CN100469442C - Fluorinated hydrogenation catalyst with silicon oxide-alumina as carrier and its production - Google Patents
Fluorinated hydrogenation catalyst with silicon oxide-alumina as carrier and its production Download PDFInfo
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Abstract
A fluoric hydrocatalyst with silicon oxide-aluminum oxide as its carrier contains nickel oxide (1-10 Wt%), molybdenum oxide and tungsten oxide (10-50), F (1-10) and carrier (rest). It has high hydrorefining performance. It is prepared by introducing F, Mo, Ni and W to carrier.
Description
Technical field
The present invention relates to a kind of hydrogenation catalyst and preparation thereof, more specifically to a kind of be the fluorine-containing hydrogenation catalyst and the preparation thereof of carrier with the silica-alumina.
Background technology
Under hydrogenation conditions, hydrocarbon feed contacts with catalyst and may comprise: reactions such as hydrogenation, hydrodesulfurization, hydrodenitrogeneration, HDM, hydrogenation aromatics-removing, hydroisomerization, Hydrodewaxing, hydrocracking and mitigation hydrocracking.Catalyst is wherein formed by carrier loaded group vib and group VIII metal component usually.The hydrogenation active metals component often is selected from Co or Ni-Mo or Co or Ni-W, and carrier often is selected from aluminium oxide, silica-alumina and their modifier.These catalyst can be made by steps such as drying, roastings then by the solution impregnating carrier that contains described metallic compound; Also carrier, group VIII metal component and group vib metal component can be adopted the method preparation of co-precipitation.Generally speaking, for the course of reaction based on desulphurization reaction, the preferred Co of hydrogenation active metals component (Ni) of catalyst-Mo combination is hydrogenated to main course of reaction for the saturated grade of aromatic hydrocarbons, preferred Ni-W combination.
Under certain condition, Mo modification NiW/Al
2O
3" Mo modification NiW/Al
2O
3The thiophene hydrodesulfurization performance of catalyst, the tenth national catalysis academic meeting paper collection, 2000,491 " or W modification NiMo/Al
2O
3(Modificationof the alumina-supported Mo-based hydrodesulfurizationcatalysts by tungsten, Catalysis Letters 53 (1998), 193-198) all to improving active favourable with the alumina support supported catalyst.
Patent CN1019502B discloses a kind of W-Mo-Ni three component catalysts of the B of containing auxiliary agent, and carrier is silica-alumina (silica 5-10 weight %), consists of WO
310-25 weight %, MoO
36-14 weight %, NiO 2-9 weight %, B
2O
32-7 weight %.This catalyst adopts and soaks W-Ni solution earlier, after soak Mo-B solution the method preparation, each dipping all carries out drying and roasting.
Compare with the hydrogenation catalyst of traditional bimetallic component, the activity of hydrocatalyst that contains three metal components that is provided by prior art increases, but the raising degree is limited, and its activity is still lower.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of new high-activity hydrogenation catalyst that contains three kinds of hydrogenation active metals components and preparation method thereof is provided.
The invention provides catalyst and contain silica-alumina carrier, fluorine, nickel, molybdenum and tungsten, consisting of after its roasting: nickel oxide 1-10 weight %, molybdenum oxide and tungsten oxide sum be greater than 10 to 50 weight %, fluorine 1-10 weight %, surplus is a carrier.
Method provided by the invention comprises to the silica-alumina carrier introduces fluorine, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after the catalyst roasting: nickel oxide 1-10 weight %, and molybdenum oxide and tungsten oxide sum are greater than 10 to 50 weight %, fluorine 1-10 weight %, surplus is a carrier.
Catalyst activity height provided by the invention, for example, employing the invention provides catalyst a kind of catalytically cracked stock is carried out the hydrogenation preliminary treatment, and the nitrogen content that generates in the oil can be reduced to 24ppm; And under same reaction conditions, adopting the trade mark is that nitrogen content in the generation oil of industrial catalyst of RN-2 is only reduced to 55ppm.
