CN1872961B - Method for hydrotreating hydrocarbon oil - Google Patents
Method for hydrotreating hydrocarbon oil Download PDFInfo
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Abstract
This invention provides a method for hydrogenation of hydrocarbon oils. The method comprises contacting hydrocarbon oils with the catalyst in the presence of hydrogen for hydrogenation. The catalyst contains carrier, nickel oxide 1-10 wt. %, molybdena oxide and tungsten oxide 10-50 wt. %. The molar ratio of tungsten oxide to molybdena oxide is 2.6-30. The method has such advantage as obviously improved hydrogenation effects.
Description
Technical field
The present invention relates to a kind of method for hydrotreating hydrocarbon oil.
Background technology
Under hydrogenation conditions, hydrocarbon oil crude material contacts with catalyzer and may comprise: reactions such as hydrogenation, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), hydrogenation aromatics-removing, hydroisomerization, Hydrodewaxing, hydrocracking and mitigation hydrocracking.Catalyzer is wherein formed by carrier loaded group vib and group VIII metal component usually.Also contain adjuvant components such as fluorine, phosphorus, boron in some catalyzer, support of the catalyst is aluminum oxide and/or silicon oxide, and some catalyzer also contains zeolite, and the hydrogenation active metals component often is selected from Co or Ni-Mo or Co or Ni-W.These catalyzer 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 reaction process based on desulphurization reaction, the preferred Co of hydrogenation active metals component (Ni) of catalyzer-Mo combination is hydrogenated to main reaction process 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 catalyzer, the tenth national catalysis academic meeting paper collection, 2000,491 " or W modification NiMo/Al
2O
3(Modificationof the alumina-supported Mo-basedhydrodesulfurization catalysts by tungsten, Catalysis Letters53 (1998) is 193-198) all to improving active favourable with the alumina supporter supported catalyst.
CN1083476C discloses a kind of catalyst for hydrorefining distillate oil and preparation method thereof, this catalyzer is an active ingredient with VIII family and group vib metal, add phosphate builder, with aluminum oxide or siliceous aluminum oxide is carrier, it is characterized in that described catalyzer is an active ingredient with W, Mo, Ni, for helping catalyst component,, then be respectively WO with P in catalyst weight
313-25 weight %, MoO
36-14 weight %, NiO2-7 weight %, P
2O
51-9 weight %; Catalyzer pore volume 0.22-0.37 milliliter/gram, specific surface area 110-170 rice
2/ gram.This Preparation of catalysts method comprises: with aluminum oxide or siliceous aluminum oxide is carrier, with W, Mo, Ni is active ingredient, add the P auxiliary agent, make W, Mo, Ni, P co-impregnated solution with W, Mo, Ni, P-compound, after 70-120 ℃ of heating, the mode impregnated carrier that described co-impregnated solution is soaked altogether with gradation, after 80-150 ℃ of drying 8 hours, 450-550 ℃ made in roasting 2-5 hour.
CN1098915C discloses a kind of Hydrobon Catalyst And Its Preparation Method, and this catalyzer is an active ingredient with VIII family and VI B family metal, adds boron additive, it is characterized in that with the weight percent being benchmark, and catalyzer comprises SiO
23-10%, MoO
35-10%, WO
310-25%, NiO2-5%, B
2O
52-5%; Described catalyzer is to make by in type carrier is only carried out single-steeping, drying and roasting with the mixing solutions that contains active ingredient and auxiliary agent.
Compare with the hydrogenation catalyst of traditional bimetal component, the activity of hydrocatalyst that contains three metal components that is provided by prior art improves, but the raising degree is limited.When adopting this type of catalyzer that hydrocarbon ils is carried out hydrotreatment, its effect is still relatively poor.
Summary of the invention
The objective of the invention is on the basis of existing technology, a kind of method for hydrotreating hydrocarbon oil new, better effects if is provided.
Method provided by the invention is included under hydrogen existence and the hydrogenation conditions, hydrocarbon oil feed is contacted with catalyzer, described catalyzer contains carrier, nickel, molybdenum and tungsten, in oxide compound and with the catalyzer is benchmark, the content of nickel is 1-10 weight %, molybdenum and tungsten sum are greater than 10 to 50 weight %, and wherein, the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is 2.6-30.
Compare with existing method, the hydrocarbon oil hydrogenation treatment effect that the invention provides method obviously improves.
