CN1552815A - Petroleum fraction hydrofining catalyst and preparing method thereof - Google Patents
Petroleum fraction hydrofining catalyst and preparing method thereof Download PDFInfo
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Abstract
A catalyst for petroleum fractions hydrogenation and its preparation are disclosed. It includes preparing silicon binder, fully mixing pseudooligaaqueous aluminum oxide, fluo-compound and compound containing VIB family metals such as molybdenum or tungsten with silicon binder, kneading, stripping, shaping, drying, and high temperature roasting to form Mo(W)/F-SiO2-Al2O3 as carrier, immersing in an aqueous phosphoric acid solution containing VIIIB family metals such as nickel or cobalt, drying and high temperature roasting to obtain the catalyst of petroleum fractions hydrogenation. Its advantages include simple preparation, easy operation, low cost, good active ingredient dispersing status, large specific area and pore volume.
Description
Technical field
The present invention relates to a kind of petroleum fractions Hydrobon Catalyst And Its Preparation Method, the high metal content Hydrobon Catalyst And Its Preparation Method that particularly a kind of specific surface area and pore volume are bigger.
Background technology
Contain hazardous compounds such as organosulfur compound, organic nitrogen compound and organo-metallic (as Ni-V-Fe) compound in the petroleum fractions, the existence of these compounds not only influences the stability in storage of oil product, in use also because of giving off deleterious sulphur, nitrogen, oxide gas contaminate environment, in some petroleum fractions courses of processing, also may cause poisoning of catalyst.Hydrorefined main purpose is these hazardous compounds that remove in the petroleum fractions.Mo (W)-Ni (Co)-Al
2O
3Catalyzer is widely used in the petroleum fractions unifining process.
The Hydrobon catalyst of an excellent property requires to possess following condition: a., and at first active metal component such as molybdenum (tungsten), nickel (cobalt) etc. will have higher chemical dispersion amount (cda) on catalyst surface; B. reactive metal will have high dispersity and good dispersion state on catalyst surface, i.e. each component (molybdenum or tungsten) and nickel or cobalt) between distribution want evenly, " interaction between metal-carrier " intensity is wanted suitably; C. (for example the hydrodenitrification reaction of nitrogenous aromatic compound etc.) is proceed step by step because some unifining process: at first be the aromatic nucleus hydrogenation is saturated, and open loop and remove heteroatoms then, back one step requires catalyzer to have certain acidity.So need in catalyzer, introduce some auxiliary agents, to strengthen the acidity of catalyst surface; D. catalyzer (carrier) will have higher specific surface area, so that the absorption of reactant molecule and desorb.In addition, from considering that economically the Preparation of catalysts process should be tried one's best simply.
The preparation method of Hydrobon catalyst mainly contains kneading method and pickling process.Pickling process is the method that usually adopts, and as USP6, institutes such as 306,289, USP4,513,097 are introduced, and process mainly was divided into for two steps: at first prepare carrier γ-Al
2O
3, with this carrier of solution impregnation that contains two or more active ingredient, catalyzer is made in drying, roasting at last then.The main deficiency of pickling process is that each active ingredient loading is subjected to certain restriction, as the higher (MoO for example of active component content
3+ NiO＞24wt% or higher) time, not only the specific surface area of catalyzer and pore volume obviously diminish, and on catalyst surface, dispersion degree of active components also can reduce, and these all can have influence on the performance of catalyst activity.In addition, when the catalyzer of preparation high-activity component content, also need to prepare the dipping solution (for example Mo-Ni-P) of corresponding high density, and when the dipping solution concentration ratio is higher, its stability is variation also, simultaneously, the viscosity of high density dipping solution is too big, has brought very big difficulty for dipping and filtration procedure.