The specific embodiment
According to catalyst provided by the invention, be benchmark in oxide and with the catalyst, consisting of after the preferred roasting: nickel oxide 1-7 weight %, molybdenum oxide and tungsten oxide sum be greater than 15 to 45 weight %, fluorine 1-7 weight %, surplus is a carrier; Further preferred wherein tungsten oxide and the mol ratio of molybdenum oxide greater than 2.6 to 30, the mol ratio of more preferred tungsten oxide and molybdenum oxide is greater than 3.1 to 25.Composition after the described roasting is meant that catalyst is formed in the sample of 550 ℃ of roastings after 4 hours under air atmosphere.
With described carrier is benchmark, and the content of the silica in the preferred silica-alumina is 2-45 weight %, and the content of aluminium oxide is 55-98 weight %; The content of further preferred silica is 5-40 weight %, and the content of aluminium oxide is 60-95 weight %.
Described silica-alumina has the specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferential oxidation silicon-aluminium oxide is a 150-350 rice
2/ gram, more preferably 180-300 rice
2/ gram, the pore volume of preferred silica-alumina is 0.4-1 milliliter/gram, more preferably 0.5-0.8 milliliter/gram.
Described silica-alumina carrier can be commercially available commodity or adopt any one prior art for preparing.Preferably by the precursor of aluminium oxide and/or aluminium oxide is mixed the method preparation of also roasting with the precursor of silica and/or silica.Wherein, be benchmark with the carrier, the consumption of each component finally preferably makes described carrier contain the silica of 2-45 weight %, the aluminium oxide of 55-98 weight %; The content that further preferably makes silica is 5-40 weight %, and the content of aluminium oxide is 60-95 weight %.It is 1-10 hour that described sintering temperature is preferably 450-650 ℃, roasting time, and further preferred sintering temperature is that 550-620 ℃, roasting time are 2-8 hour.
Described carrier is looked different the article shaped that require can be made into various easy operatings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, can be with aluminium oxide and/or its precursor mix with the precursor of silica and/or silica, the method preparation of extruded moulding and roasting.Wherein, the precursor of described aluminium oxide can be selected from one or more in various hydrated aluminas, the aluminium colloidal sol.The precursor of described silica can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in aqueous medium forms silicon gel, colloidal sol, as in the compounds such as waterglass, the hydrosol and esters of silicon acis one or more.When extrusion molding, can add an amount of extrusion aid and/or adhesive, extrusion molding then.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not give unnecessary details at this.
Can also contain one or more in the catalyst provided by the invention and be selected from and contain oxygen or nitrogenous organic matter, preferred oxygen-containing organic compound is selected from one or more in organic alcohol, the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetate, maleic acid, oxalic acid, aminotriacetic acid, 1, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, organic compounds containing nitrogen can be ethylenediamine, EDTA and ammonium salt thereof.Described organic matter is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide, is preferably 0.08-1.5.
According to method provided by the invention, to the introducing method of described fluorine, molybdenum, nickel and tungsten without limits, preferable methods can be by the precursor of precursor, silica and/or the silica of aluminium oxide and/or aluminium oxide being mixed with a kind of fluorochemical and the method for roasting is directly introduced fluorine, introducing other components with the method for dipping afterwards; Also can be to introduce by the method with the solution impregnation silica-alumina carrier of fluorine-containing, molybdenum, nickel and tungsten compound individually or simultaneously.Wherein, the consumption of each component preferably makes consisting of after the catalyst roasting: nickel oxide is 1-7 weight %, and molybdenum oxide and tungsten oxide sum be greater than 15 to 45 weight %, fluorine 1-7 weight %, and surplus is a carrier.Described dipping method is a conventional method, by adjusting and control, prepare that to specify the method for fluorine, molybdenum, nickel and tungsten metals content catalysts be conventionally known to one of skill in the art to concentration, consumption or the alumina support consumption of one or more solution in fluorine-containing, nickel, molybdenum, the tungsten compound.