For example, adopt existing method (catalyzer is commercial catalysts RN-1) and the inventive method (consisting of after the catalyzer roasting: respectively in oxide compound, the content of nickel is 2.5 weight %, molybdenum and tungsten sum are 26.5 weight %, phosphorus 2.4 weight %, in element, fluorine 1.5 weight %, the mol ratio of Tungsten oxide 99.999 and molybdenum oxide is 3.2) (sulphur content is 18000ppm to a kind of decompressed wax oil, nitrogen content is 1200ppm) make with extra care, activity with existing method is 100, and then the relative reactivity of the hydrogenating desulfurization of the inventive method is at least 139, and the relative reactivity of hydrodenitrification is at least 127.
Embodiment
According to method provided by the invention, in oxide compound and with the catalyzer is benchmark, the content of the preferred nickel of wherein said catalyzer is 1-7 weight %, and molybdenum oxide and Tungsten oxide 99.999 sum are greater than 15 to 45 weight %, and wherein the mole Bill ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 3.1 to 24.
According to method provided by the invention, the carrier in the wherein said catalyzer can be any one carrier that is commonly used for the preparation catalyzer, for example, is selected from the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix one or more.The optional self-alumina of described heat-resistant inorganic oxide, silicon oxide, zirconium white, titanium oxide, magnesium oxide, Thorotrast, beryllium oxide, aluminium oxide-silicon oxide, aluminium oxide-titanium oxide, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, oxidation titania-zirconia, silica-alumina-zirconium white, silica-alumina-Thorotrast, silica-alumina-titanium oxide or silica-alumina-magnesium oxide are preferably aluminum oxide, aluminium oxide-silicon oxide.In preferred aluminum oxide, silica-alumina, molecular sieve and their mixture wherein one or more.
Further preferred aluminum oxide is selected from one or more among γ, η, θ, δ and the x; Containing one or more is selected from titanium, magnesium, boron, zirconium, thorium, niobium, rare earth and doses among γ, η, θ, δ and the x of component one or more.More preferred aluminum oxide is gama-alumina or contains one or more and be selected from the gama-alumina that titanium, magnesium, boron, zirconium, thorium, niobium, rare earth are dosed component.
Described aluminum oxide can be that commercially available commodity also can be by any one method preparation in the prior art.For example, can be after roasting, to make by one or more the mixture that is selected among hibbsite, monohydrate alumina and the amorphous hydroted alumina; Or one or more the mixture among hibbsite, monohydrate alumina and the amorphous hydroted alumina of titaniferous, magnesium, boron, zirconium, thorium, niobium, rare earth makes after roasting.
With described carrier is benchmark, and the silica content in the further preferred silica-alumina is 2-45 weight %, and the content of aluminum oxide is 55-98 weight %; The content of more preferred silicon oxide is 5-40 weight %, and the content of aluminum oxide is 60-95 weight %.
Described silica-alumina carrier can be commercially available commodity or adopt any one prior art for preparing.For example, the trade mark is the silica-alumina (German Condea company product) of Siral40, or by the silica-alumina that the precursor of aluminum oxide and/or aluminum oxide is mixed with the precursor of silicon oxide and/or silicon oxide and roasting obtains.The precursor of described aluminum oxide can be selected from one or more in various hydrated aluminum oxides, the aluminium colloidal sol.The precursor of described silicon oxide can be any water-soluble silicon-containing compound and the silicon-containing compound that can hydrolysis in water medium forms silicon gel, colloidal sol.For example, one or more in the compounds such as water glass, the water-sol and silicon ester.It is 1-10 hour that described maturing temperature is preferably 450-650 ℃, roasting time, and further preferred maturing temperature is that 500-620 ℃, roasting time are 2-8 hour.
Described molecular screening is from the zeolite molecular sieve of Chang Zuowei catalytic cracking activity component, in the non-zeolitic molecular sieves one or more.For example, be selected from ZRP, Y zeolite, beta zeolite, mordenite, ZSM-5, MCM-41, Ω, ZSM-12, the MCM-22 zeolite molecular sieve one or more.In the preferred Y zeolite, be ta zeolite, mordenite, ZSM-5 wherein one or more.The mixture of one or more in the further preferred Y zeolite, beta zeolite, ZSM-5 wherein.Described molecular sieve can be commercially available commodity, also can adopt any one prior art for preparing.
When described carrier is the mixture of aluminum oxide and/or silica-alumina and molecular sieve, be benchmark with described carrier, the content of described molecular sieve is preferably 0.5-85 weight %, more preferably 5-50 weight %.
