CN103374393A - Hydrotreatment method for hydrocarbon oil - Google Patents

Abstract

The invention relates to a hydrotreatment method for hydrocarbon oil. The method comprises the following step of: contacting hydrocarbon oil feedstock with a catalyst in the presence of hydrogen and under a hydrogenation reaction condition, wherein the catalyst contains vectors, at least one metal component selected from a VIII group and at least one metal component selected from a VIB group. The method is characterized in that the VIB-group metal component exists in a form of metal oxide, and the VIII-group metal component exists in a form of metal salt. Compared with the existing method, the hydrotreatment method provided by the invention has the advantage that the hydrotreatment effect of the hydrocarbon oil is obviously improved.

Description

A kind of method for hydrotreating hydrocarbon oil

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: the reactions such as hydrogenation, hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), hydrogenation aromatics-removing, hydroisomerization, Hydrodewaxing, hydrocracking and mitigation hydrocracking.Hydrobon catalyst wherein or hydrotreating catalyst generally contain group vib metal oxide and VIII family metal oxide, catalyzer usually carries out one or many by the solution that will contain group vib metallic compound and/or VIII family metallic compound with carrier and contacts, and method dry by one or many and roasting prepares again.

Patent ZL97112397 discloses a kind of catalyst for hydrorefining distillate oil, and it consists of the heavy % of nickel oxide 1-5, the heavy % of Tungsten oxide 99.999 12-35, and the heavy % of fluorine 1-9, all the other are aluminum oxide.This catalyzer is used the precursor aqueous solution dipping of aqueous solution containing fluoride and nickel, tungsten successively by comprising the moulding of aluminum oxide precursor after the roasting, the method preparation of drying and roasting behind each dipping.

Patent ZL96194541 discloses a kind of hydrogenation catalyst, this catalyzer contains with the VIII family metal oxide of carrier supported and VI family metal oxide, the additive of selected at least a compound in the compound of other also self-contained at least two hydroxyls of this catalyzer and 2-10 carbon atom and the polyethers of these compounds, wherein VIII family metallic compound and VI family metallic compound are the form of oxide compound.

Patent ZL94103999 discloses a kind of hydrotreating catalyst take aluminum oxide as carrier, and it consists of: γ-Al ₂O ₃60-80%, NiO 3-6%, MoO ₃15-27%, P ₂O ₅2-%, used aluminum oxide is for adopting the pH value swing method to make.Described catalyzer obtains in 100-140 ℃ of drying and 450-650 ℃ of roasting by with the Ni-Mo-P solution impregnation of alumina carrier again.

The document (" CoMo/Al of different methods preparation ₂O ₃The sign of Hydrobon catalyst ", catalysis journal,, the 8th phase of 26 volumes, 639 pages in 2005) reported preparation CoMo/Al ₂O ₃The various preparation methods of catalyzer comprise: (1) wet mixing method: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate and organic acid are made into homogeneous transparent solution, then form through kneading, extrusion, oven dry and roasting with pseudo-boehmite; (2) dry mix: Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate are directly mixed with pseudo-boehmite, then add binding agent, form through kneading, extrusion, oven dry and roasting; (3) pickling process: with pseudo-boehmite with binding agent and expanding agent through mediate.Alumina supporter is made in extrusion, oven dry and roasting, then adopts equi-volume impregnating to steep with Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES and ammonium molybdate solution total immersion, and drying and roasting form again.Aforesaid method has all comprised the roasting process of catalyzer, and metal component all exists with oxide form in catalyzer.

Document (" CoMo/ γ-Al ₂O ₃The preparation of catalyzer and hydrogenation deoxidation performance thereof ", petrochemical complex,, the 1st phase of 39 volumes, 42 pages in 2010) reported CoMo/ γ-Al ₂O ₃The preparation method of catalyzer comprises: (1) uses Ammonium Heptamolybdate aqueous solution oxide impregnation alumina supporter 2h in ultrasonic wave field, 100 ℃ of lower dry 4h, 500 ℃ of lower roasting 4h; (2) adopt same procedure, carry out the dipping second time with cobalt nitrate solution again, carry out equally drying and roasting.

Patent ZL94114194 discloses a kind of with γ-Al ₂O ₃Be carrier, active ingredient is the Hydrodevulcanizing catalyst for hydro-carbons of cobalt, molybdenum, and the preparation of this catalyzer comprises: (1) at high temperature prepares the alumina supporter of Zn modification; (2) with the ammonia soln dipping Zn modified support that contains quadrol, ammonium molybdate and cobalt salt, then in 110-150 ℃ of oven dry 2-6 hour, 480-600 ℃ roasting 3-8 hour, thereby obtain described catalyzer.

In the prior art, also have some reports to relate to the catalyst preparation technology that preparation process does not comprise calcination steps, vib metal and VIII family metal obviously exist with the form of non-oxidized substance in these catalyzer.Even in preparation process, adopted metal oxide for example molybdenum oxide because its solubleness extremely low in the aqueous solution, thereby also need to be converted into other compound effects salt or complex compound or the heteropolyacid etc. of solubility as precursor.

Patent ZL200710176737 discloses a kind of preparation method who exempts from the petroleum fractions oil hydrogenation catalysts of roasting, and the method comprises: (1) joins organic sequestering agent in the deionized water, and organic sequestering agent is dissolved fully; (2) add the salt that contains group vib and VIII family metal; (3) obtain the steeping fluid of pH value 6-8, according to equi-volume impregnating dipping catalyst carrier for hydrgenating, 100-150 ℃ of drying obtains described catalyzer.Obviously, group vib and VIII family metal all exist with the metal-salt form in the described catalyzer.

Patent ZL200380106678 discloses a kind of catalyzer for hydrotreatment light oil, this catalyzer comprises on the inorganic oxide carrier at least a metal that is selected from periodictable VI family metal, at least a metal that is selected from periodictable group VIII metal of 1-15 % by weight and the phosphorus of 1.5-8 % by weight in 10 % by weight-40 % by weight of oxide compound, and in the carbon of the 2-14 % by weight of carbon, the preparation of this catalyzer comprises that the solution that will contain said components is carried on the inorganic oxide carrier, carries out drying afterwards under 200 ℃ or lower temperature.