According to method provided by the invention, after finishing, described dipping also comprises the step of drying, roasting or not roasting, the condition of described drying and roasting all is conventional, for example, baking temperature is 100-300 ℃, and excellent is 100-280 ℃, be 1-12 hour drying time, is preferably 2-8 hour; Sintering temperature is 350-550 ℃, is preferably 400-500 ℃, and roasting time is 1-8 hour, is preferably 2-6 hour.
Described fluorochemical is selected from fluorine-containing soluble compound, as in hydrofluoric acid, hydrofluoride, fluosilicic acid, fluosilicate, the ammonium fluoride one or more.Preferred fluorinated ammonium and/or ammonium fluosilicate.
The described compound that contains molybdenum is selected from the soluble compound that contains molybdenum, as in ammonium molybdate, ammonium paramolybdate and the ammonium phosphomolybdate one or more.
Described nickeliferous compound is selected from nickeliferous soluble compound, as in nickel nitrate, basic nickel carbonate, nickel chloride, the nickelous sulfate one or more.
The compound of described tungstenic is selected from the soluble compound of tungstenic, as in ammonium metatungstate, the ethyl ammonium metatungstate one or more.
When described catalyst contains organic matter, described organic introducing method, can be with described organic matter with contain the compound of other component, be mixed with the described carrier of dipping and dry behind the mixed solution as in fluorine-containing, molybdenum, nickel, the tungsten metallization compound one or more; Can also be with the described carrier of dipping behind the independent obtain solution of organic matter and dry.When being introduced separately into organic matter, preferably at first introduce other components, as at first introducing fluorine, molybdenum, nickel and tungsten metal component, introduce organic matter afterwards again.It is 0.03-2.0 that described organic introducing amount makes organic matter in the catalyst and mol ratio in nickel, molybdenum and the tungsten sum of oxide, is preferably 0.08-1.5.The described dry conventional process that adopts is carried out, and baking temperature wherein is preferably 100-300 ℃, is preferably 1-12 hour drying time, and further preferred baking temperature is 100-280 ℃, and be 2-8 hour drying time.
According to the conventional method in this area, catalyst provided by the invention is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
Compare with the catalyst that existing method provides, Hydrobon catalyst provided by the invention is active high, can be used for the hydrofinishing of petroleum distillate, is specially adapted to the hydrotreatment process of heavy distillate.
The following examples will the invention will be further described, but not thereby limiting the invention.
Example 1
Take by weighing the 2000 gram aluminium hydrate powder (dry glue powders that Chang Ling refinery company catalyst plant is produced, butt 70 weight %) and 631 grams contain the Ludox (Haiyang Chemical Plant, Qingdao's product) of silica 25%, mixing the back, to be extruded into circumscribed circle diameter with banded extruder be 1.3 millimeters butterfly bar, wet bar was in 120 ℃ of dryings 4 hours, roasting is 3 hours under 600 ℃ of conditions, make carrier S 1, silica content is 10.1 weight % in the S1 carrier.