Described carrier is looked different the forming composition that require can be made into various easy handlings, for example microballoon, sphere, tablet or bar shaped etc.Moulding can be carried out according to a conventional method, for example, can be through the preparation of the method for extruded moulding and roasting with the precursor of aluminum oxide and/or its precursor, silicon oxide and/or silicon oxide, one or more mixture in the molecular sieve.When extrusion moulding, can add an amount of extrusion aid and/or peptizing agent, extrusion moulding 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.
According to method provided by the invention, wherein said Preparation of catalysts method comprises introduces molybdenum, nickel and tungsten in carrier, to the introducing method of described molybdenum, nickel and tungsten without limits, preferable methods can be to introduce by the method with the solution impregnating carrier that contains molybdenum, nickel and tungsten compound individually or simultaneously.Wherein, it is 1-7 weight % that the consumption of each component preferably makes the content of nickel oxide in the catalyzer, and molybdenum oxide and Tungsten oxide 99.999 sum are greater than 15 to 45 weight %, and wherein the mole Bill ratio of Tungsten oxide 99.999 and molybdenum oxide is greater than 3.1 to 24.Described dipping method is an ordinary method, by adjusting and control, prepare that to specify the method for molybdenum, nickel and tungsten metals content catalysts be conventionally known to one of skill in the art to concentration, consumption or the carrier consumption of one or more solution in nickeliferous, 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, drying temperature is 100-300 ℃, and excellent is 100-280 ℃, be 1-12 hour time of drying, is preferably 2-8 hour; Maturing temperature is 350-550 ℃, is preferably 400-500 ℃, and roasting time is 2-8 hour, is preferably 3-6 hour.
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 nickelous nitrate, basic nickel carbonate, nickelous chloride, the single nickel salt one or more.
The compound of described tungstenic is selected from the soluble compound of tungstenic, as in ammonium metawolframate, the ethyl ammonium metawolframate one or more.
According to method provided by the invention, also contain one or more the adjuvant component that is selected from fluorine, phosphorus and the boron in the wherein said catalyzer, be benchmark in element and with the catalyzer, the content of described auxiliary agent is 0-10 weight %, is preferably 0.5-7 weight %.
When also containing one or more the adjuvant component that is selected from fluorine, phosphorus and the boron in the described catalyzer, its introducing method can be will contain described auxiliary agent compound directly and the precursor of aluminum oxide and/or its precursor, silicon oxide and/or silicon oxide, one or more the mixture in the molecular sieve through extruded moulding and roasting; Can be the compound that to contain described auxiliary agent and contain molybdenum, nickel and contact with described carrier after the tungsten metallization compound is mixed with mixing solutions; Can also be to contact and roasting with described carrier behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and group VIII and group vib metal are introduced described carrier respectively, preferably at first auxiliary compound solution contacts with described carrier and roasting with containing, contact with the group vib solution of metal compound with containing group VIII more afterwards, for example method by flooding.Described maturing temperature is 350-550 ℃, is preferably 400-500 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.
According to method provided by the invention, wherein said catalyzer can also contain one or more and be selected from and contain oxygen or nitrogenous organism, preferred organic alcohol, in the organic acid one or more wherein of oxygen-containing organic compound, organic compounds containing nitrogen are wherein organic amine preferably.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be quadrol or EDTA and ammonium salt thereof.Described organism is 0-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide compound, is preferably 0.08-1.5.
When described catalyzer contains organism, described organic introducing method can be with described organism with contain the compound of other components, as contain molybdenum, nickeliferous and tungsten metallization compound and be mixed with the described carrier of dipping behind the mixing solutions; Can also be with the described carrier of dipping behind the independent obtain solution of organism.When as described in organism and other components are introduced respectively as molybdenum or nickel, tungsten metal component during carrier, preferably at first introduce other components, as with carrier as described in the solution impregnation that contains molybdenum, nickeliferous and tungsten metallization compound, dry, roasting or not roasting are afterwards again with containing organic solution impregnation and drying.The described dry conventional process that adopts is carried out, and drying temperature wherein is preferably 100-300 ℃, is preferably 1-12 hour time of drying, and further preferred drying temperature is 100-250 ℃, and be 2-8 hour time of drying.It is 0.03-2.0 that described organic introducing amount makes organism in the final catalyzer and mol ratio in nickel, molybdenum and the tungsten sum of oxide compound, is preferably 0.08-1.5.
According to the ordinary method in this area, described hydrotreating catalyst is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out prevulcanized with sulphur, hydrogen sulfide or sulfur-bearing raw material, this prevulcanized can be carried out also can original position vulcanizing in device outside device, is translated into sulfide type.