(" citric acid is to NiW/Al for document ₂O ₃The impact of Hydrobon catalyst sulfidation ", petroleum journal (refining of petroleum), the 3rd phase of 2010,26 volumes, 329 pages) reported a kind of NiW/Al ₂O ₃The preparation of catalyzer comprises and adopts the saturated pickling process in hole, to contain the Ni-W solution impregnation commercial alumina carrier of citric acid, makes the NiW/Al that contains citric acid complexing agent after 120 ℃ of dryings ₂O ₃Catalyzer.

All kinds of hydrocarbon oil hydrogenations processing provide guarantee to the catalyzer that prior art provides in the production reality in order to solve, but this type of catalyst performance remains to be further improved and improves.

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.

The present invention relates to following invention:

1, a kind of method for hydrotreating hydrocarbon oil, be included under hydrogen existence and the hydrogenation conditions, hydrocarbon oil feed is contacted with hydrotreating catalyst, described hydrotreating catalyst contains carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described group vib metal component exists with the form of metal oxide, and described VIII family metal component exists with the form of metal-salt.

According to 1 described method, it is characterized in that 2, take described hydrotreating catalyst as benchmark and with oxide compound, the content of described VIII family metal component is the 1-10 % by weight, the content of group vib metal component is the 5-40 % by weight.

According to 2 described methods, it is characterized in that 3, take described hydrotreating catalyst as benchmark and with oxide compound, the content of described VIII family metal component is the 1.5-7 % by weight, the content of group vib metal component is the 7-35 % by weight.

According to 1 described method, it is characterized in that 4, described group vib metal component is selected from one or more among Cr, Mo, the W, described VIII family metal component is selected from one or more among Fe, Co, the Ni.

According to 4 described methods, it is characterized in that 5, described group vib metal is Mo and/or W, described VIII family metal component is Co and/or Ni.

According to 1 described method, it is characterized in that 6, described metal-salt is selected from the inorganic salt of VIII family metal component or one or more in the organic salt.

According to 6 described methods, it is characterized in that 7, described inorganic salt are selected from one or more in carbonate, subcarbonate, the nitrate; Described organic salt is organic carboxylate.

According to 1 described method, it is characterized in that 8, the carrier in the described hydrotreating catalyst is selected from one or more in aluminum oxide, silicon oxide, silica-alumina, titanium oxide, titanium dioxide-aluminum oxide, Zirconia-alumina, the molecular sieve.

According to 8 described methods, it is characterized in that 9, described aluminum oxide is selected from one or more among γ, η, θ, δ and the χ; Perhaps be selected from and contain one or more and be selected from fluorine, phosphorus, silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth and dose among γ, η, θ, δ and the χ of component one or more.

According to 9 described methods, it is characterized in that 10, described aluminum oxide is gama-alumina or contains one or more and be selected from the gama-alumina that fluorine, phosphorus, silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth are dosed component.

According to 8 described methods, it is characterized in that 11, take described carrier as benchmark, the silica content in the described silica-alumina is the 2-45 % by weight, the content of aluminum oxide is the 55-98 % by weight.

According to 11 described methods, it is characterized in that 12, the content of silicon oxide is the 5-40 % by weight in the described silica-alumina, the content of aluminum oxide is the 60-95 % by weight.

According to 8 described methods, it is characterized in that 13, described molecular screening is from the zeolite molecular sieve of Chang Zuowei catalytic cracking activity component, one or more in the non-zeolitic molecular sieves, take described carrier as benchmark, the content of described molecular sieve is the 0.5-85 % by weight.

14, according to 13 described methods, it is characterized in that, one or more in Y zeolite, be t a zeolite, mordenite, ZSM-5 of described molecular screening, take described carrier as benchmark, the content of described molecular sieve is the 1-55 % by weight.

15, according to 14 described methods, it is characterized in that, one or more the mixture of described molecular screening in Y zeolite, be ta zeolite, ZSM-5, take described carrier as benchmark, the content of described molecular sieve is the 5-50 % by weight.

According to 8 described methods, it is characterized in that 16, take described carrier as benchmark, the content of titanium oxide is the 1-50 % by weight in the described titanium dioxide-aluminum oxide carrier, the content of aluminum oxide is the 50-99 % by weight.

According to 8 described methods, it is characterized in that 17, take described carrier as benchmark, the content of titanium oxide is the 2-40 % by weight in the described titanium dioxide-aluminum oxide carrier, the content of aluminum oxide is the 60-98 % by weight.

According to 8 described methods, it is characterized in that 18, in oxide compound, the content of titanium oxide is the 3-35 % by weight in the described titanium dioxide-aluminum oxide carrier, the content of aluminum oxide is the 65-97 % by weight.

According to 8 described methods, it is characterized in that 19, take described carrier as benchmark, zirconic content is the 1-40 % by weight in the described Zirconia-alumina carrier, the content of aluminum oxide is the 60-99 % by weight.

According to 8 described methods, it is characterized in that 20, take described carrier as benchmark, zirconic content is the 2-35 % by weight in the described Zirconia-alumina carrier, the content of aluminum oxide is the 65-98 % by weight.

According to 8 described methods, it is characterized in that 21, take described carrier as benchmark, zirconic content is the 3-30 % by weight in the described Zirconia-alumina carrier, the content of aluminum oxide is the 70-97 % by weight.

According to 8 described methods, it is characterized in that 22,, it is characterized in that take described carrier as benchmark, the content of boron oxide is the 0.5-10 % by weight in the described boron-containing alumina carrier.

According to 8 described methods, it is characterized in that 23,, it is characterized in that take described carrier as benchmark, the content of boron oxide is the 1-7 % by weight in the described boron-containing alumina carrier.

According to 1 described method, it is characterized in that 24, described hydrotreating catalyst also contains one or more auxiliary agents that are selected from phosphorus, fluorine, boron, the silicon, in element and take catalyzer as benchmark, the content of described auxiliary agent is no more than 10 % by weight.

According to 1 to 24 described method, it is characterized in that 25, described hydrotreating catalyst also contains organic additive, take described catalyzer as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight.

26, according to 1 described method, it is characterized in that, comprised the hydrogenation activity guard catalyst before described hydrotreating catalyst, by volume and take the catalyzer total amount as benchmark, the content of described hydrogenation activity guard catalyst is below 30%.

According to 26 described methods, it is characterized in that 27, by volume and take the catalyzer total amount as benchmark, the content of described hydrogenation activity guard catalyst is 5-20%.

According to 1 described method, it is characterized in that 28, described hydrogenation conditions comprises: temperature of reaction 200-420 ℃, hydrogen dividing potential drop 2-18 MPa, liquid hourly space velocity 0.3-10 hour ^-1, hydrogen to oil volume ratio 50-5000.

