CN105498792A - Catalyst combination for hydrogenation treatment and application thereof - Google Patents

Abstract

The invention relates to a catalyst combination for hydrogenation treatment and application thereof. The catalyst combination comprises a hydrofining catalyst I and a hydrofining catalyst II. The hydrofining catalyst I contains an alumina carrier, cobalt and molybdenum hydrogenation active metal components, and on the basis of the catalyst I, in terms of CoO, the cobalt content of the catalyst I is 1-10wt.%, in terms of MoO3, the molybdenum content is 5-50wt.%; the hydrofining catalyst II contains an alumina carrier, nickel and tungsten hydrogenation active metal components, and on the basis of the catalyst II, in terms of NiO, the nickel content of the catalyst II is 1-10wt.%, and in terms of WO3, the tungsten content is 5-60 wt%. By volume and on the basis of the total amount of the catalyst combination, the catalyst combination contains 5-95% of the catalyst I and 5-95% of the catalyst II. Compared with the prior art, the catalyst composition provided by the invention has better hydrogenation performance.

Description

A kind of catalyst combination for hydrotreatment and application thereof

Technical field

The present invention relates to a kind of catalyst combination for hydrotreatment and application thereof.

Background technology

Along with environmental requirement increasingly stringent in world wide, various countries are day by day harsh to the quality requirement of vehicle fuel.In addition, because petroleum resources reduce, oil property becomes and heavily becomes bad, and refinery has to process crude oil more inferior.Therefore, significantly reduce bavin well cuts and polycyclic aromatic hydrocarbon content, significantly improve diesel quality, become the problem that oil refining enterprise is in the urgent need to address.Hydrogen addition technology reduces one of oil product impurity content, the major technique improving oil quality, and its core is hydrogenation catalyst.Prior art shows, the effect adopting the combination of different hydrogenation catalyst to carry out hydrocarbon oil hydrogenation process for some reactions is better than the effect of single dose usually.

CN1896191A discloses a kind of combined technical method of converting coal liquefied oil at maximum, liquefied coal coil after filtration and hydrogen enter stable hydrogenation reactor, with hydrogenation protecting agent, Hydrobon catalyst contacts, stable hydrogenation reactor effluent is isolated to gas, naphtha cut, diesel oil distillate and tail oil fraction, wherein stable hydrogenation diesel oil distillate, part tail oil fraction enters hydro-upgrading reactor respectively, hydrocracking reactor, reactor effluent is isolated to gas, naphtha cut and diesel oil distillate product, hydrogen rich stream loops back each reactor.The method energy maximum ground produces fine-quality diesel oil, and the total recovery of diesel oil is more than 92 % by weight, and Cetane number is more than 45.

In CN96109738, disclose a kind of hydrogenation post-refining process for lubricant oil.This technique is included in reaction temperature 200-350 DEG C, hydrogen dividing potential drop 1.0-10.0MPa, liquid volume air speed 10.5-5.0 hour ^-1, hydrogen to oil volume ratio 80-500 condition under, be that the catalyst I that 0.05-0.75 layering is loaded contacts with II successively with volume ratio by crude lube stock, catalyst I is made up of 0.5-3.0 heavy % at least one VIII race element, 3.5-14.5 heavy % at least one VI B race's element and aluminium oxide; Catalyst II is made up of 1.0-5.0 heavy % at least one VIII race element, 10.0-34.0 heavy % at least one VI B race's element and aluminium oxide.

In US5068025, disclose the Hydrofining Technology of the desulfurization of a kind of diesel oil distillate two-stage hydrogenation, aromatic saturation.This technology first paragraph adopts the heavy % of a kind of nickeliferous 1-5, the heavy % of tungsten 10-35, the heavy % of phosphorus 1-5, all the other Hydrobon catalysts being alumina support carry out hydrodesulfurization, denitrogenation, second segment adopts a kind of nickeliferous or heavy % of cobalt 1-5, the heavy % of tungsten 8-20 heavy %, phosphorus 1-5, all the other are that the Hydrobon catalyst of alumina support carries out aromatic saturated hydrogenation desulfurization.

CN102051217A discloses a kind of method of hydrotreating producing ultra-low sulfur clean diesel.Enter reactor after diesel oil distillate feedstock oil mixes with hydrogen, successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreaction, its reaction effluent carries out being separated and fractionation, obtains diesel product; The load hydrogenation catalyst for refining of described Hydrobon catalyst I to be activated metal component be cobalt-molybdenum, described Hydrobon catalyst II is body phase Hydrobon catalyst.Adopt the method that this invention provides, under mitigation condition, process poor-quality diesel-oil by cut fraction, the clean diesel product of low-sulfur or super-low sulfur can be obtained.Compared with the existing technology, when reaching the identical hydrodesulfurization degree of depth, the chemical hydrogen consumption of hydrogenation process is lower than prior art by 5 % by weight ~ 10 % by weight in this invention.