Kneading method is support material, containing metal compound to be added with binding liquid be in the same place, and through steps such as mixing, kneading, moulding, drying and roastings, makes catalyzer.The advantage that adopts kneading method to prepare catalyzer is that process is simple, but catalyst activity is relatively low.The researchist who has think this be since metal dispersity relatively poor due to.Nearest result of study shows: adopt kneading method to prepare catalyzer, owing to interact between metal and the carrier in the preparation process, making reactive metal can be high dispersing in its surface, but its dispersion state (dispersed uniform between each metal component) is relatively poor.Mo (W)-Ni (Co)/Al for example
2O
3Mix and to pinch the type catalyzer, under transmission electron microscope, can observe: catalyzer some " microcell " (with 1,000nm
2Be a microcell), molybdenum (or tungsten) is more concentrated, and at other " microcell ", then is that nickel (or cobalt) is more concentrated.This is considered to influence the important factor that kneading method prepares catalyst activity.CN1098433A has introduced a kind of employing and mix-has soaked the bonded method and prepare Hydrobon catalyst, with a water aluminum oxide (intend thin water aluminum oxide) mix with required whole nickel compound containings and required part molybdate compound, moulding, pass through the pickling process molybdenum of the required surplus of load more then.This method does not solve the problem of the catalyst activity metal dispersion state difference of kneading method preparation yet.
In order to improve the performance of catalyzer, need to use various auxiliary agents, as P, Si, F, B, Zr etc.But the difference of auxiliary agent adds mode, and catalyst performance is had bigger influence.The adding mode of auxiliary agent Si is mainly in the carrier moulding process silicon sol and the thin water aluminum oxide of plan is mixed together modes such as adding in the prior art.US4758338, EP0788270 etc. have introduced the preparation method of amorphous silicon aluminium, but silicone content height, the acidity of amorphous silicon aluminium are stronger, are not suitable for Hydrobon catalyst.CN1110304A has announced a kind of preparation method of aluminum oxide of siliceous and phosphorus of macropore, in the preparation process of this aluminum oxide, silicon becomes the glue method to add with phosphorus with substep, this procedure complexity, the production cost height, and the add-on of silicon is limited, is generally about 1wt%～4wt%, and is limited to the regulating effect of catalyst performance.CN1321726A introduces a kind of hydrotreating catalyst and preparation method thereof, adds silicon sol in a water-aluminum hydroxide (intending thin water aluminum oxide) kneading process, but because silicon sol is the bigger material of micelle, is difficult for being uniformly dispersed, and its effect can not be given full play to.
Summary of the invention
At the deficiencies in the prior art, the invention provides the preparation method of the Hydrobon catalyst that a kind of preparation process is simple, production cost is low, performance is good.Simultaneously, the invention provides a kind of by the inventive method preparation active metal component and the auxiliary agent dispersion state is good, specific surface area and big, the active high Hydrobon catalyst of pore volume.
Petroleum fractions Hydrobon catalyst preparation process of the present invention is as follows:
(1). prepare siliceous binding agent;
(2). with aluminum oxide precursor, fluorochemicals, contain the compound of molybdenum or tungsten, (1) made binding agent above adding through moulding, drying, roasting, is made the fluoro-silicon-aluminum oxide that contains molybdenum or tungsten;
(3). with nickeliferous or the molybdenum that cobalt phosphate aqueous solution impregnation steps (2) obtains or the fluoro-silicon-aluminum oxide of tungsten, Mo (W) Ni (Co) P/F-SiO is made in drying and roasting
2-Al
2O
3Hydrobon catalyst.
Final catalyzer has following composition and character:
Catalyzer is formed in weight and is comprised MoO
3Or WO
323%～40%, NiO or CoO 5.0%～12%, P1.5%～4.0%, SiO
24.0%～10%, F2.0%～10.0%, Al
2O
330%～60%.The specific surface area of catalyzer is 230～330m
2/ g, pore volume are 0.33～0.42ml/g.