According to 28 described methods, it is characterized in that 29, 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.

According to 1 described method, it is characterized in that 30, 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.

According to method provided by the invention, the carrier in the wherein said hydrotreating catalyst can be the carrier that is commonly used for arbitrarily Kaolinite Preparation of Catalyst, for example, is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.The optional self-alumina of described heat-resistant inorganic oxide, silicon oxide, zirconium white, titanium oxide, magnesium oxide, Thorotrast, beryllium oxide, boron oxide-aluminum oxide, aluminium oxide-silicon oxide, aluminium oxide-titanium oxide, aluminium oxide-zirconium oxide, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silicon oxide-Thorotrast, silicon oxide-beryllium oxide, silicon oxide-titanium oxide, the oxidation titania-zirconia, silica-alumina-zirconium white, silica-alumina-Thorotrast, silica-alumina-titanium oxide or silica-alumina-magnesium oxide, in molecular sieve and their mixture one or more.

Further preferred aluminum oxide is selected from one or more among γ, η, θ, δ and the χ; Containing one or more is selected from titanium, magnesium, boron, zirconium, thorium, niobium, rare earth and doses among γ, η, θ, δ and the χ 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 to be made after roasting 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.

Further preferred silica-alumina (aluminium oxide-silicon oxide), take described carrier as benchmark, silica content wherein is the 2-45 % by weight, the content of aluminum oxide is the 55-98 % by weight; More the content of preferential oxidation silicon is the 5-40 % by weight, and the content of aluminum oxide is the 60-95 % by weight.

Described silica-alumina carrier can be commercially available commodity or adopt any one prior art preparation.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 can be hydrolyzed the silicon-containing compound that forms silicon gel, colloidal sol in water medium.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.

Further preferred boron-containing alumina (boron oxide-aluminum oxide), take described carrier as benchmark, the content of boron oxide wherein is the 2-35 % by weight, the content of aluminum oxide is the 65-98 % by weight; Further the content of preferential oxidation boron is the 3-30 % by weight, and the content of aluminum oxide is the 70-97 % by weight.

Described boron-containing alumina has specific surface and the pore volume of conventional boron-containing alumina carrier, and the specific surface of preferred boron-containing alumina is 100-350 rice ²/ gram, more preferably 120-300 rice ²/ gram, the pore volume of preferred boron-containing alumina is 0.4-1.2 ml/g, more preferably 0.5-1.0 ml/g.Described boron-containing alumina can be that commercially available commodity can be commercially available commodity, or adopts any one prior art preparation, such as pickling process, sol-gel method and coprecipitation method etc.A method that preferably prepares boron-containing alumina, be with the precursor of aluminum oxide and/or aluminum oxide mix with the precursor of boron oxide and/or boron oxide, roasting obtains.The mixing of boron-containing compound and aluminum contained compound can be undertaken by mixing, soak, flood, deposit, be total to the modes such as glue, precipitation such as kneading, stone roller.In case of necessity, boron-containing compound can be scattered in the middle of the solvent, mix with aluminum contained compound again.Described maturing temperature is 400-650 ℃, and roasting time is 1-10 hour, and preferred maturing temperature is 450-620 ℃, and roasting time is 2-8 hour.The consumption of the boron-containing compound of selecting should be so that final carrier contains the boron oxide of aequum.

Described boron-containing compound can be selected from one or more among boron oxide, boric acid, ammonium biborate, tetraboric acid ammonium, ammonium pentaborate, Sodium Tetraborate, ammonium borofluoride, boron trifluoride, the methyl-borate.

Further preferred titanium dioxide-aluminum oxide (aluminium oxide-titanium oxide), take described carrier as benchmark, the content of titanium oxide wherein is the 2-40 % by weight, the content of aluminum oxide is the 60-98 % by weight; Further the content of preferential oxidation titanium is the 3-35 % by weight, and the content of aluminum oxide is the 65-97 % by weight.

Described titanium dioxide-aluminum oxide has specific surface and the pore volume of conventional titanium dioxide-aluminum oxide carrier, and the specific surface of preferential oxidation titanium-aluminum oxide is 100-350 rice ²/ gram, more preferably 120-300 rice ²/ gram, the pore volume of preferential oxidation titanium-aluminum oxide is 0.4-1.2 ml/g, more preferably 0.5-0.9 ml/g.Described titanium dioxide-aluminum oxide carrier can be commercially available commodity, or adopts any one prior art preparation.A method that preferably prepares titanium dioxide-aluminum oxide, be with the precursor of aluminum oxide and/or aluminum oxide mix with the precursor of titanium oxide and/or titanium oxide, roasting obtains.The mixing of titanium-containing compound and aluminum contained compound can be by carrying out such as modes such as mediating, grind mixed, immersion, dipping, deposition, precipitation.In case of necessity, titanium-containing compound can be scattered in the middle of the solvent, mix with aluminum contained compound again.Described maturing temperature is 400-650 ℃, and roasting time is 1-10 hour, and preferred maturing temperature is 450-620 ℃, and roasting time is 2-8 hour.The consumption of the titanium-containing compound of selecting should be so that final carrier contains the titanium dioxide of aequum.

Described titanium-containing compound can be selected from inorganic titanium-containing compound, such as titanium colloidal sol, titanium hydroxide colloidal sol, titanium hydroxide, titanium gel, titanium dioxide, titanium dioxide hydrates, metatitanic acid, titanium dioxide, Titanium Nitrate, titanyl nitrate, titanium tetrachloride, titanium sulfate, ammonium titanium fluoride, titanyl sulfate, metatitanic acid, also can be selected from organic titanium-containing compound, such as titanium ethanolate, butyl (tetra) titanate, titanium isopropylate, titanous oxalate, the derivative of ammonium titanyl oxalate, titanium oxyoxalate acid, acetic acid titanium, peroxide nitrilotriacetic acid(NTA) titanium, Titanium Citrate, titanium acetylacetone and these compounds.

Further preferred Zirconia-alumina (aluminium oxide-zirconium oxide), take described carrier as benchmark, zirconic content is the 2-35 % by weight in the Zirconia-alumina wherein, the content of aluminum oxide is the 65-98 % by weight; Further the content of preferential oxidation zirconium is the 3-30 % by weight, and the content of aluminum oxide is the 70-97 % by weight.