CN102851070A discloses a kind of method of producing ultra-low-sulphur diesel, diesel oil distillate feedstock oil enters into reactor from top, above-mentioned reactor is entered into from bottom after supplemental hydrogen and recycle hydrogen mixing, under hydrofining reaction condition, diesel oil distillate feedstock oil successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreaction, its reaction effluent carries out being separated and fractionation, obtains diesel product; The load hydrogenation catalyst for refining of described Hydrobon catalyst I to be activated metal component be nickel-molybdenum or nickel-molybdenum-tungsten, described Hydrobon catalyst II is body phase Hydrobon catalyst.Soluble is prior art when producing ultra-low sulfur clean diesel, and operating condition is harsh, the problems such as air speed is low.

Summary of the invention

The technical problem to be solved in the present invention is on the basis of existing technology, provides a kind of catalyst combination for hydrotreatment, and the application of this catalyst combination in hydrotreatment reaction.

The content that the present invention relates to comprises:

1., for a catalyst combination for hydrotreatment, comprise Hydrobon catalyst I and Hydrobon catalyst II, wherein,

Described Hydrobon catalyst I contains alumina support, cobalt and molybdenum hydrogenation active metals component, with described catalyst I for benchmark, in described catalyst I in the cobalt content of CoO for 1-10 % by weight, with MoO ₃the molybdenum content of meter is 5-50 % by weight;

Described Hydrobon catalyst II containing alumina support, nickel and tungsten hydrogenation active metals component, with described catalyst II for benchmark, in described catalyst II in the nickel content of NiO for 1-10 % by weight, with WO ₃the W content of meter is 5-60 % by weight;

By volume and with the total amount of described catalyst combination for benchmark, the content of the catalyst I in described catalyst combination is 5-95%, the content of catalyst II is 5-95%.

2. the catalyst combination according to 1, is characterized in that, with described catalyst I for benchmark, in described catalyst I in the cobalt content of CoO for 1-7 % by weight, more preferably 3-7 % by weight, with MoO ₃the molybdenum content of meter is 8-45 % by weight, more preferably 12-30 % by weight.

3. the catalyst combination according to 1, is characterized in that, with described catalyst II for benchmark, in described catalyst II in the nickel content of NiO for 1-8 % by weight, more preferably 2-6 % by weight, with WO ₃the W content of meter is 8-50 % by weight, more preferably 20-40 % by weight.

4. the catalyst combination according to 1, it is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of described Hydrobon catalyst I is 10-80%, more preferably 20-70%, the content of described Hydrobon catalyst II is 20-90%, more preferably 30-80%.

5. the catalyst combination according to 1, it is characterized in that, the preparation method of described Hydrobon catalyst I comprises employing dipping solution impregnated carrier, described dipping solution contains cobalt compound, molybdate compound, phosphorus-containing compound and citric acid, in described dipping solution in the concentration of the cobalt compound of cobalt for 0.01-0.1g/mL, in the concentration of the molybdate compound of molybdenum for 0.05-0.4g/mL, in the concentration of the phosphorus-containing compound of phosphorus for 0.005-0.10g/mL, the concentration of citric acid is 0.05-0.5g/mL, with UV-Vis diffuse reflection spectroscopy analysis and characterization, λ≤1 of described dipping solution, λ is that in ultraviolet-visible spectrum, the high ratio of peak-to-peak is composed at spectrum peak, 517 ± 10nm place and 772 ± 10nm place.

6. the catalyst combination according to 5, it is characterized in that, in described dipping solution in the concentration of the cobalt compound of cobalt for 0.02-0.09g/mL, in the concentration of the molybdate compound of molybdenum for 0.08-0.35g/mL, in the concentration of the phosphorus-containing compound of phosphorus for 0.007-0.08g/mL, the concentration of citric acid is 0.1-0.4g/mL, with ultraviolet-visible spectrum analysis and characterization, and the λ=0-0.95 of described dipping solution.

7. the catalyst combination according to 6, is characterized in that, described dipping solution with ultraviolet-visible spectrum analysis and characterization, the λ=0-0.80 of described dipping solution.

8. the catalyst combination according to 5, is characterized in that, after described employing dipping solution impregnated carrier, comprise dry step, described drying condition comprises: baking temperature is 100-300 DEG C, is preferably 120-280 DEG C, time is 1-12 hour, is preferably 2-8 hour.

9. a method for hydrotreating hydrocarbon oil, comprises at hydrotreating reaction conditions, uses the catalyst combination described in aforementioned 1-8 any one to carry out hydrotreatment to hydrocarbon oil crude material oil.

