100ml solution can contain MoO
350～80g, NiO 10～20g, CoO 0～15g, P/MoO
3Weight ratio is 0.08～0.20.
(2), other composition can be added as required in solution, as silicon sol, tartrate, materials such as oxalic acid or citric acid.
(3), this solution at room temperature can be stablized the endless time (more than at least 6 years) and not produce muddiness or precipitation.
Hydrocarbon hydrogenizing treamtent catalyst preparation process of the present invention is as follows:
(1), with the thin water aluminum oxide (powder) of Mo-Ni (Co)-P solution and plan and dual-function compound such as BF
3Or HBF
4GaF
3Or GaF
33H
2Thorough mixing such as O, kneading are extruded into strip or trifolium strip then to becoming plastic shape.Dry in the air, dry down at 110 ℃～130 ℃ then.
(2), dry sample is placed High Temperature Furnaces Heating Apparatus, the speed with 2 ℃～5 ℃/minute in air is warming up to 238 ℃～371 ℃, constant temperature calcining 0.5 hour～2 hours.Then, be warming up to 398 ℃～450 ℃, constant temperature calcining 2 hours～5 hours with 2 ℃～5 ℃/minute speed.Be warming up to 471 ℃～560 ℃, constant temperature calcining 1 hour～4 hours with 2 ℃～5 ℃/minute speed again.
Prepared hydrocarbon hydrogenizing treamtent catalyst has following character according to the present invention:
(1), this catalyzer consists of MoO
324w%～40w%, NiO and/or CoO 4.0w%～12w%, P 2.0w%～5.0w%, B 1.0 w%～3.0 or Ga 5.0w%～10.0w%, F 4.0w%～7.0w%.All the other are Al
2O
3
(2), specific surface area is 160～300m
2/ g; Pore volume is 0.25～0.38ml/g.
(3), active ingredient Mo-Ni (Co)-P has higher dispersity and preferable dispersion state on catalyst surface, and allow bigger dispersion amount, thereby the hydrotreatment activity is higher.
Advantage of the present invention is:
(1), adopt the present invention to prepare hydrocarbon hydrogenizing treamtent catalyst, simple to operate, easy row.
(2), catalyzer of the present invention is suitable for the hydrofining (hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated, hydrodemetallation (HDM) etc.) of heavy (as VGO) and low-density oil cut.The processing condition that catalyzer is suitable for are: temperature of reaction is 230 ℃～420 ℃; Reaction pressure 5.0MPa～15.0MPa; LHSV 0.5h
-1～3.0h
-1Hydrogen/oil volume ratio is 100～1500.
(3), Mo of the present invention, Ni (Co)-P solution, even under very high metal concentration also quite stable.At room temperature can stablize the endless time (more than at least 6 years) does not produce muddiness or precipitation.
(4), catalyzer of the present invention, the anti-nitrogen performance of its hydrogenation reaction activity and catalyzer all is better than the catalyzer that makes with usual way.
In order to further specify all main points of the present invention, enumerate following examples and comparative example.
Embodiment 1
(1), the preparation of Mo-Ni-P solution
With 30.0ml phosphoric acid H
3PO
4(85%) is dissolved in the 780ml water.Under agitation solution is joined 140g molybdenum oxide MoO
3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add 100g nitric acid nickel (NO
3)
26H
2O, heating up is heated to throw out and dissolves substantially again.With the filtrate evaporation concentration to 330ml.
(2), Preparation of Catalyst
450g is intended thin water aluminum oxide, 42g BF
3Mo-Ni-P solution thorough mixing, kneading twice with top step (1) preparation add 133ml HNO
3(3%) solution is mediated two times again, makes to be extruded into trifolium strip (φ=1.2mm) behind the plastic.After moist catalysis dried in air and spends the night, drying was 3 hours under 120 ℃.The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 270 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 3 ℃ of/minute speed again, constant temperature 3 hours.Be warming up to 500 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Embodiment 2
(1) step of Mo-Ni-P formulations prepared from solutions is identical with embodiment 1 (1).Phosphoric acid H
3PO
4(85%) and the add-on of water be respectively 30.0ml and 980ml.Molybdenum oxide MoO
3With nitric acid nickel (NO
3)
26H
2The O add-on is respectively 180g and 129g.The filtrate evaporation concentration is to 330ml.