Described Zirconia-alumina has specific surface and the pore volume of conventional Zirconia-alumina carrier, and the specific surface of preferential oxidation zirconium-aluminum oxide is 100-350 rice ²/ gram, more preferably 120-300 rice ²/ gram, the pore volume of preferential oxidation zirconium-aluminum oxide is 0.4-1.2 ml/g, more preferably 0.5-1.0 ml/g.Described Zirconia-alumina carrier can be commercially available commodity, or adopts any one prior art preparation, for example dipper precipitation method, alkoxide sol-gel method and coprecipitation method.The dipper precipitation method generally is with pseudo-boehmite or γ-Al ₂O ₃Then inorganic salt or the alkoxide solution of dipping zirconium add precipitation agent and make zirconium ion be deposited in its surface, namely get ZrO through washing, drying and roasting ₂-Al ₂O ₃Complex carrier.The preparation process of alkoxide sol-gel method generally is that the alkoxide with zirconium and aluminium is dissolved in the corresponding alcohol, then adds a certain amount of water and alcohol and makes its hydrolysis, and hydrolysate drying, roasting namely get mixed oxide.The preparation process of coprecipitation method is that a certain amount of precipitation agent of adding after the inorganic salt solution mixing of zirconium and aluminium is made its coprecipitation.A method that preferably prepares Zirconia-alumina, be with the precursor of aluminum oxide and/or aluminum oxide mix with zirconium white and/or zirconic precursor, roasting obtains.The mixing of zirconium-containing compound and aluminum contained compound can be by carrying out such as modes such as mediating, grind mixed, immersion, dipping, deposition, precipitation.In case of necessity, zirconium-containing compound can be scattered in the middle of the solvent, mix with aluminum contained compound again.Described solvent can be water or organism solvent such as the alcohols that dissolves each other with zirconium-containing compound.Described maturing temperature is 400-650 ℃, and roasting time is 1-10 hour, and preferred maturing temperature is 450-620 ℃, and roasting time is 2-8 hour.The consumption of the zirconium-containing compound of selecting should be so that final carrier contains the zirconium white of aequum.

Described zirconium-containing compound can be selected from inorganic zirconium-containing compound, such as zirconium dioxide, zirconia sol, zirconium hydroxide, zirconium dioxide hydrate, inclined to one side zirconic acid, zirconium nitrate, Zircosol ZN, zirconium tetrachloride, basic zirconium chloride, zirconium sulfate, ammonium fluozirconate, also can be selected from organic zirconium-containing compound, such as tetrabutyl zirconate, four n-propyl zirconates, zirconyl oxalate, zirconium acetate, citric acid zirconium, methyl ethyl diketone zirconium.

Described molecular screening is from the zeolite molecular sieve of Chang Zuowei catalytic cracking activity component, one or more in the non-zeolitic molecular sieves.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, beta zeolite, mordenite, ZSM-5 wherein one or more.The further mixture of one or more in the preferred Y zeolite, beta zeolite, ZSM-5 wherein.Described molecular sieve can be commercially available commodity, also can adopt any one prior art preparation.

When described carrier is that take described carrier as benchmark, the content of described molecular sieve is preferably the 0.5-85 % by weight, more preferably the 5-50 % by weight when comprising the mixture of aluminum oxide and/or silica-alumina etc. and molecular sieve.

Described carrier is looked different the forming composition that require can be made into various easy handlings, such as 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, then extrusion moulding.The kind of described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, are not repeated herein.

According to method provided by the invention, the preparation method of wherein said catalyzer comprises and introduces at least a VIII of being selected from family and at least a metal component that is selected from group vib in the carrier, be enough to the described at least a VIII of being selected from family and at least a metal component that is selected from group vib is carried on the described alumina supporter and described group vib metal component is existed with the form of metal oxide, under the prerequisite that described VIII family metal component exists with the form of metal-salt, concrete operation step is not particularly limited.For example, the method that the described VIII of being selected from family and at least a metal component that is selected from group vib is carried on the described alumina supporter is pickling process.Described dipping can be excessive liquid dipping, the saturated dipping in hole according to steeping fluid consumption difference, and the mode difference that realizes according to dipping can be that impregnating is soaked, sprayed to infusion method.By the regulation and control to concentration, consumption or the carrier consumption of dipping solution, can prepare the described catalyzer of specifying content, it is intelligible that this is that those skilled in the art hold.

Wherein, described group vib metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in silicotungstic acid, silicotungstate, phospho-molybdic acid, phosphomolybdate, molybdate, paramolybdate, tungstate, metatungstate, the ethyl metatungstate one or more.

Described group VIII metal-salt is at least a of inorganic salt or organic salt, described inorganic salt are selected from one or more in the partially decomposed product of nitrate, carbonate, subcarbonate, hypophosphite, phosphoric acid salt, vitriol, muriate and these salts, preferably, be selected from nitrate, carbonate or the subcarbonate one or more.Described organic salt is salt or the soluble complexes that organism and VIII family melts combine generate, and described organism can be organic bases, organic carboxyl acid, amine, ketone, ethers, alkyls, is preferably organic carboxylate.

In a concrete embodiment, the preparation method of described catalyzer comprises:

(1) with the solution impregnating carrier of the compound that contains VIB group metal, carry out afterwards drying and roasting, the condition of described roasting makes the compound of the described VIB of containing group metal be enough to be converted into oxide compound;

(2) product that obtains with the solution impregnation step (1) that contains VIII family metal-salt carries out drying afterwards, and the condition of described drying makes VIII family metal-salt be not enough to be decomposed into oxide compound.

Wherein, the drying temperature of preferred described step (1) is 80-300 ℃, and be 1-12 hour time of drying, and described maturing temperature is 350-550 ℃, and roasting time is 2-10 hour; The drying temperature of described step (2) is 30-250 ℃, 1-8 hour time of drying.Further the drying temperature of preferred described step (1) is 100-250 ℃, and be 2-8 hour time of drying, and described maturing temperature is 400-500 ℃, and roasting time is 3-6 hour; The drying temperature of described step (2) is 60-200 ℃, 2-6 hour time of drying.

The method of described drying and roasting and condition can be drying usual in the catalyzer preparation and method and the condition of roasting, and there is no particular limitation to this present invention.