10. the method according to 9, is characterized in that, it is 300-400 DEG C that described hydrogenation conditions comprises temperature, and be preferably 320-380 DEG C, pressure is 1-10MPa, is preferably 1-8MPa, and during the liquid of hydrocarbon ils, volume space velocity is 0.5-3 hour ^-1, be preferably 0.5-2.5 hour ^-1, hydrogen to oil volume ratio is 100-800, is preferably 100-700.

In the present invention, the carrier of described Hydrobon catalyst I is selected from the aluminium oxide that Chang Zuowei catalyst carrier uses, such as, be selected from γ-, δ-, η-, one or more in θ-aluminium oxide, preferably gama-alumina wherein; Described hydrogenation active metals component is cobalt and molybdenum.On this basis, described Hydrobon catalyst I can be commercially available commodity or adopt arbitrary prior art to prepare.

Inventor finds, when heating further the cobalt compound adopting conventional method to configure, molybdate compound, phosphorus-containing compound and citric acid maceration extract, the character of solution changes, and the Hydrogenation of cobaltmolybdate catalyst prepared by the solution changed by this character is improved.Particularly when the nickel tungsten catalyst this catalyst and prior art provided combinationally uses, show good hydrodesulfurization, hydrodenitrogeneration performance.

The change of described maceration extract character can adopt UV-Vis diffuse reflection spectroscopy analysis and characterization, cobalt-molybdenum-phosphorus-citric acid the dipping solution conventionally prepared (such as, after adding phosphoric acid, citric acid, basic cobaltous carbonate and molybdenum trioxide respectively in deionized water, this suspension is heated to 80 DEG C to be easy to dissolve through stirring, obtain the solution containing cobalt and molybdenum component), the λ > 1 of this solution.Wherein, λ is that in ultraviolet-visible spectrum, the high ratio of peak-to-peak is composed at spectrum peak, 517 ± 10nm place and 772 ± 10nm place.When being heated further by this solution, the spectrum peak, 517 ± 10nm place of dipping solution dies down (peak height reduction) or disappears.According to the definition of the present invention about λ, when spectrum peak, 517 ± 10nm place disappears, λ=0 of its correspondence.Control λ≤1 of described dipping solution, preferred λ=0-0.95, more preferably during λ=0-0.80, the Hydrogenation of the catalyst prepared by this record solution significantly improves.

In the preferred embodiment of the present invention, described Hydrobon catalyst I adopts aforesaid character to there occurs the method preparation of the dipping solution oxide impregnation alumina supporter of change.Wherein, the preparation method of described maceration extract comprises: cobalt compound, molybdate compound, phosphorus-containing compound and citric acid mix with water, are dissolved into solution by (1); (2) solution step (1) obtained, at 60 DEG C-300 DEG C, is preferably 75 DEG C-180 DEG C, and more preferably reaction 0.5 hour-200 hours at 80 DEG C-150 DEG C, is preferably 1 hour-100 hours, more preferably 2 hours-50 hours; Wherein, the consumption of described each component to make in final described dipping solution in the concentration of the cobalt compound of cobalt as 0.01-0.1g/mL, in the concentration of the molybdate compound of molybdenum for 0.05-0.4g/mL, in the concentration of the phosphorus-containing compound of phosphorus for 0.005-0.1g/mL, the concentration of citric acid is 0.05-0.5g/mL.With UV-Vis diffuse reflection spectroscopy analysis and characterization, λ≤1 of this dipping solution, λ is that in ultraviolet-visible spectrum, the high ratio of peak-to-peak is composed at spectrum peak, 517 ± 10nm place and 772 ± 10nm place.

In further preferred embodiment, the consumption of described each component to make in final described dipping solution in the concentration of the cobalt compound of cobalt, for 0.02-0.09g/mL, to be more preferably 0.03-0.08g/mL; In the concentration of the molybdate compound of molybdenum for 0.08-0.35g/mL, be more preferably 0.10-0.3g/mL; In the concentration of the phosphorus-containing compound of phosphorus for 0.007-0.08g/mL, be more preferably 0.01-0.03g/mL; The concentration of citric acid is 0.1-0.4g/mL, is more preferably 0.15-0.3g/mL.With ultraviolet-visible spectrum analysis and characterization, the λ=0-0.95 of described dipping solution, more preferably λ=0-0.80.

In the present invention, the described cobalt compound in prepared by described hydrogenation catalyst I is selected from water miscible cobalt compound.Such as, containing the salt of cobalt metal component, oxide and hydroxide.They can be selected from one or more in the nitrate of cobalt, chloride, sulfate, formates, acetate, phosphate, citrate, oxalates, carbonate, subcarbonate, hydroxide, phosphate, phosphide, sulfide, aluminate, molybdate, tungstates, oxide.One or more preferably in oxalates wherein, carbonate, subcarbonate, hydroxide, phosphate, molybdate, tungstates, oxide, more preferred subcarbonate wherein and carbonate.