Take by weighing carrier S 1 200 gram, the aqueous solution of this carrier with fluorinated ammonium (analyzes pure, Beijing Chemical Plant's product) 16.9 grams were flooded 2 hours for 176 milliliters, 120 ℃ of dryings 3 hours, 480 ℃ of roastings 3 hours make fluorinated silicon oxide-alumina support.With containing ammonium paramolybdate (chemical pure, Beijing Chemical Plant's product) 170 milliliters of above-mentioned carriers of dipping of the aqueous solution of 11.9 grams are 3 hours, 120 ℃ of dryings 8 hours, 400 ℃ of roastings 3 hours, afterwards with 162 milliliters of dippings of the aqueous solution that contain nickel nitrate (analyze pure, Beijing Chemical Plant's product) 27.2 grams, ammonium metatungstate (technical grade, Sichuan Zigong Hard Alloy Foundry product) 57.3 grams 3 hours, wet bar obtains catalyst C1 in 4 hours, 450 ℃ roastings of 120 ℃ of dryings 4 hours.Composition after the catalyst C1 roasting is listed in table 1
Example 2
Take by weighing carrier S 1 200 gram, with this carrier with 176 milliliters of dippings of the aqueous solution of fluorinated ammonium 19.1 grams 2 hours, 120 ℃ of dryings 3 hours, 420 ℃ of roastings 3 hours make fluorinated silicon oxide-alumina support.Flooded above-mentioned carriers 3 hours for 170 milliliters with the aqueous solution that contains ammonium paramolybdate 24.7 grams, 280 ℃ of dryings 8 hours, flooded 3 hours for 160 milliliters with the aqueous solution that contains nickel nitrate 24.6 grams, ammonium metatungstate 66.7 grams afterwards, wet bar obtains catalyst C2 in 4 hours, 500 ℃ roastings of 120 ℃ of dryings 4 hours.Composition after the catalyst C2 roasting is listed in the table 1.
Example 3
Take by weighing carrier S 1 200 gram, with this carrier with 176 milliliters of dippings of the aqueous solution of fluorinated ammonium 8.9 grams 2 hours, 120 ℃ of dryings 3 hours, 420 ℃ of roastings 3 hours make fluorinated silicon oxide-alumina support.Flooded above-mentioned carriers 3 hours for 170 milliliters with the aqueous solution that contains ammonium paramolybdate 17.5 grams, 280 ℃ of dryings 8 hours, flooded 3 hours for 162 milliliters with the aqueous solution that contains nickel nitrate 44.3 grams, ammonium metatungstate 74.4 grams afterwards, wet bar obtains catalyst C3 in 4 hours, 500 ℃ roastings of 120 ℃ of dryings 4 hours.Composition after the catalyst C3 roasting is listed in the table 1.
Example 4
The Ludox (with example 1) and the 130 gram ammonium fluorides that 800 gram aluminium hydrate powders (with example 1), 779 grams are contained silica 30 weight % mix, be extruded into the cylindrical bar that is of a size of 1.3mm with banded extruder, 120 ℃ of dryings 4 hours, 580 ℃ of roastings 3 hours, make fluorine-containing silica-alumina carrier S 2, silica content is 27.0 weight % in the final carrier.
Get S2 carrier 200g, with this carrier of 172 milliliters of dippings of the aqueous solution that contains ammonium paramolybdate 7.5 gram 3 hours, 120 ℃ of dryings 4 hours, 200 ℃ of dryings are 4 hours again, obtain containing the molybdenum carrier.Then with this carrier of 166 milliliters of dippings of the aqueous solution that contains nickel nitrate 40.9 grams, ammonium metatungstate 100.3 grams 3 hours, 120 ℃ of dryings 4 hours in 250 ℃ of dryings 4 hours, obtain catalyst C4 then.Composition after the catalyst C4 roasting is listed in the table 1.
Example 5
Get S2 carrier 200g, with this carrier of 172 milliliters of dippings of the aqueous solution that contains ammonium paramolybdate 7.5 gram 3 hours, 120 ℃ of dryings 4 hours, 200 ℃ of dryings are 4 hours again, obtain containing the molybdenum carrier.Then with this carrier of 170 milliliters of dippings of the aqueous solution that contains nickel nitrate 40.9 grams, ammonium metatungstate 100.3 grams, citric acid 12.2 grams 3 hours, 230 ℃ of dryings 4 hours obtain catalyst C5.Calculating citric acid is 0.1 with mol ratio in nickel, molybdenum and the tungsten of oxide.Composition after the catalyst C5 roasting is listed in the table 1.