During one or both adjuvant components in also containing components such as being selected from boron, phosphorus or fluorine in the described catalyzer, in the preparation method of described catalyzer, also comprise and introduce the step that is selected from one or more components in the components such as boron, phosphorus or fluorine, the described introducing method that is selected from the components such as boron, phosphorus or fluorine can pass through number of ways, as can be with the compound of auxiliary agent as described in containing directly and the precursor (such as pseudo-boehmite) of aluminum oxide and/or aluminum oxide and comprise or do not comprise contain as described in compound, moulding and the roasting of promoter metal component; Can be will contain compound and the compound that contains the hydrogenation active metals component of described auxiliary agent be mixed with the described carrier of dipping behind the mixing solutions; Can also be that dipping behind the independent obtain solution of the compound that contains auxiliary agent is stated carrier and roasting.When described when being selected from the components such as boron, phosphorus or fluorine and hydrogenation active metals and introducing described carrier respectively, preferred at first with the described carrier of solution impregnation and the roasting of the compound that contains components such as being selected from boron, phosphorus or fluorine, use again afterwards the solution impregnation of the compound that contains the hydrogenation active metals component.Herein, described maturing temperature is 250-600 ℃, is preferably 350-500 ℃, and roasting time is 2-8 hour, is preferably 3-6 hour.

When catalyzer of the present invention further contains organic compound, in the preparation method of described catalyzer, also comprise the step of introducing organic compound, described organic compound can be introduced together with the group VIII metal, also can after introducing the group VIII metal, introduce, and carry out drying, preferably organism and group VIII metal are mixed with mixing solutions and introduce simultaneously by the mode of dipping, carry out afterwards drying.The selection of described drying temperature and time except deficiency so that VIII family metal-salt or complex compound decompose, also should allow in catalyzer, to keep most of organism of introducing, for example keep the organism more than 50%, more preferably, keep the organism more than 70%.Its method can be any one method that can realize above-mentioned purpose in the prior art.For example, heat drying, drying under reduced pressure and add the methods such as thermal bond drying under reduced pressure.When described drying means was heat drying, preferred drying temperature was no more than 250 ℃, further preferably is no more than 200 ℃, is more preferably and is no more than 180 ℃.For example, one preferred embodiment in, described drying temperature is 70 ℃～180 ℃.When preparation contains the described catalyzer of organic compound, in carbon and take described catalyzer as benchmark, preferably pass through to select the introducing amount of described organic compound so that in the final catalyzer, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.

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 outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metallic sulfide component.

When before described hydrotreating catalyst, comprising the hydrogenation activity guard catalyst; the effect of described hydrogenation activity guard catalyst is to remove the macromole such as colloid that may exist in the raw material and gives birth to charcoal precursor and metal impurities so that stock oil be purified before described hydrotreating catalyst contacts.Therefore, described hydrogenation activity guard catalyst can be selected from one or more in the catalyzer that can realize arbitrarily this function in the prior art.They can be commercially available commodity or adopt arbitrarily existing method preparation.

This type of catalyzer contains heat-resistant inorganic oxide carrier and the hydrogenation active metals component that loads on this carrier usually.Wherein, described heat-resistant inorganic oxide carrier is selected from one or more in the various heat-resistant inorganic oxides that are commonly used for support of the catalyst and/or matrix.For example, in optional self-alumina, silicon oxide, titanium oxide, magnesium oxide, silica-alumina, aluminum oxide-magnesium oxide, silicon oxide-magnesium oxide, silicon oxide-zirconium white, silica-alumina-titanium oxide, the silica-alumina-magnesium oxide one or more are preferably aluminum oxide.Described hydrogenation activity component is selected from molybdenum and or tungsten, nickel and or cobalt.

For example, the disclosed a kind of catalyzer of ZL200310117322, this catalyzer contains a kind of macropore alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel that load on this carrier, in oxide compound and take catalyzer as benchmark, described catalyzer contains the carrier of the cobalt of the molybdenum of 0.5-15 % by weight and/or tungsten, 0.3-8 % by weight and/or nickel, equal amount, it is characterized in that described carrier contains a kind of halogen, take the carrier total amount as benchmark, this carrier contains the aluminum oxide of 95-99 % by weight.

ZL200410037670 discloses a kind of alumina supporter and the molybdenum and/or tungsten and cobalt and/or the nickel that load on this carrier with double-hole, in oxide compound and take catalyzer as benchmark, described catalyzer contains the carrier of the cobalt of the molybdenum of 0.5-15 % by weight and/or tungsten, 0.3-8 % by weight and/or nickel, equal amount.

ZL200410096309 discloses a kind of residuum hydrogenating and metal-eliminating catalyst, this catalyzer contains a kind of bimodal porous aluminum oxide carrier and the molybdenum and/or tungsten and nickel and/or the cobalt metal component that load on this carrier, the pore volume of wherein said bimodal porous aluminum oxide carrier is 0.8-1.6 ml/g, and specific surface area is 150-350m ²/ g, the aperture accounts for total pore volume 40～90% at the pore volume of 10～30 nanometers, and the aperture accounts for total pore volume 10～60% at the pore volume of 100～2000 nanometers.

ZL200510115349 discloses a kind of hydrogenation activity protective material and preparation method thereof; this protective material contains alumina supporter, loads on hydrogenation active metals component and the halogen of significant quantity on this carrier; in element and take catalyzer as benchmark; the content of described halogen is the 0.5-10 % by weight, and the specific surface area of described carrier is 2-50m ²/ g, pore volume 0.4-1.2 ml/g, described carrier is by comprising the precursor of one or more aluminum oxide and/or aluminum oxide and the method preparation of at least a halogen-containing compound, moulding and roasting.

These catalyzer all can be selected to be used for the present invention as described catalyst I.About the more detailed preparation method of above-mentioned catalyzer, all on the books in above-mentioned patent documentation, in the lump they are quoted as the part of content of the present invention here.

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 raw material can be various heavy mineral oils or synthetic oil or their mixed fraction oil, such as straight run gas oil, vacuum gas oil, metal removal oil, long residuum, diasphaltene vacuum residuum, coker distillate, catalytic cracking distilled oil, shale oil, asphalt sand oil, Fischer-Tropsch synthesis oil.

Compare with existing method, the hydrocarbon oil hydrogenation treatment effect that the invention provides method obviously improves.

Embodiment

Following example will the present invention will be further described, but therefore do not limit content of the present invention.

Carbon content in the catalyzer adopts analyses, and other components all adopt x-ray fluorescence spectrometry except specifying.