Described molybdate compound is selected from water miscible molybdate compound, such as, containing salt, the oxide of molybdenum component.They can be selected from one or more in ammonium molybdate, heteropolyacid salt, molybdenum oxide.

Described phosphorus-containing compound can be selected from one or more in phosphoric acid, ammonium dihydrogen phosphate (ADP), diammonium hydrogen phosphate, sodium dihydrogen phosphate and sodium hydrogen phosphate, preferably phosphoric acid wherein.

According to the preparation method of described hydrogenation catalyst I dipping solution provided by the invention, described heating can be carried out at the container situ of obtain solution, also can not carry out in position.Described heating can be carried out in the quiescent state, also can in a dynamic state, such as, carry out under stirring.

When heating maceration extract, evaporation of water and loss can be attended by, therefore, described process can be carried out in airtight system (such as at airtight reactor), when process is carried out in open system, carry out at relatively high temperatures, such as, when temperature is more than 90 DEG C, process can be carried out in the container being configured with reflux.

According to hydrogenation catalyst I provided by the invention, wherein said carrier optionally can be made into the article shaped of arbitrary convenient operation, as spherical, compressing tablet and bar shaped.Describedly shapingly can be undertaken by conventional process, as the method such as precursor compressing tablet, spin, extrusion of aluminium oxide and/or aluminium oxide.When adopting customary way shaping, for guaranteeing that shaping to carry out smoothly introducing auxiliary agent in material to be formed be allow, such as when the precursor extrusion of aluminium oxide and/or aluminium oxide, appropriate extrusion aid and/or adhesive and water, then extrusion molding can be added.The kind of described extrusion aid, peptizing agent and consumption are this area routine, such as common extrusion aid can be selected from one or more in sesbania powder, methylcellulose, starch, polyvinyl alcohol, PVOH, and common peptizing agent can be selected from a kind of in nitric acid, citric acid or their mixture.Described article shaped drying, roasting obtain carrier of the present invention.Here, described drying and the method for roasting and operating condition are conventional method and operating condition.Such as, described drying means is heat drying, and baking temperature is 100-300 DEG C, is preferably 120-280 DEG C; Drying time is 1-12 hour, is preferably 2-8 hour; The condition of described roasting can be the routine selection of this area.Usually, the condition of described roasting comprises: temperature can be 350-650 DEG C, is preferably 400-600 DEG C; The time of described roasting can be 2-6 hour, is preferably 3-5 hour.

The dipping method preparing described hydrogenation catalyst I is conventional impregnation methods, and comprise the saturated infusion process in hole, excessive infusion process and multiple maceration etc., carry out drying, roasting or not roasting afterwards, these methods all can be applicable to for preparing catalyst of the present invention.In concrete enforcement, preferred dip operation condition comprises: solution is by volume 0.5-10:1, more preferably 0.7-8:1 with the ratio of carrier by weight.When in described dipping process be maceration extract excessive time, have free solution to exist in the impregnation product after having flooded, now the preferred step comprising filtration before carrying out drying, to remove free solution.Drying of the present invention can be that the routine of this area is selected.Usually, the condition of described drying comprises: temperature can be 100-300 DEG C, is preferably 120-280 DEG C; Time can be 1-12 hour, is preferably 2-8 hour.When needs carry out roasting, the method for described roasting and condition can be that the routine of this area is selected.Usually, the condition of described roasting comprises: temperature can be 350-550 DEG C, is preferably 400-500 DEG C; Time can be 1-8 hour, is preferably 2-6 hour.

According to catalyst I provided by the invention, can also not affect containing any the material that the performance that the invention provides catalyst maybe can improve catalyst performance provided by the invention.As contained the components such as boron, be benchmark in element and with catalyst, the content of boron is no more than 10 % by weight, is preferably 0.5-6 % by weight.

According to preparation method provided by the invention, when in described catalyst I also containing being selected from the components such as boron, also comprise introducing and be selected from the step of the components such as boron, described in be selected from the introducing method of the components such as boron can by number of ways, as can be introduce in carrier preparation process; Can be that the method for flooding described carrier after the compound obtain solution containing auxiliary agent is introduced.When auxiliary agent introduces described carrier with the method for dipping, comprise the step of carrying out roasting, described sintering temperature is 250-600 DEG C, and be preferably 350-500 DEG C, roasting time is 2-8 hour, is preferably 3-6 hour.

In the present invention, the support selected from alumina of described Hydrobon catalyst II, preferably gama-alumina wherein; Described hydrogenation active metals component is nickel and tungsten.On this basis, described Hydrobon catalyst II can be commercially available commodity or adopt arbitrary prior art to prepare.

Such as, Hydrobon catalyst disclosed in CN85104438, it is by γ-Al ₂o ₃support tungsten and nickel oxide and auxiliary agent fluorine formed, it forms (weight): nickel oxide 1 ~ 5%, tungsten oxide 12 ~ 35%, and fluorine is 1 ~ 9%.