Example 6
Get S1 carrier 200g, with 176 milliliters of dippings of the aqueous solution of fluorinated ammonium 49.4 grams 2 hours, 120 ℃ of dryings 3 hours, 400 ℃ of roastings 3 hours make fluorinated silicon oxide-alumina support.With this carrier of 165 milliliters of dippings of the aqueous solution that contains ammonium paramolybdate 6.2 gram, nickel nitrate 85.5 grams, ammonium metatungstate 190.2 grams 3 hours, 120 ℃ of dryings 4 hours were then in 450 ℃ of roastings 4 hours.With the 122 milliliters of above-mentioned containing metal carriers of dipping of the aqueous solution that contain ethylene glycol 95.6 grams, 120 ℃ of dryings obtain catalyst C4 after 6 hours.Calculating ethylene glycol is 1.5 with mol ratio in nickel, molybdenum and the tungsten of oxide.Composition after the catalyst C4 roasting is listed in the table 1.
Table 1
Example 7-11
The explanation of this example the invention provides the performance of catalyst.
The pyridine hydrogenation reaction performance of evaluate catalysts C1～C5 on the little inverse spectral apparatus of continuous-flow, feedstock oil is the n-hexane that contains pyridine 10 weight %, the catalyst loading amount is 150 milligrams.
Before formal charging, be that sulfurized oil carries out presulfurization to catalyst with the mixed solution that contains 5 weight % carbon disulfide and cyclohexane earlier, conditions of vulcanization is: pressure 4.1 MPas, 360 ℃ of temperature, 4 hours time, sulfurized oil feed rate 0.4 ml/min, H
2Flow velocity 400 ml/min; Cut feedstock oil afterwards and react, reaction condition is: pressure 4.1 MPas, and feedstock oil input 0.2 ml/min, volume of hydrogen oil ratio are 2000, temperature is 360 ℃, reacts the online gas chromatographic analysis of sampling after 3 hours.Pyridine hydrogenation reaction activity is calculated as follows:
X is the pyridine denitrification percent in the formula, and the pyridine hydrogenation reaction speed of getting catalyst C2 is 100, and then the relative pyridine hydrodenitrogenationactivity activity of other catalyst can be represented by the formula: relative activity=A
Cn/ A
C2* 100%.A in the formula
CnBe the activity of catalyst C1 of the present invention, C3, C4, C5, A
C2Activity for catalyst C2.The results are shown in Table 2.
Table 2
| Example | Catalyst | Relative hydrodenitrogenationactivity activity, % |
| 7 | C1 | 116 |
| 8 | C2 | 100 |
| 9 | C3 | 111 |
| 10 | C4 | 140 |
| 11 | C5 | 182 |
| 12 | C6 | 189 |
The result of table 2 can illustrate, the invention provides the raising of the pyridine hydrodenitrogenationactivity activity of catalyst with the molar ratio of tungsten oxide and molybdenum oxide, active increasing.In addition, in catalyst, introduce the pyridine hydrodenitrogenationactivity activity that organic matter can further improve catalyst.
Example 13-14
The serviceability of present embodiment explanation catalyst of the present invention in hydrocracking raw material oil preprocessing process.
Evaluate catalysts C5, the trade mark are RN-2 (industrial catalyst, the product of Chang Ling branch company catalyst plant) on 250 milliliters of hydrogenation plants.Raw materials used oil nature sees Table 3, and reaction condition is: hydrogen dividing potential drop 15.0MPa, air speed 1.0h
-1, hydrogen-oil ratio 800:1, reaction temperature is 380 ℃.React sampling after 48 hours, the results are shown in Table 4.The assay method of nitrogen is SH/T 0657-1998, and the assay method of sulphur is SH/T0253-92.