(2) Preparation of Catalyst
450g is intended thin aluminum oxide and 42g BF
3With Mo-Ni-P solution thorough mixing, the kneading of top (1), add 133ml HNO
3(3%) solution is mediated two times again, makes to be extruded into trifolium strip (φ=1.2mm) behind the plastic.After moist catalysis dried in air and spends the night, drying was 3 hours under 120 ℃.
The dry sample of crossing places High Temperature Furnaces Heating Apparatus, is warming up to 270 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 3 ℃ of/minute speed again, constant temperature 3 hours.Be warming up to 500 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Embodiment 3
(1), the preparation of Mo-Ni-P solution
With embodiment 2 steps (1).
(2), Preparation of Catalyst
Preparation of Catalyst is identical with embodiment 2 steps (2).But do not add 42g BF
3, change into and add GaF
3GaF
3Add-on is 57g.HNO
3(3%) the solution add-on is 138ml.
Comparative example 1
(1) preparation of Mo-Ni-P solution
With 20.0ml phosphoric acid H
3PO
4(85%) is dissolved in the 520ml water.Under agitation solution is joined 93g molybdenum oxide MoO
3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add 67g nitric acid nickel (NO
3)
26H
2O, heating up is heated to throw out and dissolves substantially again.With the filtrate evaporation concentration to 220ml.
(2) Preparation of Catalyst
Mo-Ni-P solution thorough mixing, kneading twice with thin water aluminum oxide of 330g plan and top step (1) preparation add 88ml HNO
3(3%) solution is mediated two times again, makes to be extruded into trifolium strip (φ=1.2mm) behind the plastic.After moist catalysis dried in air and spends the night, drying was 3 hours under 120 ℃.The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 270 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 410 ℃ with 3 ℃ of/minute speed again, constant temperature 3 hours.Be warming up to 520 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 2 hours.
Comparative example 2
(1) preparing carriers
Take by weighing and intend thin water aluminum oxide 200g, add the 2.9ml Glacial acetic acid, 179ml HNO
3(concentration is 3%) and an amount of water.Through thorough mixing, be kneaded into plastic shape after, be extruded into trifolium strip (φ=1.2mm).After moist catalysis dried in air and spends the night, drying was 3 hours under 110 ℃.
The catalyzer that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 220 ℃ with 8 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 478 ℃ with 9 ℃ of/minute speed again, constant temperature 2.5 hours.Be warming up to 640 ℃ with 8 ℃ of/minute speed at last, constant temperature calcining 3 hours.
(2) preparation of Mo-Ni (Co)-P solution
With 18.5ml phosphoric acid H
3PO
4(85%) is dissolved in the 560ml water.Under agitation solution is joined 97g molybdenum oxide MoO
3In, be warming up to and littlely boil and heat 3 hours to the most of dissolving of molybdenum oxide.Be cooled to 65 ℃, under agitation slowly add the 48g basic nickel carbonate, be warming up to again little boil and be heated to throw out dissolve substantially.Filtrate is concentrated into 200ml.
(3) Preparation of Catalyst
Take by weighing the γ-Al of step (1) preparation
2O
3Carrier 100g adds the Mo-Ni-P solution of 150ml according to step (2) preparation, at room temperature flood 4 hours after, leach redundant solution.After moist catalysis dries in air and spends the night, dried 3 hours down at 110 ℃.
The dry catalyst sample of crossing is warming up to 190 ℃ with 3 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 368 ℃ with 3 ℃ of/minute speed again, constant temperature calcining 0.5 hour.Be warming up to 470 ℃ with 3 ℃ of/minute speed at last, constant temperature calcining 3 hours.
More than each routine prepared γ-Al
2O
3See Table 1 with the physico-chemical property of catalyzer.Raw materials used oil properties of evaluation of catalyst activity and reaction process condition see Table 2 and table 3.