Catalyst for hydrorefining distillate oil disclosed in CN1169336, it consists of the heavy % of nickel oxide 1-5, the heavy % of tungsten oxide 12-35, the heavy % of fluorine 1-9, all the other are aluminium oxide, this aluminium oxide be by one or more little porous aluminum oxides and one or more macroporous aluminium oxides according to 75: 25-50: 50 weight ratio be composited, wherein little porous aluminum oxide is the aluminium oxide that pore volume that bore dia is less than 80 dust holes accounts for total pore volume more than 95%, and macroporous aluminium oxide is the aluminium oxide that the pore volume in bore dia 60-600 dust hole accounts for total pore volume more than 70%.This catalyst is specially adapted to the hydrofinishing that boiling range is the inferior distillate oil of 80-550 DEG C of high sulfur content.

Hydrocracking catalyst disclosed in CN101733149A, this catalyst contains carrier and load group vib on this carrier and VIII hydrogenation active component and organic additive, with the total amount of catalyst for benchmark, in described catalyst, the content of carrier is 40-90 % by weight, the content of organic additive is 0.5-30 % by weight, with oxide basis, the content of described group vib hydrogenation active component is 5-35 % by weight, the content of group VIII hydrogenation active component is 1-15 % by weight, described carrier contains Y zeolite, silica binder, the weight ratio of silica binder and molecular sieve is 0.01 ~ 10.This catalyst by comprise by comprise Y zeolite and silica binder precursor mix, shaping, dry and carrier is prepared in roasting, backward described carrier in introduce hydrogenation active metals component and the preparation of organic method.

These catalyst all can be used as described catalyst II for the present invention.About the more detailed preparation method of above-mentioned catalyst, all on the books in above-mentioned patent document, in the lump their parts as content of the present invention are quoted here.

In described catalyst combination of the present invention, preferred described catalyst I and catalyst II layered arrangement, described layered arrangement makes described hydrocarbon oil crude material oil contact with Hydrobon catalyst II with Hydrobon catalyst I successively when applying; Or described layered arrangement makes described hydrocarbon oil crude material oil contact with Hydrobon catalyst I with Hydrobon catalyst II successively.

According to hydrofinishing process provided by the invention, the method be the catalyst combination of the application of the invention to improve the catalytic activity in unifining process, other condition for hydrofinishing process is not particularly limited, can be this area routine select.Usually, described hydrorefined condition comprises: temperature is 300-400 DEG C; Pressure is 1.0-10.0MPa (in gauge pressure); During the liquid of hydrocarbon ils, volume space velocity is 0.5-3.0 hour ^-1; Hydrogen to oil volume ratio is 100-800.Described hydrogen to oil volume ratio refers to the ratio of the volume flow rate of hydrogen and the volume flow rate of hydrocarbon ils.

According to the invention provides method, optionally described catalyst combination can with other agent conbined usage, to reach better result of use.Such as, combinationally use in described catalyst combination and protective agent (Hydrogenation active protective agent).When described catalyst combination and other agent (as protective agent) conbined usage, the consumption of other agent is to realize, for the purpose of its function, being not particularly limited this.Such as, when described catalyst combination and protective agent conbined usage, by volume and with catalyst total amount for benchmark, protectant consumption can be 5-15%.

According to hydrofinishing process of the present invention, described carbon monoxide-olefin polymeric preferably adopts the conventional method of this area to carry out sulfuration before use.Usually, the condition of described sulfuration can comprise: in presence of hydrogen, at the temperature of 360-400 DEG C, carries out the presulfurization of 2-4 hour with one or more in sulphur, hydrogen sulfide, carbon disulfide, DMDS or polysulfide.According to hydrofinishing process of the present invention, described presulfurization can be carried out outside reactor, also can be In-situ sulphiding in reactor.

Hydrofinishing process according to the present invention is applicable to the subtractive process such as hydrodesulfurization, hydrodenitrogeneration of various hydrocarbon oil crude material.Described hydrocarbon oil crude material can be such as gasoline, diesel oil, lubricating oil, kerosene and naphtha; Also can be reduced crude, decompression residuum, pertroleum wax and Fischer-Tropsch synthesis oil.

Detailed description of the invention

The present invention is described further for the following examples.

UV-Vis diffuse reflection spectroscopy analyzes (UV-Vis), adopt the multi-functional spectrophotometry instrument of Lambda35 type of Perkin-Elmer company of the U.S., under the experiment condition of light neon source, measurement wavelength 286nm, slit width 1.0nm, sample detection time 4.5min, detection step-length 2.0s, measure the ultra-violet absorption spectrum of solution within the scope of 450-900nm.