According to method provided by the invention, described hydrofining condition is temperature of reaction 200-420 ℃, is preferably 220-400 ℃, hydrogen dividing potential drop 2-18 MPa, is preferably the 2-15 MPa, liquid hourly space velocity 0.3-10 hour
-1, be preferably 0.3-5 hour
-1, hydrogen to oil volume ratio 50-5000, be preferably 50-4000.
Employing the invention provides method can directly process all kinds of hydrocarbon raw materials, so that it is carried out hydrotreatment.Described hydrocarbon ils is selected from one or more in crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, frivolous asphalt oil, the heavy deasphalted oil.。
The following examples will the present invention is described further.
Example 1
Take by weighing 1000 gram aluminum hydroxide solid elastomer powder (Chang Ling refinery company catalyst plant product, butt 71.0 weight %), be extruded into circumscribed circle diameter and be 1.3 millimeters cloverleaf pattern bar, wet bar is in 120 ℃ of dryings after 4 hours, and 600 ℃ of roastings 4 hours obtain carrier S 1.
Get the S1200 gram, with containing ammonium paramolybdate (analytical pure, Beijing Chemical Plant's product) 176 milliliters of dippings of the aqueous solution of 13.2 grams are 1 hour, 120 ℃ of dryings 4 hours, reduce to room temperature after, with containing nickelous nitrate (analytical pure, Beijing Chemical Plant's product) 26.0 grams, ammonium metawolframate (technical grade, Sichuan Zigong Hard Alloy Foundry product) 166 milliliters of the aqueous solution dipping of 68.8 grams is 1 hour, and 120 ℃ of dryings in 450 ℃ of roastings 4 hours, obtained catalyzer C1 after 4 hours.Composition after the catalyzer C1 roasting is listed in the table 1.
Comparative Examples 1
Get the carrier S of example 1 preparation
1200 grams, with 176 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 22.4 gram, nickelous nitrate 28.7 grams, ammonium metawolframate 61.4 1 hour, 120 ℃ of dryings 4 hours in 450 ℃ of roastings 4 hours, obtained catalyzer D1.Composition after the catalyzer D1 roasting is listed in the table 1.
Table 1
Example 2
The explanation of this example the invention provides the effect of method in straight-run diesel oil hydrofining.
Evaluation is carried out on 250 milliliters of fixed-bed reactor, and stock oil character sees Table 2.Catalyzer C1 is broken into the particle of diameter 2-4 millimeter, and 100 milliliters of catalyst levelss are before formal charging, with the kerosene that contains 2.5 weight %DMDS catalyzer is vulcanized earlier, cure conditions is: pressure 3.2 MPas, 290 ℃ of temperature, 8 hours time, vulcanized oil charging air speed 2.0 hours
-1, hydrogen to oil volume ratio 300 is cut raw material afterwards and is reacted, and the hydrogen dividing potential drop is 3.2 MPas, and hydrogen to oil volume ratio is 300, liquid hourly space velocity 2.0h
-1, temperature of reaction is 340 ℃.
Comparative Examples 2
The explanation of this Comparative Examples adopts the Comparative Examples catalyzer to carry out the effect of diesel oil hydrofining.
Adopt with example 15 same procedure and estimate Comparative Examples catalyzer D1.
The measuring method of sulphur is SH/T 0253-92, and the measuring method of nitrogen is SH/T 0657-1998.The hydrodesulfurization activity of catalyzer calculates by 1.65 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related calculation formula is as follows.
With the D1 activity of such catalysts is 100, and the evaluation result of catalyzer C1 and D1 is listed in the table 3.
Table 2
| Density, g/ml | 0.840 |
| Refractive power, n D 20 | 1.4684 |
| S, weight % | 0.83 |
| N，μg/g | 204 |
| Boiling range D-86, ℃ | |
| Initial boiling point | 189 |
| Density, g/ml | 0.840 |
| 50% point | 280 |
| Final boiling point | 392 |
Table 3
| Catalyzer | Desulphurizing activated relatively, % | Relative denitrification activity, % | |
| Example 2 | C1 | 110 | 116 |
| Comparative Examples 2 | D1 | 100 | 100 |
Data by table 3 can show that when diesel oil distillate was carried out hydrofining, the method for the invention provides had better hydrofining effect.