Table 3
| Density (20 ℃), g/ml | 0.9171 |
| S， ppm | 7200 |
| N， ppm | 1800 |
| Condensation point, ℃ | 40 |
| Boiling range D1160, ℃ | |
| Initial boiling point | 265 |
| 50% point | 460 |
| 95% point | 526 |
Table 4
| Example | Catalyst | Hydrotreatment oil nitrogen content, ppm |
| 13 | RN-2 | 55 |
| 14 | C5 | 24 |
Result in the table 5 shows that with respect to industrial catalyst, catalyst provided by the invention has higher hydrodenitrogenationactivity activity.
Claims (15)
1, with the silica-alumina is the fluorine-containing hydrogenation catalyst of carrier, consisting of after its roasting: nickel oxide 1-10 weight %, molybdenum oxide and tungsten oxide sum greater than 10 to smaller or equal to 50 weight %, fluorine 1-10 weight %, surplus is a carrier, the mol ratio of wherein said tungsten oxide and molybdenum oxide is greater than 2.6 to smaller or equal to 30, and the composition after the described roasting is meant that catalyst is formed in the sample of 550 ℃ of roastings after 4 hours under air atmosphere.
2, catalyst according to claim 1 is characterized in that, consisting of after the described roasting: nickel oxide 1-7 weight %, and molybdenum oxide and tungsten oxide sum be greater than 15 to smaller or equal to 45 weight %, fluorine 1-7 weight %, surplus is a carrier.
3, catalyst according to claim 1 is characterized in that, the mol ratio of described tungsten oxide and molybdenum oxide greater than 3.1 to smaller or equal to 24.
4, catalyst according to claim 1 is characterized in that, is benchmark with described carrier, and the silica content in the described silica-alumina is 2-45 weight %, and the content of aluminium oxide is 55-98 weight %.
5, catalyst according to claim 4 is characterized in that, is benchmark with described silica-alumina, and the content of the silica in the described silica-alumina is 5-40 weight %, and the content of aluminium oxide is 60-95 weight %.
6, catalyst according to claim 1 is characterized in that, described catalyst contains to be selected from and contains in oxygen or the nitrogenous organic matter one or more, and oxygen containing organic matter is selected from one or more in organic alcohol, the organic acid; Nitrogenous organic matter is selected from one or more in organic amine, the organic ammonium salt, and described organic matter is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide.
7, catalyst according to claim 6, it is characterized in that, it is 200-1500 polyethylene glycol, diethylene glycol, butanediol, acetate, maleic acid, oxalic acid, aminotriacetic acid, 1 that oxygen containing organic matter is selected from ethylene glycol, glycerine, molecular weight, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, nitrogenous organic matter is selected from one or more in ethylenediamine, EDTA and the ammonium salt thereof, and described organic matter is 0.08-1.5 with mol ratio in nickel, molybdenum and the tungsten sum of oxide.
8, with the silica-alumina is the fluorine-containing hydrogenization catalyst preparation method of carrier, this method comprises to the silica-alumina carrier introduces fluorine, molybdenum, nickel and tungsten, wherein, the consumption of each component makes consisting of after the catalyst roasting: nickel oxide 1-10 weight %, molybdenum oxide and tungsten oxide sum greater than 10 to smaller or equal to 50 weight %, fluorine 1-10 weight %, surplus is a carrier, the mol ratio of wherein said tungsten oxide and molybdenum oxide greater than 2.6 to smaller or equal to 30, composition after the described roasting is meant that catalyst is formed in the sample of 550 ℃ of roastings after 4 hours under air atmosphere.
9, method according to claim 8, it is characterized in that the consumption of described component makes consisting of after the catalyst roasting: described nickel oxide 1-7 weight %, molybdenum oxide and tungsten oxide sum greater than 15 to smaller or equal to 45 weight %, fluorine 1-7 weight %, surplus is a carrier.