In catalyst, the content of each element is analyzed, and adopts to be purchased to measure from the 3271E type Xray fluorescence spectrometer of Rigaku electric machine industry Co., Ltd..

Embodiment 1-3 illustrates that preparation the invention provides the maceration extract conventionally prepared of catalyst I.

Embodiment 1

Take 27.2 grams of molybdenum trioxides respectively, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving 1 hour, obtain clarifying dipping solution, add water to 85mL, obtain solution L1.The λ value of dipping solution L1, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 2

Take 28.2 grams of molybdenum trioxides respectively, 9.5 grams of basic cobaltous carbonates, 11.4 grams of phosphoric acid put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving 1 hour, obtain clarifying dipping solution, add water to 85mL, obtain solution L2.The λ value of dipping solution L2, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 3

Take 11.5 grams of molybdenum trioxides respectively, 3.5 grams of basic cobaltous carbonates, 5.8 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving 1 hour, obtain clarifying dipping solution, add water to 85mL, obtain solution L3.The λ value of dipping solution L3, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 4-9 illustrates that preparation the invention provides the maceration extract prepared according to the preferred process of the present invention of catalyst I.

Embodiment 4

Cobalt molybdenum solution provided by the invention:

Take 27.2 grams of molybdenum trioxides respectively, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving, after about 1 hour, become brownish red settled solution.This solution is heated to 90 DEG C and under agitation constant temperature 8 hours in beaker, adds water to 85mL, obtains clarification dipping solution S1.The λ value of dipping solution S1, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 5

Cobalt molybdenum solution provided by the invention:

Take 20 grams of molybdenum trioxides respectively, 14.5 grams of basic cobaltous carbonates, 8.7 grams of phosphoric acid, 18 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving, after about 1 hour, become brownish red settled solution.This solution is heated to 100 DEG C and constant temperature 1 hour in closed container, adds water to 85mL, obtains clarification dipping solution S2.The λ value of dipping solution S2, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 6

Cobalt molybdenum solution provided by the invention:

Take 38 grams of molybdenum trioxides respectively, 8.6 grams of basic cobaltous carbonates, 4.7 grams of phosphoric acid, 10.7 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving, after about 1 hour, become brownish red settled solution.This solution is heated to 70 DEG C and under agitation constant temperature 18 hours in beaker, adds water to 85mL, obtains clarification dipping solution S3.The λ value of dipping solution S3, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 7

Cobalt molybdenum solution provided by the invention:

Take 27.2 grams of molybdenum trioxides respectively, 9.1 grams of basic cobaltous carbonates, 6.5 grams of phosphoric acid, 15 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving, after about 1 hour, become brownish red settled solution.This solution is heated to 120 DEG C and constant temperature 12 hours in closed container, adds water to 85mL, obtains clarification dipping solution S4.The λ value of dipping solution S4, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 8

Cobalt molybdenum solution provided by the invention:

Take 24 grams of molybdenum trioxides respectively, 10 grams of basic cobaltous carbonates, 6.5 grams of phosphoric acid, 8.4 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving, after about 1 hour, become brownish red settled solution.This solution is heated to 120 DEG C and constant temperature 2 hours in closed container, adds water to 85mL, obtains clarification dipping solution S5.The λ value of dipping solution S5, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Embodiment 9

Cobalt molybdenum solution provided by the invention:

Take 27.2 grams of molybdenum trioxides respectively, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 19 grams of citric acids put into 55mL deionized water, be heated to 80 DEG C and carry out stirring and dissolving, after about 1 hour, become brownish red settled solution.This solution is heated to 140 DEG C and constant temperature 10 hours in closed container, adds water to 85mL, obtains clarification dipping solution S6.The λ value of dipping solution S6, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) of citric acid (MTA) and the mol ratio (n of phosphorus and molybdenum _p/ n _mo), the mol ratio (n of molybdenum and cobalt _mo/ n _co), the molar ratio (n of citric acid and cobalt _cTA/ n _co) list table 1 in.

Table 1

, there is spectrum peak, 517nm place in the spectrogram of solution, but do not occur that 772nm composes peak, solution λ=∞ now in note: with ultraviolet-visible spectrum analysis and characterization.

The carrier that below the invention provides catalyst I and reference catalyst I use is prepared as follows: take 2000 grams of aluminium hydrate powders (dry glue powder that Chang Ling branch company catalyst plant is produced, butt 72 % by weight), the butterfly bar that circumscribed circle diameter is 1.3 millimeters is extruded into banded extruder, wet bar was in 120 DEG C of dryings 4 hours, roasting 3 hours under 600 DEG C of conditions, obtained carrier Z1.The water absorption rate of Z1 is 0.85.

Embodiment 10-16 illustrates catalyst I provided by the invention and preparation thereof.