Example 3
Take by weighing the 1000 gram aluminium hydrate powder (dry glue powders that Chang Ling refinery company catalyst plant is produced, butt 71 weight %) and 520 grams contain the silicon sol (Haiyang Chemical Plant, Qingdao's product) of silicon-dioxide 30%, mixing the back, to be extruded into circumscribed circle diameter with banded extruder be 1.4 millimeters butterfly bar, wet bar was in 120 ℃ of dryings 4 hours, roasting is 3 hours under 600 ℃ of conditions, make carrier S 2, silica content is 18.0 weight % in the S2 carrier.
Take by weighing carrier S 2200 grams, with containing ammonium paramolybdate 13.3 grams, phosphoric acid (chemical pure, 85% concentration, Beijing Chemical Plant's product) this carrier of 176 milliliters of dippings of the aqueous solution of 18.3 grams, nickelous nitrate 24.0 grams, ammonium metawolframate 54.3 grams is 3 hours, 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours obtain catalyzer C2.Composition after the catalyzer C2 roasting is listed in the table 4.
Comparative Examples 3
Comparative catalyst D2 is according to the leaching method preparation altogether of the 8 disclosed substeps of example among the Chinese patent CN1083476C, and the composition after its roasting sees Table 1.
Example 4
Take by weighing carrier S 2200 grams, flooded above-mentioned carriers 3 hours for 176 milliliters with the aqueous solution that contains ammonium paramolybdate 19.9 grams, 120 ℃ of dryings 4 hours, 280 ℃ of dryings are 4 hours again, with this carrier of 165 milliliters of dippings of the aqueous solution that contains nickelous nitrate 50.4 gram, ammonium metawolframate 82.8 grams, phosphatase 11 5.5 grams 3 hours, 120 ℃ of dryings 6 hours were afterwards with 120 milliliters of dippings of the aqueous solution that contains ethylene glycol 51.1 grams 3 hours, 120 ℃ of dryings 4 hours obtain catalyzer C3.Calculating ethylene glycol is 1.4 with mol ratio in nickel, molybdenum and the tungsten of oxide compound.Composition after the catalyzer C3 roasting is listed in the table 4.
Table 4
Example 5-6
The effect of present embodiment explanation the inventive method in diesel oil hydrofining.
Evaluate catalysts C2 on 20 milliliters of diesel hydrotreating units, C3.Raw materials used oil is the catalytic diesel oil of density (20 ℃) 0.9026g/ml, refractive power (20 ℃) 1.4699, nitrogen content 100ppm, sulphur content 1.1 weight %, reaction conditions: hydrogen dividing potential drop 3.2MPa, liquid hourly space velocity 2.0h
-1, hydrogen to oil volume ratio 300: 1, temperature of reaction is 350 ℃.
Comparative Examples 4
The explanation of this Comparative Examples adopts comparative catalyst D2 to carry out the effect of diesel oil hydrofining, and evaluation method is with example 5.
Desulphurizing activated and denitrification activity method of calculation are with example 2.
With the D2 activity of such catalysts is 100, adopts C2, and the diesel oil hydrofining effect of C3 catalyzer sees Table 5.
Table 5
The result of table 5 shows, compares with existing method, and the inventive method has higher diesel hydrogenation for removal sulphur activity and hydrodenitrogenationactivity activity.
Example 7
Take by weighing the 1000 gram aluminium hydrate powder (dry glue powders that Chang Ling refinery company catalyst plant is produced, butt 70 weight %) and 150 grams contain the silicon sol (Haiyang Chemical Plant, Qingdao's product) of silicon-dioxide 25%, being extruded into circumscribed circle diameter with banded extruder is 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 3, silica content is 5.0 weight % in the S3 carrier.
Take by weighing carrier S 3200 gram, with this carrier with 176 milliliters of dippings of the aqueous solution of fluorinated ammonium (analytical pure, Beijing Chemical Plant's product) 26.8 grams 2 hours, 120 ℃ of dryings 3 hours, 400 ℃ of roastings 5 hours make fluorinated silicon oxide-alumina supporter.Flooded above-mentioned carriers 3 hours for 172 milliliters with the aqueous solution that contains ammonium paramolybdate 17.9 grams, 250 ℃ of dryings 5 hours, afterwards with this carrier of 166 milliliters of dippings of the aqueous solution that contains nickelous nitrate 26.2 gram, ammonium metawolframate 86.7 grams, phosphatase 79 .2 gram 3 hours, 120 ℃ of dryings 8 hours obtain catalyzer C4.Composition after the catalyzer C4 roasting is listed in the table 6.