Method for preparing catalyst of the present invention is incorporated into the active ingredient molybdenum of main (also being maximum) of hydrotreating catalyst or tungsten and auxiliary agent in the carrier by " kneading method ", then, floods this carrier with the phosphate aqueous solution of nickel or cobalt, promptly makes catalyzer.In a first step, owing in preparation process, can interact between metal-carrier, make even under the situation of high molybdenum or high W content, can reach the ideal dispersity equally by molybdenum or tungsten meeting homodisperse on carrier surface itself.Second step adopts nickeliferous or cobalt phosphate aqueous solution dipping to contain the carrier of molybdenum or tungsten, can guarantee that reactive metal disperses more evenly each other, promptly has good dispersion state.In addition, preparation VIIIB family contains the phosphate aqueous solution of Ni or Co, and than Mo (W)-Ni (Co-P) solution of preparation high density and full-bodied two-pack, process is much quick, easy.Ni (Co)-the P soltion viscosity is also little, can not bring any inconvenience to steeping process.Simultaneously, because silicon-containing compound is to add in the preparation adhesive process, can guarantee silicon be present in the carrier body mutually among (with aluminium in conjunction with generating Si-Al mutually), thereby make the carrier that makes that higher specific surface area and bigger pore volume not only be arranged, also have the carrying out that suitable acidity is beneficial to hydrofining reaction (for example HDN etc.).Again owing to add fluorochemicals in preparation (mix pinch) process, further modulation the interaction between metal-carrier, the hydrogenation activity of catalyzer is further improved.The inventive method row simple to operate, easy makes that the catalyst metal dispersion state is good, specific surface area and pore volume be big, acid suitable, and its hydrofining reaction activity is better than the catalyzer that existing method makes.
Embodiment
Petroleum fractions Hydrobon catalyst preparation process of the present invention is specific as follows:
(1). at first will intend thin water aluminum oxide, silicon-containing compound and 2%～4%HNO
3The aqueous solution is mixed together and places certain hour, makes gelatinous binding agent; Wherein in aluminum oxide and silicon oxide, part by weight is: 96w%～98w%: 4w%～2w%.
(2). the compound that will intend thin water aluminum oxide, fluorochemicals, contains molybdenum or tungsten mixes together, and (1) made binding agent above adding through thorough mixing, kneading, extruded moulding, again through super-dry and roasting, is made the fluoro-silicon-aluminum oxide that contains molybdenum or tungsten;
(3). the phosphate aqueous solution of preparation nickel or cobalt;
(4). with the nickel or the saturated dipping of cobalt phosphate aqueous solution of step (3) preparation or spray the fluoro-silicon-alumina supporter that contains molybdenum or tungsten, Mo (W) Ni (Co) P/F-SiO is made in drying and roasting
2-Al
2O
3Hydrobon catalyst.
Various materials can be determined the add-on of raw material by the composition of final catalyst prod.
Said silicon-containing compound silicon sol preferably in the step (1) wherein.
Fluorochemicals in the step (2) is AlF preferably
3, (NH
4)
2SiF
6Or BF
3The compound of molybdenum is preferably molybdenum oxide or ammonium molybdate; The compound of tungsten is preferably ammonium metawolframate.
The phosphate aqueous solution of preparation nickel or cobalt can directly be prepared according to concentration requirement in the step (3), nickelous nitrate or basic nickel carbonate or Xiao Suangu or cobaltous dihydroxycarbonate are dissolved in the water of phosphoric acid, consisting of of Ni or Co solution: every 100ml solution contains NiO or CoO 4～12g, contains P2～5g.
Drying in the preparation process and roasting can be adopted method and condition conventional in this area.Wherein the roasting of carrier preferred below condition: the speed with 3 ℃～5 ℃/minute in air is warming up to 300 ℃～380 ℃, constant temperature calcining 0.5 hour～2 hours; Then, be warming up to 400 ℃～500 ℃, constant temperature calcining 2 hours～5 hours with 3 ℃～5 ℃/minute speed.The roasting condition of catalyzer is preferably: the speed with 3 ℃～5 ℃/minute in air was warming up to 200 ℃～260 ℃ constant temperature calcinings 0.5 hour～2 hours; Then, be warming up to 300 ℃～430 ℃, constant temperature calcining 2 hours～5 hours with 3 ℃～5 ℃/minute speed.
Catalyzer of the present invention is suitable for the hydrofining (hydrogenating desulfurization, hydrodenitrification, hydrogenation are saturated, hydrodemetallation (HDM) etc.) of various petroleum fractionss such as heavy (VGO, paraffin, Vaseline etc.) 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, LHSV0.5h
-1～3.0h
-1Hydrogen/oil volume ratio is 300～2000 (V/V).
Further specify the solution of the present invention and effect below by embodiment.