Embodiment 10

Catalyst I-1 prepared by cobalt molybdenum solution provided by the invention:

By saturated for 85mL solution S 1 dipping 100 grams of Z1 carriers 2 hours, 250 DEG C of dryings 3 hours, obtain catalyst I-1, its composition was in table 2.

Embodiment 11

Catalyst I-2 prepared by cobalt molybdenum solution provided by the invention:

By saturated for 85mL solution S 2 dipping 100 grams of Z1 carriers 2 hours, 200 DEG C of dryings 3 hours, obtain catalyst I-2, its composition was in table 2.

Embodiment 12

Catalyst I-3 prepared by cobalt molybdenum solution provided by the invention:

By saturated for 85mL solution S 3 dipping 100 grams of Z1 carriers 3 hours, 250 DEG C of dryings 3 hours, obtain catalyst I-3, its composition was in table 2.

Embodiment 13

Catalyst I-4 prepared by cobalt molybdenum solution provided by the invention:

By saturated for 85mL solution S 4 dipping 100 grams of Z1 carriers 2 hours, 150 DEG C of dryings 5 hours, obtain catalyst I-4, its composition was in table 2.

Embodiment 14

Catalyst I-5 prepared by cobalt molybdenum solution provided by the invention:

By saturated for 85mL solution S 5 dipping 100 grams of Z1 carriers 2 hours, 200 DEG C of dryings 4 hours, obtain catalyst I-5, its composition was in table 2.

Embodiment 15

Catalyst I-6 prepared by cobalt molybdenum solution provided by the invention:

By saturated for 85mL solution S 6 leaching 100 grams of stain Z1 carriers 2 hours, 200 DEG C of dryings 3 hours, obtain catalyst I-6, its composition was in table 2.

Embodiment 16

By saturated for 85mL solution L1 dipping 100 grams of Z1 carriers 2 hours, 180 DEG C of dryings 3 hours, obtain catalyst C1, its composition was in table 2.

Table 2

Embodiment	Catalyst is numbered	MoO 3(% by weight)	CoO (% by weight)	P 2O 5(% by weight)
					10	I-1	20.5	4.0	2.2
11	I-2	15.2	6.4	3.9
					12	I-3	25.5	3.5	1.7
13	I-4	20.1	3.9	2.8
					14	I-5	18.2	4.5	2.8
15	I-6	20.3	4.0	2.2
					16	C1	20.1	3.9	2.1

Embodiment 17-19 illustrates the preparation method of catalyst II.

Embodiment 17

Hydrogenation catalyst II-1: adopt patent CN85104438 method to prepare hydrogenation catalyst II-1, it comprises the nickel oxide of 3 % by weight, the tungsten oxide of 25 % by weight, the fluorine (calculating with element fluorine) of 2 % by weight, all the other are aluminium oxide.

Embodiment 18

Hydrogenation catalyst II-2: adopt patent ZL97112397 method to prepare hydrogenation catalyst II-2, it comprises the nickel oxide of 3 % by weight, the tungsten oxide of 25 % by weight, the fluorine (calculating with element fluorine) of 2 % by weight, all the other are aluminium oxide.

Embodiment 19

Hydrogenation catalyst II-3: adopt patent ZL97112397 method to prepare hydrogenation catalyst II-3, it comprises the nickel (in NiO) of 4 % by weight, the tungsten (in tungsten oxide) of 30 % by weight, the fluorine (calculating with element fluorine) of 4 % by weight, all the other are aluminium oxide.

Embodiment 20-26

This example illustrates the diesel oil hydrofining performance of hydrogenating catalyst composition provided by the invention.

Respectively evaluate catalysts composition on 30 milliliters of diesel hydrotreating units, in catalyst combination and combination, in table 3, result illustrates in table 3 for the content (amount of catalyst II is surplus) of each catalyst.

Raw materials used is Middle East straight-run diesel oil, and its character is as follows:

S content: 9700wppm

N content: 97wppm

Density (20 DEG C): 0.8321g/cm ³

Refraction index (20 DEG C): 1.4658

Use following process condition:

Volume space velocity during liquid: 2.0h ^-1; Hydrogen to oil volume ratio: 300; Hydrogen dividing potential drop: 3.2MPa; Reaction temperature: 330 DEG C

Adopt relative hydrodesulfurization activity to carry out the hydrodesulfurization activity of evaluate catalysts, computational methods be using hydrodesulfurization reaction as 1.65 order reaction process, be calculated as follows the reaction rate constant k (X) of catalyst X _hDS:

In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction.