Example 8
Take by weighing carrier S 3200 grams, the aqueous solution of this carrier with fluorinated ammonium 31.3 grams was flooded 2 hours for 176 milliliters, 120 ℃ of dryings 3 hours, 400 ℃ of roastings 3 hours, make fluorinated silicon oxide-alumina supporter. flooded above-mentioned carriers 3 hours for 170 milliliters with the aqueous solution that contains ammonium molybdate 21.5 grams, 120 ℃ of dryings 4 hours, 250 ℃ of dryings are 4 hours again, obtain containing the molybdenum carrier. then with containing nickelous nitrate 86.3 grams, ammonium metawolframate 197.7 grams, phosphatase 11 6.9 grams, this carrier of 159 milliliters of dippings of the aqueous solution of citric acid 19.2 grams 3 hours, 120 ℃ of dryings 4 hours, then in 230 ℃ of dryings 4 hours, obtain catalyzer C5. and calculate citric acid and nickel in oxide compound, the mol ratio of molybdenum and tungsten is that the composition after the 0.08. catalyzer C5 roasting is listed in the table 6.
Table 6
Embodiment 9-10
The effect of the inventive method hydrotreatment decompressed wax oil is adopted in the present embodiment explanation.
Evaluate catalysts C4, C5 on 250 milliliters of hydrogenation units.Raw materials used oil nature, reaction conditions see Table 7.
Comparative Examples 5
The effect of commercial catalysts RN-1 (commercial catalysts, Chang Ling refinery company catalyst plant product) hydrotreatment decompressed wax oil is adopted in the explanation of this Comparative Examples, and evaluation method is with example 9.
The hydrodesulfurization activity of catalyzer calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and the denitrification activity calculation formula is with example 2, and desulphurizing activated calculation formula is as follows.
With the RN-1 activity of such catalysts is 100, and the relative reactivity of other catalyzer sees Table 8.
Table 7
| Stock oil character | |
| Density (20 ℃), g/ml | 0.9077 |
| S，ppm | 18000 |
| N，ppm | 1200 |
| Condensation point, ℃ | 34 |
| Boiling range (D1160), ℃ |
| Stock oil character | |
| Initial boiling point | 242 |
| 50% point | 446 |
| 95% point | 511 |
| Reaction conditions | |
| The hydrogen dividing potential drop, MPa | 8.0 |
| Catalyst volume, ml | 100 |
| Temperature, ℃ | 375 |
| Volume space velocity, h -1 | 1.0 |
| Hydrogen-oil ratio, v/v | 800 |
Table 8
Result in the table 8 shows that with respect to the existing method that adopts commercial catalysts, the inventive method has better decompressed wax oil hydrogenating desulfurization and hydrodenitrification effect.
Example 11
With 87 gram Siral, 40 (silica-aluminas, butt 78.5 weight %, silica content is 40 weight %, Germany Condea company produces), 488 gram pseudo-boehmite (Shandong Aluminum Plant's products, butt 68 weight %) with 133 gram USY type molecular sieve (Chang Ling refinery company catalyst plant products, lattice constant 24.62 dusts, the heavy % of butt 75) mix, be extruded into circumscribed circle diameter and be 1.5 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, 500 ℃ of roastings obtained carrier S 4 in 4 hours, the content of silica-alumina is 13.7% among the S4, and the content of aluminum oxide is 66.3%, and the content of USY type molecular sieve is 20.0%.
Getting S4 carrier 100 grams flooded 2 hours for 90 milliliters with the aqueous solution that contains ammonium paramolybdate 9.3 grams, after 400 ℃ of roasting 4 hours and being cooled to room temperature, getting 80 grams flooded 2 hours for 68 milliliters once more with the aqueous solution that contains ammonium metawolframate 33.0 grams, nickelous nitrate 19.4 grams, citric acid 8.2 grams, afterwards in 200 ℃ of oven dry 6 hours, the composition that obtains citric acid among the catalyzer C6. catalyzer C6 and mol ratio in nickel, molybdenum and the tungsten sum of oxide compound and be after the 0.2. catalyzer C6 roasting sees Table 9.
Example 12
With 200 gram SB powder (German Condea company produce butt 75.0 weight %) and 88.1 gram PY type molecular sieve (Chang Ling refinery company catalyst plant product, lattice constant 24.60 dusts, P
2O
5Content: 6 weight %, butt 73 weight %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, 550 ℃ of roastings obtained carrier S 5 in 4 hours, and the content of aluminum oxide is 70.0 weight %, and the content of PY type molecular sieve is 30.0 weight %.