Embodiment 1
(1). contain fluoro-silicon-aluminum oxide (Mo/F-SiO of molybdenum
2-Al
2O
3) preparation
(a). adhesive preparation: 55g is intended thin water aluminum oxide, and the 800g silicon sol (contains 30wt%SiO
2), with 110ml 3%HNO
3Solution mixes, and after stirring, places 6 hours;
(b). contain the fluoro-silicon-aluminum oxide preparation of molybdenum: 370g is intended thin water aluminum oxide, 92g MoO
3, 38g AlF
3, 430ml 3%HNO
3Solution is mixed together, and adds (a) prepared binding agent, thorough mixing, is kneaded into plastic shape, is extruded into trifolium strip (φ=1.4mm).After wet bar 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 330 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 430 ℃ with 3 ℃ of/minute speed again, constant temperature 3 hours.
(2), the preparation of nickeliferous-phosphorus solution
With 100gNi (NO
3)
26H
2O is dissolved in the 470ml water, adds 33ml H
3PO
4(85wt%), stir.
(3), Preparation of Catalyst
Fluoro-silicon-the aluminum oxide that 100g is contained molybdenum places the 250ml beaker, add 90ml nickeliferous-phosphorus solution.Stir for several times at interval, moist catalysis dries in air and spends the night, and then, drying is 3 hours under 120 ℃.The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 230 ℃ with 3 ℃ of/minute speed, constant temperature 1 hour.Be warming up to 390 ℃ with 3 ℃ of/minute speed again, constant temperature 2 hours.
Embodiment 2
(1), the fluoro-silicon-aluminum oxide (Mo/F-SiO that contains molybdenum
2-Al
2O
3) preparation
(a). adhesive preparation: identical with embodiment 1 (1-a);
(b). contain the fluoro-silicon-aluminum oxide preparation of molybdenum: identical with embodiment 1 (1-b).But MoO
3Add-on change 105g into;
(2), the preparation of solution containing nickel
With 120gNi (NO
3)
26H
2O is dissolved in the 470ml water, adds 35ml H
3PO
4(85%), stirs.
(3), Preparation of Catalyst
Identical with embodiment 1 (3).
Embodiment 3
(1). contain fluoro-silicon-aluminum oxide (Mo/F-SiO of molybdenum
2-Al
2O
3) preparation
(a). adhesive preparation: identical with embodiment 1 (1-a);
(b). contain the fluoro-silicon-aluminum oxide preparation of molybdenum: 370g is intended thin water aluminum oxide, 92g MoO
3, 38g AlF
3, 430ml 3%HNO
3Solution is mixed together, and adds (a) prepared binding agent, thorough mixing, is kneaded into plastic shape, is extruded into trifolium strip (φ=1.4mm).After wet bar 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 330 ℃ with 3 ℃ of/minute speed, and constant temperature 1 is little
(2), the preparation of nickeliferous-phosphorus solution
With 100gNi (NO
3)
26H
2O is dissolved in the 470ml water, adds 33ml H
3PO
4(85wt%), stir.
(3), Preparation of Catalyst
Identical with embodiment 1 (3).
Comparative example 1
(1), the fluoro-silicon-aluminum oxide (Mo/F-SiO that contains molybdenum
2-Al
2O
3) preparation
The 425g macropore is intended thin water aluminum oxide, 92gMoO
3, 48gAlF
3, the 80g silicon sol (contains 30wt%SiO
2) and 540ml 3%HNO
3Solution is mixed together, and is kneaded into plastic shape, is extruded into trifolium strip (φ=1.4mm).All the other steps are identical with embodiment 1 (b).
(2), the preparation of nickeliferous-phosphorus solution
Identical with embodiment 1 (2).
(3), Preparation of Catalyst
Identical with embodiment 1 (3).
Comparative example 2
(1) preparing carriers
Take by weighing and intend thin water aluminum oxide 200g, silicon sol 38g (contains 30wt%SiO
2), add 138ml 3%HNO
3With an amount of water.Through thorough mixing, be kneaded into plastic shape after, be extruded into trifolium strip (φ=1.4mm).After wet bar dried in air and spends the night, drying was 3 hours under 110 ℃.
The sample that drying is crossed places High Temperature Furnaces Heating Apparatus, is warming up to 220 ℃ with 5 ℃ of/minute speed, constant temperature calcining 0.5 hour.Be warming up to 478 ℃ with 4 ℃ of/minute speed again, constant temperature calcining 2.5 hours.Be warming up to 640 ℃ with 5 ℃ of/minute speed at last, constant temperature calcining 3 hours.