Embodiment 1-1,1-2, the 1-3 explanation is suitable for hydrotreating catalyst take aluminum oxide as carrier of the present invention and preparation method thereof; Comparative Examples 1-1,1-2,1-3,1-4,1-5,1-6 explanation reference hydrotreating catalyst take aluminum oxide as carrier and preparation method thereof.

Preparing catalyzer of the present invention and reference catalyst is prepared by following methods with alumina supporter:

(Chang Ling refinery catalyst plant is produced pseudo-boehmite with 4000 gram CL dry glue powders, butt 70%) and after sesbania powder 110 gram mixes, again with 80 milliliters of nitric acid (concentration 65-68%, analytical pure, chemical plant, Gansu Province, west, Shantou) and the mixing of 4900 ml waters, it is even that this mixture is continued kneading at double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains alumina supporter A through 120 ℃ of dryings.Adopt BET N ₂Absorption method is analyzed the A carrier, and the specific surface area of this carrier is 250 meters squared per gram, 0.66 ml/g of pore volume.

The employed raw material sources of Kaolinite Preparation of Catalyst are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry company limited product, technical grade; Ammonium metawolframate, Zhuzhou diamond tungsten product company limited product, technical grade; Nickelous nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product, analytical pure; Basic nickel carbonate, Yixing Xu Chi chemical industry company limited product, chemical pure; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Beijing Yili Fine Chemicals Co., Ltd., analytical pure; Phosphoric acid, Beijing Chemical Plant's product, analytical pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product, analytical pure; Citric acid monohydrate Food grade, Beijing Chemical Plant's product, analytical pure; Neutral ammonium fluoride, chemical plant, Jinan product, analytical pure.

Embodiment 1-1

Get alumina supporter A 200 grams, flooded 2 hours with 170 milliliters of dilute ammonia solutions (10% concentration) that contain ammonium paramolybdate 36 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contain the molybdenum carrier 2 hours with 130 milliliters of aqueous solution dippings that contain Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 18 gram afterwards, in 120 ℃ of dryings 4 hours, make catalyzer C1-1.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Comparative Examples 1-1

Get alumina supporter A 200 grams, flooded 2 hours with 170 milliliters of dilute ammonia solutions (10% concentration) that contain ammonium paramolybdate 28 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours, contained the molybdenum carrier 2 hours with the 130 milliliters of dippings of the aqueous solution that contain Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 18 grams afterwards, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtained comparative catalyst DC1-1A.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Comparative Examples 1-2

Get alumina supporter A 200 gram, flooded 2 hours with 170 milliliters of dilute ammonia solutions that contain ammonium paramolybdate 28 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 18 grams, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC1-1B.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Embodiment 1-2

Get alumina supporter A 200 grams, flooded 2 hours with 170 milliliters of aqueous solution that contain ammonium paramolybdate 70 grams, phosphoric acid 23 grams, in 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, afterwards with 100 milliliters of dippings of the aqueous solution that contains nickelous nitrate 57 gram 2 hours, in 120 ℃ of dryings 4 hours, obtain catalyzer C1-2.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Comparative Examples 1-3

Get alumina supporter A 200 gram, flooded 2 hours with containing 170 milliliters of ammonium molybdate 70 grams, nickelous nitrate 57 grams, phosphoric acid 23 grams, lemon aqueous acid, in 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours obtained comparative catalyst DC1-2A.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Comparative Examples 1-4

Get alumina supporter A 200 gram, with 170 milliliters of dippings of the aqueous solution that contain molybdenum oxide 70 grams, basic nickel carbonate 28 grams, phosphoric acid 23 grams 2 hours, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC1-2B.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Embodiment 1-3

Get alumina supporter A 200 gram, with the aqueous solution dipping of 170 milliliters of fluorinated ammoniums, 19 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Get fluorine-containing carrier 200 grams, flooded fluorine-containing carriers 2 hours with 155 milliliters of the aqueous solution that contains ammonium metawolframate 109 grams, and in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours, obtain the tungstenic carrier of load Tungsten oxide 99.999, afterwards with the aqueous solution dipping tungstenic carrier of basic nickel carbonate 22 gram, citric acid 32 grams 2 hours, in 180 ℃ of dryings 4 hours, obtain catalyzer C1-3.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Comparative Examples 1-5

Get alumina supporter A 200 gram, with the aqueous solution dipping of 170 milliliters of fluorinated ammoniums, 19 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Get fluorine-containing carrier 200 grams, with 155 milliliters of fluorine-containing carriers of dipping of the aqueous solution that contain ammonium metawolframate 109 grams, basic nickel carbonate 22 grams, citric acid 32 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained comparative catalyst DC1-3A.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Comparative Examples 1-6

Get alumina supporter A 200 gram, with the aqueous solution dipping of 170 milliliters of fluorinated ammoniums, 19 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Get fluorine-containing carrier 200 grams, with 155 milliliters of fluorine-containing carriers of dipping of the aqueous solution that contain ammonium metawolframate 109 grams, basic nickel carbonate 22 grams, citric acid 32 grams 2 hours, in 180 ℃ of dryings 4 hours, obtain comparative catalyst DC1-3B.Take catalyst weight as benchmark, measure the results are shown in of forming and show 1-1.

Table 1-1

Embodiment 1-4,1-5, the 1-6 explanation the invention provides the effect of method.

Comparative Examples 1-7,1-8,1-9,1-10,1-11, the effect of 1-12 explanation reference method.

Embodiment 1-4

Present embodiment explanation the present invention is used for the effect of residual hydrocracking, and catalyzer is C1-1.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C1-1 on 250 milliliters of hydrogenation units, raw materials used oil nature, reaction conditions see Table 1-2, and reaction result sees Table 1-3.

The measuring method of sulphur is SH/T 0253-92, and the nitrogen determination method is SH/T 0657-1998.Desulfurization degree and the denitrification percent of catalyzer are calculated as follows.

Table 1-2

Stock oil character	Normal slag in the sand
		Density (20 ℃), g/cm 3	0.9846
S，ppm	47000
		N，ppm	2900
MCR，m％	13.10
		Metal content, ppm
Ni	29.1
		V	88.8
Reaction conditions
		The hydrogen dividing potential drop, MPa	15.0
Catalyst volume, ml	100
		Temperature, ℃	385
Volume space velocity, h -1	0.5
		Hydrogen-oil ratio, v/v	800

Comparative Examples 1-7

This Comparative Examples explanation reference method is used for the effect of residual hydrocracking, and catalyzer is DC1-1A.According to the method evaluation comparative catalyst DC1-1A of embodiment 1-4, reaction result sees Table 1-3.