Get S5 carrier 100 gram with 84 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 2.0 grams, ammonium metawolframate 61.4 grams, nickelous nitrate 22.2 grams 2 hours,, obtain catalyzer C7 through 140 ℃ of dryings 3 hours.Composition after the catalyzer C7 roasting sees Table 9.
Comparative Examples 6
Get carrier S 4100 grams, flooded 2 hours for 80 milliliters, in 120 ℃ of oven dry 4 hours,, obtain catalyzer D3 afterwards 480 ℃ of roastings 4 hours with the aqueous solution that contains ammonium metawolframate 33.2 grams, nickelous nitrate 27.2 grams.Composition after the catalyzer D3 roasting sees Table 9.
Table 9
Example 13-14
The effect of this example explanation the inventive method in diesel oil hydrogenation is handled.
With density is 0.9258 gram per centimeter
3Sulphur content is that 2700ppm, nitrogen content are 1483ppm, the catalytic cracking diesel oil of cetane index (D4737) 27.3 is a raw material, on 100 milliliters of fixed bed devices, estimate the performance of catalyzer C6 provided by the invention and C7, the catalyzer loading amount is 100 milliliters, and reaction conditions is: 350 ℃ of temperature, pressure 6.4MPa, liquid hourly space velocity 1.0 hours
-1, hydrogen to oil volume ratio 700, the results are shown in Table 10.
Comparative Examples 6
According to example 13 identical condition evaluating reference catalyst D3, the results are shown in Table 10.
Table 10
| Example | 13 | 14 | Comparative Examples 6 |
| Catalyzer | C6 | C7 | D3 |
| Product density, gram per centimeter 3 | 0.8883 | 0.8901 | 0.8920 |
| Example | 13 | 14 | Comparative Examples 6 |
| Desulfurization degree, heavy % | 93.7 | 91.8 | 90.3 |
| Denitrification percent, heavy % | 97.2 | 95.9 | 94.8 |
| Product cetane index (D4737) | 36.1 | 35.5 | 35.2 |
| The cetane index increased value | 9.0 | 8.7 | 7.9 |
| Density reduction value, gram per centimeter 3 | 0.0375 | 0.0357 | 0.0338 |
| Diesel yield, V% | ＞96 | ＞96 | ＞96 |
The result that table 10 provides shows, compares with reference catalyst, and catalyzer provided by the invention not only has higher desulfurization, denitrification activity, can make at least 0.8 unit of diesel cetane-number increase rate increase simultaneously.
Claims (15)
1. method for hydrotreating hydrocarbon oil, this method is included under hydrogen existence and the hydrogenation conditions, hydrocarbon oil feed is contacted with catalyzer, described catalyzer contains carrier, nickel, molybdenum and tungsten, in oxide compound and with the catalyzer is benchmark, and the content of nickel is 1-10 weight %, 10＜molybdenum and tungsten sum≤50 weight %, wherein, the mol ratio of 2.6＜Tungsten oxide 99.999 and molybdenum oxide≤30.
2. method according to claim 1, it is characterized in that, in oxide compound and with the catalyzer is benchmark, nickel content in the described catalyzer is 1-7 weight %, 15＜molybdenum and tungsten sum≤45 weight %, wherein, mol ratio≤24 of the mol ratio 3.1＜Tungsten oxide 99.999 of Tungsten oxide 99.999 and molybdenum oxide and molybdenum oxide.
3. method according to claim 1 is characterized in that, the carrier in the described catalyzer is selected from one or more in aluminum oxide, silica-alumina, molecular sieve and their mixture.
4. method according to claim 3 is characterized in that described aluminum oxide is selected from one or more among γ, η, θ, δ and the χ; Be selected from and contain one or more and be selected from titanium, magnesium, boron, zirconium, thorium, niobium, rare earth and dose among γ, η, θ, δ and the χ of component one or more.
5. method according to claim 4 is characterized in that, described aluminum oxide is gama-alumina or contains one or more and be selected from the gama-alumina that titanium, magnesium, boron, zirconium, thorium, niobium, rare earth are dosed component.
6. method according to claim 3 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 aluminum oxide is 55-98 weight %.
7. method according to claim 6 is characterized in that, the content of silicon oxide is 5-40 weight % in the described silica-alumina, and the content of aluminum oxide is 60-95 weight %.
8. method according to claim 3, it is characterized in that, described molecular screening is benchmark from the zeolite molecular sieve of Chang Zuowei catalytic cracking activity component, in the non-zeolitic molecular sieves one or more with described carrier, and the content of described molecular sieve is 0.5-85 weight %.