(2) preparation of Mo-Ni-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 150m 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 the physico-chemical property of each routine catalyzer see Table 1.
The physico-chemical property of each routine catalyzer of table 1
| Embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 |
| Specific surface, m 2/g | ??265 | ??250 | ??231 | ??242 | ??152 |
| Pore volume, ml/g | ??0.380 | ??0.365 | ??0.330 | ??0.360 | ??0.271 |
| Chemical constitution, wt% MoO 3????NiO ????SiO 2????P ????F ????Al 2O 3 | 24.7 4.60 5.5 2.69 4.63 surpluses | 26.2 5.10 5.4 2.68 4.62 surpluses | 28.0 5.52 5.4 2.80 4.62 surpluses | 24.8 4.61 5.5 2.69 4.62 surpluses | 24.8 4.62 5.4 2.70---surplus |
Raw materials used oil properties of evaluation of catalyst activity and reaction process condition see Table 2 and table 3.
Estimate catalyst system therefor with containing CS
2The aviation kerosene cut of 1.5% (V), under 230 ℃, 260 ℃, 300 ℃ and 370 ℃, the constant temperature sulfuration is 6 hours respectively.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 95wt%, i.e. it is 0.0077wt% 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.
Table 2 stock oil character
| Stock oil | Triumph VGO |
| Proportion d 4 20，g/ml | ????0.901 |
| Sulphur, wt% | ????0.522 |
| Nitrogen, wt% | ????0.153 |
| Zero pour, ℃ | ????36 |
| Carbon residue, wt% | ????0.05 |
| Boiling range, ℃ | |
| ????IBP/10％ | ????290/352 |
| ????30％/50％ | ????377/394 |
| ????70％/90％ | ????412/441 |
| ????95％/EBP | ????450/469 |
Table 3 hydrodenitrification reaction process condition
| Reaction pressure, MPa | ????6.7 |
| ????LHSV，h -1 | ????1.20 |
| 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, ℃ | 376 | 374 | 272 | 378 | 381 |
The result shows: adopt the prepared petroleum fractions Hydrobon catalyst of the present invention close at metal (molybdenum, nickel) content, fluorine-containing and adopt (embodiment 1) under the new situation that adds the silicon mode, the specific surface area of catalyzer, pore volume (table 1) and HDN (hydrodenitrification) reactive behavior (comparative example 2) obviously improve at the mixed catalyzer that directly adds the silicon preparation when pinching than not fluorine-containing and employing, reaching under the situation that identical HDN leads, temperature of reaction will be hanged down 5 ℃.If improve activity of such catalysts metal (Mo, Ni) content, prepared catalyzer will have higher hydrodenitrification reactive behavior (embodiment 2, embodiment 3).If only introduce fluorine during the preparation catalyzer, and adopt, then prepared catalyst specific surface area, pore volume (table 1) and HDN activity slightly weaker (comparing) with embodiment 1 at the mixed silicon (comparative example 1) that directly adds when pinching.
This shows, adopt the present invention to prepare the petroleum fractions Hydrobon catalyst, not only simple to operate, and also catalytic activity can be higher.
Claims (10)
1, a kind of preparation method of petroleum fractions Hydrobon catalyst is characterized in that adopting following steps:
(1). prepare siliceous binding agent;
(2). with aluminum oxide precursor, fluorochemicals, contain the compound of molybdenum or tungsten, add the made binding agent of step (1),, make the fluoro-silicon-aluminum oxide that contains molybdenum or tungsten through moulding, drying, roasting;
(3). with nickeliferous or the molybdenum that cobalt phosphate aqueous solution impregnation steps (2) obtains or the fluoro-silicon-aluminum oxide of tungsten, final Hydrobon catalyst is made in drying and roasting.
2, in accordance with the method for claim 1, it is characterized in that the described binding agent of step (1) is by intending thin water aluminum oxide, silicon-containing compound and 2%～4%HNO
3Aqueous solution is made, and wherein in aluminum oxide and silicon oxide, part by weight is: 96w%～98w%: 4w%～2w%.