Comparative Examples 1-8

This Comparative Examples explanation reference method is used for the effect of residual hydrocracking, and catalyzer is DC1-1B.

According to the method evaluation comparative catalyst DC1-1B of embodiment 1-4, reaction result sees Table 1-3.

Table 1-3

By table 1-3 result as can be known, with respect to reference method, the method for the invention provides has better residuum hydrodesulfurization performance and hydrodenitrification effect.

Embodiment 1-5

The present embodiment explanation the invention provides method and is used for the decompressed wax oil hydrotreatment, and catalyzer is C1-2.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C1-2 on 250 milliliters of hydrogenation units, raw materials used oil nature, reaction conditions see Table 1-4, and reaction result sees Table 1-5.

The measuring method of sulphur is SH/T 0253-92, and the nitrogen determination method is SH/T 0657-1998.The hydrodesulfurization activity of catalyzer calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related calculation formula is as follows.

Comparative Examples 1-9

This Comparative Examples explanation reference method is used for the decompressed wax oil hydrotreatment, and catalyzer is DC1-2A.

According to the method evaluation comparative catalyst DC1-2A of embodiment 1-5, reaction result sees Table 1-5, take the activity of DC1-2A catalyzer as 100.

Comparative Examples 1-10

This Comparative Examples explanation reference method is used for the decompressed wax oil hydrotreatment, and catalyzer is DC1-2B.

According to the method evaluation comparative catalyst DC1-2B of embodiment 1-5, reaction result sees Table 1-5.

Table 1-4

Stock oil character	Decompressed wax oil
		Density (20 ℃), g/cm 3	0.9113
S，ppm	20000
		N，ppm	1100
Refractive index (70 ℃)	1.4875
		Boiling range (D1160), ℃
Initial boiling point	258
		50% point	452
95% point	515
		Reaction conditions
The hydrogen dividing potential drop, Mpa	8.0
		Catalyst volume, ml	100
Temperature, ℃	375
		Volume space velocity, h -1	1.4
Hydrogen-oil ratio, v/v	800

Table 1-5

Table 1-5 result shows that with respect to reference method, the method for the invention provides has better wax oil hydrogenation treatment effect.

Embodiment 1-6

The present embodiment explanation the invention provides method and is used for the hydrorefined effect of straight-run diesel oil, and catalyzer is C1-3.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C1-3 on 30 milliliters of hydrogenation units, raw materials used oil nature, reaction conditions see Table 1-6, and reaction result sees Table 1-7.The hydrodesulfurization activity of catalyzer calculates by 1.65 order reactions, and related calculation formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and calculation formula is seen embodiment 1-5.

Table 1-6

Stock oil character	Straight-run diesel oil
		Density (20 ℃), g/cm 3	0.8456
S，ppm	8000
		N，ppm	144
Refractive index (20 ℃)	1.4723
		Reaction conditions
The hydrogen dividing potential drop, Mpa	3.2
		Catalyst volume, ml	30
Temperature, ℃	350
		Volume space velocity, h -1	2.0
Hydrogen-oil ratio, v/v	300

Comparative Examples 1-11

This Comparative Examples explanation reference method is used for the hydrorefined effect of straight-run diesel oil, and catalyzer is DC1-3A.

According to the method evaluation reference catalyst DC1-3A of embodiment 1-6, reaction result is listed in table 1-7, take the activity of DC1-3A catalyzer as 100.

Comparative Examples 1-12

This Comparative Examples explanation reference method is used for the hydrorefined effect of straight-run diesel oil, and catalyzer is DC1-3B.

According to the method evaluation reference catalyst DC1-3B of embodiment 1-6, reaction result is listed in table 1-7.

Table 1-7

Table 1-7 result shows that with respect to reference method, the method for the invention provides has better diesel oil hydrofining effect.

Embodiment 1-7

The difference on effect that is used for residual hydrocracking when using the hydrogenation activity protective material in present embodiment comparison the inventive method and not using the hydrogenation activity protective material.

I does not use the hydrogenation activity protective material.Stock oil, evaluation method and condition are with embodiment 1-5, and Primary Catalysts is C1-1, and volume is 100 milliliters.When carrying out 100 hours and 1000h, reaction the results are shown in Table 1-8.

II uses the hydrogenation activity protective material.20 milliliters of hydrogenation activity protective material G-1 of filling before Primary Catalysts C1-1, this protective material is Sinopec catalyzer Chang Ling branch office product, it consists of molybdenum oxide 5.5% weight, NiO1.1% weight, equal amount carrier.Primary Catalysts (C1-1) volume space velocity is 0.5h-1.All the other conditions and stock oil are with embodiment 1-5.When carrying out 100 hours and 1000h, reaction the results are shown in Table 1-8.Take 100 hours desulfurization degrees as 100, obtain relative desulfurization degree by 1000 hours desulfurization degrees with the ratio of 100 hours desulfurization degree, this numerical value can be used for the deactivation rate of reflection catalyzer.

Table 1-8

By table 1-8 as can be known, when adopting hydrogenation protecting agent G-1 and Primary Catalysts C1-1 combination in the inventive method, with respect to not using the hydrogenation protecting agent, combination catalyst has better sweetening effectiveness, especially better activity stability.

Embodiment 2-1,2-2, the 2-3 explanation is suitable for hydrotreating catalyst take boron-containing alumina as carrier of the present invention and preparation method thereof; Comparative Examples 2-1,2-2,2-3,2-4,2-5,2-6 explanation reference hydrotreating catalyst take boron-containing alumina as carrier and preparation method thereof.

Preparing catalyzer of the present invention and reference catalyst is prepared by following methods with boron-containing alumina carrier:

First with the 1000 gram aluminum hydroxide solid elastomer powder (pseudo-boehmites that Sinopec catalyzer Chang Ling branch office produces, butt 70%) mixes with 33 gram sesbania powder, again with this mixture and boronic acid containing (chemical reagents corporation of Beijing Jin Hui the Pacific-Asian production, analytical pure) 52 aqueous solution that restrain are 870 milliliters, 25 milliliters of nitric acid (concentration 65-68%, analytical pure, chemical plant, Gansu Province, west, Shantou) mixes, it is even to continue kneading at double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain boron-containing alumina carrier BA.Adopt x-ray fluorescence method to measure the composition of BA, in oxide compound and take described carrier as benchmark, boron oxide content is 4.0 % by weight.