9. method according to claim 8 is characterized in that, described molecular screening one or more in Y zeolite, beta zeolite, mordenite, ZSM-5 are benchmark with described carrier, and the content of described molecular sieve is 5-50 weight %.
10. method according to claim 9 is characterized in that, one or more the mixture of described molecular screening in Y zeolite, beta zeolite, ZSM-5 is benchmark with described carrier, and the content of described molecular sieve is 5-50 weight %.
11. method according to claim 1 is characterized in that, described catalyzer contains a kind of and blended adjuvant component that is selected from fluorine, phosphorus and the boron, is benchmark in element and catalyzer, and the content of described adjuvant component is 0.5-10 weight %.
12. method according to claim 1 is characterized in that, described catalyzer contains to be selected from and contains in oxygen or the nitrogenous organism one or more, and described organism is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide compound.
13. method according to claim 1 is characterized in that, described hydrogenation conditions comprises: temperature of reaction 200-420 ℃, and hydrogen dividing potential drop 2-18 MPa, liquid hourly space velocity 0.3-10 hour-1, hydrogen to oil volume ratio 50-5000.
14. method according to claim 13 is characterized in that, described hydrogenation conditions comprises: temperature of reaction 220-400 ℃, hydrogen dividing potential drop 2-15 MPa, liquid hourly space velocity 0.3-5 hour-1, hydrogen to oil volume ratio 50-4000.
15. method according to claim 1 is characterized in that, described hydrocarbon ils is selected from one or more in crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, frivolous asphalt oil, the heavy deasphalted oil.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
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| CN200510073100A CN1872961B (en) | 2005-05-31 | 2005-05-31 | Method for hydrotreating hydrocarbon oil |
| EP06722384A EP1880760A4 (en) | 2005-04-21 | 2006-04-20 | A hydrogenation catalyst and its application |
| 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 |
| PCT/CN2006/000743 WO2006111093A1 (en) | 2005-04-21 | 2006-04-20 | A hydrogenation catalyst and its application |
| EP12158777A EP2463025A1 (en) | 2005-04-21 | 2006-04-20 | Ni/Mo/W supported hydrogenation catalyst containing P or F and process for hydrocarbon hydrogenation |
| US11/918,851 US8697598B2 (en) | 2005-04-21 | 2006-04-20 | Hydrogenation catalyst and use thereof |
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| CN200510073100A CN1872961B (en) | 2005-05-31 | 2005-05-31 | Method for hydrotreating hydrocarbon oil |
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| 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 |
| CN103285871B (en) * | 2012-02-23 | 2016-07-06 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst containing promoter metal component and preparation thereof and application |
| CN103374393A (en) * | 2012-04-26 | 2013-10-30 | 中国石油化工股份有限公司 | Hydrotreatment method for hydrocarbon oil |
| CN103962164B (en) * | 2013-02-05 | 2016-03-30 | 神华集团有限责任公司 | Fischer-Tropsch oil hydrofining catalyst and preparation method thereof |
| EP2786978B1 (en) * | 2013-04-03 | 2016-12-07 | Scg Chemicals Co. Ltd. | Process for converting paraffin to olefin and catalyst for use therein |
| CN103191754A (en) * | 2013-04-17 | 2013-07-10 | 上海兖矿能源科技研发有限公司 | Catalyst for hydrogenation refining of Fischer-Tropsch synthetic oil, as well as preparation method and application thereof |
| CN105032474B (en) * | 2015-05-25 | 2018-01-12 | 安徽海德石油化工有限公司 | A kind of cracking c_4 cut produces 1 butylene load-type nanometer metal catalyst |
| CN106475109B (en) * | 2016-09-22 | 2019-02-12 | 中国石油大学(华东) | The preparation method of super-active hydrogenation catalyst |
| CN106475110B (en) * | 2016-09-22 | 2019-02-12 | 中国石油大学(华东) | The preparation method of superelevation content of metal hydrogenation catalyst |
| CN110090636B (en) * | 2018-01-30 | 2021-11-12 | 中国石油化工股份有限公司 | Cerium-containing aluminum hydroxide dry glue powder and preparation method thereof, and alumina carrier and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
| CN1289830A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst and its preparing process |
-
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| CN1289828A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst for fraction oil and its preparing process |
| CN1289830A (en) * | 1999-09-29 | 2001-04-04 | 中国石油化工集团公司 | Hydrorefining catalyst and its preparing process |
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