3, according to the described method of claim 2, it is characterized in that described silicon-containing compound is a silicon sol.
4, in accordance with the method for claim 1, it is characterized in that the described aluminum oxide precursor of step (2) for intending thin water aluminum oxide, described fluorine cpd are AlF
3, (NH
4)
2SiF
6Or BF
3, molybdate compound is molybdenum oxide or ammonium molybdate, Tungstenic compound is an ammonium metawolframate.
5, in accordance with the method for claim 1, it is characterized in that the described concentration nickeliferous or the cobalt phosphate aqueous solution of step (3) is that every 100ml solution contains NiO or CoO 4～12g, contain P 2～5g.
6, in accordance with the method for claim 1, it is characterized in that each raw material add-on weight content below final catalyzer is definite: MoO
3Or WO
323%～40%, NiO or CoO5.0%～12%, P1.5%～4.0%, SiO
24.0%～10%, F2.0%～10.0%, Al
2O
330%～60%.
7, in accordance with the method for claim 1, it is characterized in that the roasting process of step (2) is: the speed with 3 ℃～5 ℃/minute in air is warming up to 300 ℃～380 ℃, constant temperature calcining 0.5 hour～2 hours; Then, be warming up to 400 ℃～500 ℃, constant temperature calcining 2 hours～5 hours with 3 ℃～5 ℃/minute speed.
8, in accordance with the method for claim 1, it is characterized in that step (3) roasting process is: the speed with 3 ℃～5 ℃/minute in air was warming up to 200 ℃～260 ℃ constant temperature calcinings 0.5 hour～2 hours; Then, be warming up to 300 ℃～430 ℃, constant temperature calcining 2 hours～5 hours with 3 ℃～5 ℃/minute speed.
9, a kind of catalyzer of claim 1～8 either party method preparation is characterized in that catalyzer has following composition and character: catalyzer is formed in weight and is comprised MoO
3Or WO
323%～40%, NiO or CoO5.0%～12%, P1.5%～4.0%, SiO
24.0%～10%, F2.0%～10.0%, Al
2O
330%～60%, the specific surface area of catalyzer is 230～330m
2/ g, pore volume are 0.33～0.42ml/g.
10, the application of the described catalyzer of a kind of claim 9 in petroleum fractions hydrofining, processing condition are: temperature of reaction is 230 ℃～420 ℃; Reaction pressure 5.0MPa～15.0MPa, LHSV0.5h
-1～3.0h
-1Hydrogen/oil volume ratio is 300～2000.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388977C (en) * | 2005-04-21 | 2008-05-21 | 中国石油化工股份有限公司 | Fluorinated and phosphor-contained hydrogenation catalyst with silicon oxide-alumina as carrier and its production |
| US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use thereof |
| CN106582738A (en) * | 2016-12-15 | 2017-04-26 | 中国海洋石油总公司 | Hydrofining catalyst and preparation method thereof |
| CN106622314A (en) * | 2016-12-15 | 2017-05-10 | 中国海洋石油总公司 | High-activity hydrofining catalyst and preparation method thereof |
-
2003
- 2003-05-31 CN CN 03133552 patent/CN1221313C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388977C (en) * | 2005-04-21 | 2008-05-21 | 中国石油化工股份有限公司 | Fluorinated and phosphor-contained hydrogenation catalyst with silicon oxide-alumina as carrier and its production |
| US8697598B2 (en) | 2005-04-21 | 2014-04-15 | China Petroleum & Chemical Corporation | Hydrogenation catalyst and use thereof |
| CN106582738A (en) * | 2016-12-15 | 2017-04-26 | 中国海洋石油总公司 | Hydrofining catalyst and preparation method thereof |
| CN106622314A (en) * | 2016-12-15 | 2017-05-10 | 中国海洋石油总公司 | High-activity hydrofining catalyst and preparation method thereof |
| CN106582738B (en) * | 2016-12-15 | 2020-01-03 | 中国海洋石油集团有限公司 | Hydrofining catalyst and preparation method thereof |
| CN106622314B (en) * | 2016-12-15 | 2020-01-07 | 中国海洋石油集团有限公司 | High-activity hydrofining catalyst and preparation method thereof |
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