10, method according to claim 8, it is characterized in that, the preparation method of described silica-alumina carrier comprises aluminium oxide and/or the precursor that is selected from a kind of and several aluminium oxide in hydrated alumina, the aluminium colloidal sol and silica and/or the precursor that is selected from one or more silica in waterglass, Ludox and the esters of silicon acis is mixed and roasting, with the carrier is benchmark, the consumption of each component finally makes described carrier contain the silica of 2-45 weight %, the aluminium oxide of 55-98 weight %.
11, method according to claim 8, it is characterized in that, the preparation method of described silica-alumina carrier comprises aluminium oxide and/or the precursor that is selected from a kind of and several aluminium oxide in hydrated alumina, the aluminium colloidal sol and silica and/or the precursor that is selected from one or more silica in waterglass, Ludox and the esters of silicon acis is mixed with a kind of fluorochemical and roasting, with the carrier is benchmark, the consumption of each component finally makes described carrier contain the silica of 2-45 weight %, the aluminium oxide of 55-98 weight %.
According to claim 10 or 11 described methods, it is characterized in that 12, the sintering temperature in the described silica-alumina preparing carriers is 450-650 ℃, roasting time is 1-10 hour.
13, method according to claim 8 is characterized in that, the mol ratio that the consumption of described each component makes tungsten oxide in the catalyst and molybdenum oxide greater than 3.1 to smaller or equal to 24.
14, method according to claim 8, it is characterized in that, described method also comprises introduces organic step, and described organic matter is selected from and contains in oxygen and the nitrogenous organic matter one or more, and oxygen containing organic matter is selected from one or more in organic alcohol, the organic acid; Nitrogenous organic matter is selected from one or more in organic amine, the organic ammonium salt, and it is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide that organic introducing amount makes the organic matter in the final catalyst.
15, method according to claim 14, it is characterized in that, described oxygen containing organic matter is selected from ethylene glycol, glycerine, molecular weight is 200-1500 polyethylene glycol, diethylene glycol, butanediol, acetate, maleic acid, oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, in the malic acid one or more, nitrogenous organic matter is selected from ethylenediamine, in EDTA and the ammonium salt thereof one or more, described organic introducing amount make in the final catalyst organic matter with in the nickel of oxide, the mol ratio of molybdenum and tungsten sum is 0.08-1.5.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100647525A CN100469442C (en) | 2005-04-21 | 2005-04-21 | Fluorinated hydrogenation catalyst with silicon oxide-alumina as carrier and its production |
| CA2605505A CA2605505C (en) | 2005-04-21 | 2006-04-20 | A hydrogenation catalyst and use thereof |
| KR1020077026993A KR101281134B1 (en) | 2005-04-21 | 2006-04-20 | A hydrogenation catalyst and its application |
| EP06722384A EP1880760A4 (en) | 2005-04-21 | 2006-04-20 | A hydrogenation catalyst and its application |
| US11/918,851 US8697598B2 (en) | 2005-04-21 | 2006-04-20 | Hydrogenation catalyst and use thereof |
| EP12158777A EP2463025A1 (en) | 2005-04-21 | 2006-04-20 | Ni/Mo/W supported hydrogenation catalyst containing P or F and process for hydrocarbon hydrogenation |
| PCT/CN2006/000743 WO2006111093A1 (en) | 2005-04-21 | 2006-04-20 | A hydrogenation catalyst and its application |
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| CNB2005100647525A CN100469442C (en) | 2005-04-21 | 2005-04-21 | Fluorinated hydrogenation catalyst with silicon oxide-alumina as carrier and its production |
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| CN103013558B (en) * | 2011-09-22 | 2015-05-20 | 中国石油化工股份有限公司 | Production method of SBS rubber filling oil |
| CN106607097B (en) * | 2015-10-26 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof |
| CN106607096B (en) * | 2015-10-26 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof |
| CN106607039B (en) * | 2015-10-26 | 2019-05-17 | 中国石油化工股份有限公司 | A kind of hydrogenation catalyst and preparation method thereof |
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