The hydrodesulfurization activity (being designated as k (C1) HDS) of the catalyst C1 prepared with embodiment 16, for benchmark, is calculated as follows the relative hydrodesulfurization activity of catalyst X:

In following examples and comparative example, adopt relative hydrodenitrogenationactivity activity to carry out the hydrodenitrogenationactivity activity of evaluate catalysts, computational methods be using hydrodenitrogeneration reaction as 1 order reaction process, be calculated as follows the reaction rate constant k (X) of catalyst X _hDN:

In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction,

The hydrodenitrogenationactivity activity (being designated as k (C1) HDN) of the catalyst C1 prepared with comparative example 4, for benchmark, is calculated as follows the relative hydrodenitrogenationactivity activity of catalyst X:

Comparative example 1,2

Adopt the method evaluation catalyst C1 identical with embodiment 20-26, II-1 activity, result illustrates in table 3.

Table 3

The result display of table 3, prepared according to the methods of the invention carbon monoxide-olefin polymeric, when the hydrofinishing for hydrocarbon ils, has higher catalytic activity.

Claims (10)

1., for a catalyst combination for hydrotreatment, comprise Hydrobon catalyst I and Hydrobon catalyst II, wherein,

Described Hydrobon catalyst I contains alumina support, cobalt and molybdenum hydrogenation active metals component, with described catalyst I for benchmark, in described catalyst I in the cobalt content of CoO for 1-10 % by weight, with MoO ₃the molybdenum content of meter is 5-50 % by weight;

Described Hydrobon catalyst II containing alumina support, nickel and tungsten hydrogenation active metals component, with described catalyst II for benchmark, in described catalyst II in the nickel content of NiO for 1-10 % by weight, with WO ₃the W content of meter is 5-60 % by weight;

By volume and with the total amount of described catalyst combination for benchmark, the content of the catalyst I in described catalyst combination is 5-95%, the content of catalyst II is 5-95%.

2. the catalyst combination according to 1, is characterized in that, with described catalyst I for benchmark, in described catalyst I in the cobalt content of CoO for 1-7 % by weight, more preferably 3-7 % by weight, with MoO ₃the molybdenum content of meter is 8-45 % by weight, more preferably 12-30 % by weight.

3. the catalyst combination according to 1, is characterized in that, with described catalyst II for benchmark, in described catalyst II in the nickel content of NiO for 1-8 % by weight, more preferably 2-6 % by weight, with WO ₃the W content of meter is 8-50 % by weight, more preferably 20-40 % by weight.

4. the catalyst combination according to 1, it is characterized in that, by volume and with the total amount of described catalyst combination for benchmark, the content of described Hydrobon catalyst I is 10-80%, more preferably 20-70%, the content of described Hydrobon catalyst II is 20-90%, more preferably 30-80%.

5. the catalyst combination according to 1, it is characterized in that, the preparation method of described Hydrobon catalyst I comprises employing dipping solution impregnated carrier, described dipping solution contains cobalt compound, molybdate compound, phosphorus-containing compound and citric acid, in described dipping solution in the concentration of the cobalt compound of cobalt for 0.01-0.1g/mL, in the concentration of the molybdate compound of molybdenum for 0.05-0.4g/mL, in the concentration of the phosphorus-containing compound of phosphorus for 0.005-0.10g/mL, the concentration of citric acid is 0.05-0.5g/mL, with UV-Vis diffuse reflection spectroscopy analysis and characterization, λ≤1 of described dipping solution, λ is that in ultraviolet-visible spectrum, the high ratio of peak-to-peak is composed at spectrum peak, 517 ± 10nm place and 772 ± 10nm place.

6. the catalyst combination according to 5, it is characterized in that, in described dipping solution in the concentration of the cobalt compound of cobalt for 0.02-0.09g/mL, in the concentration of the molybdate compound of molybdenum for 0.08-0.35g/mL, in the concentration of the phosphorus-containing compound of phosphorus for 0.007-0.08g/mL, the concentration of citric acid is 0.1-0.4g/mL, with ultraviolet-visible spectrum analysis and characterization, and the λ=0-0.95 of described dipping solution.

7. the catalyst combination according to 6, is characterized in that, described dipping solution with ultraviolet-visible spectrum analysis and characterization, the λ=0-0.80 of described dipping solution.

8. the catalyst combination according to 5, is characterized in that, after described employing dipping solution impregnated carrier, comprise dry step, described drying condition comprises: baking temperature is 100-300 DEG C, is preferably 120-280 DEG C, time is 1-12 hour, is preferably 2-8 hour.

9. a method for hydrotreating hydrocarbon oil, comprises at hydrotreating reaction conditions, uses the catalyst combination described in aforementioned 1-8 any one to carry out hydrotreatment to hydrocarbon oil crude material oil.

10. the method according to 9, is characterized in that, it is 300-400 DEG C that described hydrogenation conditions comprises temperature, and be preferably 320-380 DEG C, pressure is 1-10MPa, is preferably 1-8MPa, and during the liquid of hydrocarbon ils, volume space velocity is 0.5-3 hour ^-1, be preferably 0.5-2.5 hour ^-1, hydrogen to oil volume ratio is 100-800, is preferably 100-700.