Estimate catalyst system therefor and use the aviation kerosene cut that contains dithiocarbonic anhydride 1.5% (V) respectively at 230 ℃, 260 ℃, 300 ℃ and 370 ℃ were vulcanized 6 hours down.Sulfuration finishes, and swap-in stock oil is stablized under reaction conditions and begun to carry out the hydrodenitrification reaction test after 8 hours.When estimating each routine catalyzer, by the conditioned reaction temperature, making total denitrification percent is 95w%, i.e. it is 0.0075w% that control generates the nitrogen content in the oil.If catalyzer just can reach this denitrification percent than low reaction temperatures the time, show that this catalyzer has higher hydrodenitrification reactive behavior.Vice versa.
Evaluation result shows: adopt the prepared hydrotreating catalyst of the present invention to have higher hydrodenitrification reactive behavior (embodiment 1).If in the dual-function compound of introducing boracic or gallium and fluorine, increase reactive metal (molybdenum, nickel) content, the hydrodenitrification reactive behavior will be higher (embodiment 2, embodiment 3).
This shows, adopt the present invention to prepare hydrotreating catalyst, not only simple to operate, and also catalytic activity can be higher.
The physico-chemical property of each routine carrier of table 1 and catalyzer
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | ||
| Catalyzer | Catalyzer | Catalyzer | Catalyzer | γ-Al 2O 3 | Catalyzer | |
| Specific surface m 2/g | ??231 | ??197 | ??191 | ??233 | ??295 | ??145 |
| Pore volume ml/g | ??0.310 | ??0.283 | ??0.286 | ??0.321 | ??0.630 | ??0.303 |
| Chemical constitution, w% | ||||||
| ????MoO 3 | ??24.3 | ??32.5 | ??32.6 | ??24.5 | ??--- | ??24.3 |
| ????NiO | ??4.35 | ??5.62 | ??5.58 | ??4.39 | ??--- | ??4.38 |
| ????P | ??2.63 | ??2.61 | ??2.65 | ??2.65 | ??--- | ??2.64 |
| ????B | ??1.50 | ??1.52 | ??--- | ??--- | ??--- | ??--- |
| ????Ga | ??--- | ??--- | ??6.97 | |||
| ????F | ??7.83 | ??7.78 | ??5.70 | |||
| ????Al 2O 3 | Surplus | Surplus | Surplus | Surplus | Surplus | |
| Bulk density g/100ml | ??90.2 | ??94.2 | ??94.9 | ??90.1 | ??62.3 | ??90.9 |
Table 2 stock oil character
| Stock oil | Triumph VGO |
| Proportion d 4 20，g/ml | ????0.902 |
| Sulphur, w% | ????0.53 |
| Nitrogen, w% | ????0.15 |
| Zero pour, ℃ | ????36.2 |
| Carbon residue, w% | ????0.06 |
| Boiling range, ℃ | |
| ????IBP/10％ | ????292/352 |
| ????30％/50％ | ????378/395 |
| ????70％/90％ | ????410/441 |
| ????95％/EBP | ????450/469 |
Table 3 hydrodenitrification reaction process condition
| Reaction pressure, MPa | ????6.00 |
| ????LHSV，h -1 | ????1.00 |
| Hydrogen/oil ratio, v/v | ????1000∶1 |
Each routine catalyst hydrogenation denitrification activity of table 4 relatively
| Catalyzer | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Temperature of reaction, ℃ | ??378 | ??373 | ??373 | ??384 | ??384 |
Claims (9)
1. preparation method of hydrotreatment catalyst, it is characterized in that to intend thin water aluminum oxide and to contain IIIB family metallic element and the dual-function compound of VIIB family non-metallic element is a raw material, with metallic solution, through mixing, kneading, extruded moulding, drying, roasting then, thus ＂ one step ground ＂ finishes the preparation process of hydrotreating catalyst.
2. preparation method according to claim 1 is characterized in that the dual-function compound of the said IIIB of containing family's metallic element and VIIB family non-metallic element is BF
3Or HBF
4GaF
3Or GaF
33H
2O.
3. preparation method according to claim 1 is characterized in that said metallic solution is Mo, Ni and/or Co, P solution.
4. preparation method according to claim 3 is characterized in that consisting of of said Mo, Ni and/or Co, P solution: every 100ml solution contains MoO
350～80g, NiO 10～20g, CoO 0～15g, wherein P/MoO
3Weight ratio is 0.08～0.20.
5. according to claim 3 or 4 described preparation methods, it is characterized in that the preparation process of said Mo, Ni and/or Co, P solution is as follows:
(1), phosphate aqueous solution is added in the molybdenum oxide, stir, slowly heat temperature raising is to little boiling, and is heated to molybdenum oxide all dissolving or basic dissolving;
(2), above-mentioned solution is cooled to 60 ℃～70 ℃ after, slowly add basic nickel carbonate or nickelous nitrate and/or Xiao Suangu, place and be warming up to little boiling again after 15 minutes, be heated to the basic dissolving of precipitation, reduce to the room temperature after-filtration to remove insoluble impurity;
(3), with above-mentioned solution concentration to needed concentration.
6. preparation method according to claim 1 is characterized in that said roasting process is: dry sample is placed High Temperature Furnaces Heating Apparatus, and the speed with 2 ℃～5 ℃/minute in air is warming up to 238 ℃～371 ℃, constant temperature calcining 0.5 hour～2 hours; Then, be warming up to 398 ℃～450 ℃, constant temperature calcining 2 hours～5 hours with 2 ℃～5 ℃/minute speed; Be warming up to 471 ℃～560 ℃, constant temperature calcining 1 hour～4 hours with 2 ℃～5 ℃/minute speed again.
7. a Mo-Ni and/or Co-P/F-B or Ga-Al
2O
3Hydrotreating catalyst is characterized in that the MoO that consists of of this catalyzer
324w%～40w%, NiO and/or CoO 4.0w%～12w%, P 2.0w%～5.0w%, B 1.0w%～3.0 or Ga 5.0w%～10.0w%, F 4.0w%～7.0w%, all the other are Al
2O
3
8. hydrotreating catalyst according to claim 7, the specific surface area that it is characterized in that catalyzer is 160～300m
2/ g; Pore volume is 0.25～0.38ml/g.
9. the application of the said hydrotreating catalyst of the present invention in the petroleum fractions unifining process, its processing condition are: 230 ℃～420 ℃ of temperature of reaction; Reaction pressure 5.0MPa～15.0MPa; LHSV 0.5h
-1～3.0h
-1Hydrogen/oil volume ratio is 100～1500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01106010 CN1132905C (en) | 2001-01-05 | 2001-01-05 | Catalyst for hydrotreatment of petroleum hydrocarbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01106010 CN1132905C (en) | 2001-01-05 | 2001-01-05 | Catalyst for hydrotreatment of petroleum hydrocarbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1362482A true CN1362482A (en) | 2002-08-07 |
| CN1132905C CN1132905C (en) | 2003-12-31 |
Family
ID=4655068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01106010 Expired - Lifetime CN1132905C (en) | 2001-01-05 | 2001-01-05 | Catalyst for hydrotreatment of petroleum hydrocarbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1132905C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733119B (en) * | 2008-11-25 | 2012-12-05 | 中科合成油技术有限公司 | Catalyst for hydrogenation of Fischer-Tropsch synthesis oil, preparation method as well as application thereof |
| CN102836736A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method for vulcanization type hydrogenation catalyst |
-
2001
- 2001-01-05 CN CN 01106010 patent/CN1132905C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733119B (en) * | 2008-11-25 | 2012-12-05 | 中科合成油技术有限公司 | Catalyst for hydrogenation of Fischer-Tropsch synthesis oil, preparation method as well as application thereof |
| CN102836736A (en) * | 2011-06-23 | 2012-12-26 | 中国石油化工股份有限公司 | Preparation method for vulcanization type hydrogenation catalyst |
| CN102836736B (en) * | 2011-06-23 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of preparation method of sulfurized hydrogenation catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1132905C (en) | 2003-12-31 |
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