Adopt BET N ₂Absorption method is analyzed the BA carrier, and the specific surface area of this carrier is 244 meters squared per gram, 0.62 ml/g of pore volume.

The employed raw material sources of Kaolinite Preparation of Catalyst are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry company limited product, technical grade; Ammonium metawolframate, Zhuzhou diamond tungsten product company limited product, technical grade; Nickelous nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product, analytical pure; Basic nickel carbonate, Yixing Xu Chi chemical industry company limited product, chemical pure; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Beijing Yili Fine Chemicals Co., Ltd., analytical pure; Phosphoric acid, Beijing Chemical Plant's product, analytical pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product, analytical pure; Citric acid monohydrate Food grade, Beijing Chemical Plant's product, analytical pure; Neutral ammonium fluoride, chemical plant, Jinan product, analytical pure.

Embodiment 2-1

Get BA carrier 150 grams, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium paramolybdate 25.4 grams, ammoniacal liquor 5.0 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contain the molybdenum carrier 2 hours with 90 milliliters of aqueous solution dippings that contain Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 13.8 gram afterwards, in 120 ℃ of dryings 4 hours, make catalyzer C2-1.Take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Comparative Examples 2-1

Get BA carrier 150 gram, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium paramolybdate 25.4 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 13.8 grams, ammoniacal liquor 5.0 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, obtain comparative catalyst DC2-1A, take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Comparative Examples 2-2

Get BA carrier 150 grams, contain ammonium paramolybdate 25.4 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 13.8 grams, the aqueous solution dipping of ammoniacal liquor 5.0 grams 2 hours with 120 milliliters, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC2-1B, take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Embodiment 2-2

Get BA carrier 150 grams, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium paramolybdate 38.7 grams, phosphatase 79 .5 gram, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contains the molybdenum carrier 2 hours with the 78 milliliters of dippings of the aqueous solution that contain basic nickel carbonate 11.5 grams, Citric acid monohydrate Food grade 22.0 grams afterwards, in 120 ℃ of dryings 4 hours, obtain catalyzer C2-2, take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Comparative Examples 2-3

Get BA carrier 150 grams, flooded described carriers 2 hours with 120 milliliters of the aqueous solution that contains ammonium paramolybdate 38.7 grams, basic nickel carbonate 11.5 grams, phosphatase 79 .5 gram and Citric acid monohydrate Food grade 22.0 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, obtain comparative catalyst DC2-2A, take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Comparative Examples 2-4

Get BA carrier 150 grams, flooded described carriers 2 hours with 120 milliliters of the aqueous solution that contains ammonium paramolybdate 38.7 grams, basic nickel carbonate 11.5 grams, phosphatase 79 .5 gram and Citric acid monohydrate Food grade 22.0 grams, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC2-2B, take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Embodiment 2-3

Get BA carrier 150 gram, with 120 milliliters of dippings of the aqueous solution of fluorinated ammonium 18.8 grams 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.

Flooded fluorine-containing carrier 2 hours with 105 milliliters of aqueous solution that contain ammonium metawolframate 71.0 gram, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours made the tungstenic carrier of load Tungsten oxide 99.999.

With 60 milliliters of above-mentioned tungstenic carriers of dipping of the aqueous solution that contains nickelous nitrate 27.5 gram, in 150 ℃ of dryings 4 hours, obtain catalyzer C2-3, take catalyst weight as benchmark, composition measuring the results are shown in table 2-1.

Comparative Examples 2-5

Get BA carrier 150 gram, with 120 milliliters of dippings of the aqueous solution of fluorinated ammonium 18.8 grams 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.

Flooded above-mentioned fluorine-containing carriers 2 hours with 105 milliliters of the aqueous solution that contains ammonium metawolframate 71.0 grams, nickelous nitrate 27.5 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained comparative catalyst DC2-3A, take catalyst weight as benchmark, 2-1 is shown in the results are shown in of composition measuring.

Comparative Examples 2-6

Get BA carrier 150 gram, with 120 milliliters of dippings of the aqueous solution of fluorinated ammonium 18.8 grams 2 hours, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours obtained fluorine-containing carrier.

With 105 milliliters of above-mentioned fluorine-containing carriers of dipping of the aqueous solution that contains ammonium metawolframate 71.0 gram, nickelous nitrate 27.5 grams 2 hours, in 150 ℃ of dryings 4 hours, obtain comparative catalyst DC2-3B, take catalyst weight as benchmark, composition measuring the results are shown in table 2-1.

Table 2-1

Embodiment 2-4,2-5, the 2-6 explanation the invention provides the effect of method.

Comparative Examples 2-7,2-8,2-9,2-10,2-11, the effect of 2-12 explanation reference method.

Embodiment 2-4

Present embodiment explanation the present invention is used for the effect of residuum hydrodesulfurization, and catalyzer is C2-1.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 100 milliliters of hydrogenation units, and reaction raw materials oil adopts normal slag in the sand, and sulphur content is 4.53%, and nitrogen content is 0.30%, and metal (nickel+vanadium) total amount is 101ppm.Reaction conditions is: 390 ℃ of temperature of reaction, hydrogen dividing potential drop 14 MPas, volume space velocity 0.5h ^-1

The measuring method of sulphur is GB/T 17040-2008.

Calculate desulfurization degree according to following formula:

The results are shown in Table 2-2.

Comparative Examples 2-7

This Comparative Examples explanation reference method is used for the effect of residuum hydrodesulfurization, and catalyzer is DC2-1A.

According to the method evaluation comparative catalyst DC2-1A of embodiment 2-4, reaction result sees Table 2-2.

Comparative Examples 2-8

This Comparative Examples explanation reference method is used for the effect of residuum hydrodesulfurization, and catalyzer is DC2-1B.

According to the method evaluation comparative catalyst DC2-1B of embodiment 2-4, reaction result sees Table 2-2.

Table 2-2

	Catalyzer	Desulfurization degree/%
			Embodiment 2-4	C2-1	87.9
Comparative Examples 2-7	DC2-1A	86.8
			Comparative Examples 2-8	DC2-1B	86.0

By table 2-2 result as can be known, with respect to reference method, the method for the invention provides has better residuum hydrodesulfurization effect.

Embodiment 2-5

Present embodiment explanation the present invention is used for the effect of wax oil hydrogenation denitrogenation, and catalyzer is C2-2.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 100 milliliters of hydrogenation units, and raw materials used oil is Middle East VGO, and sulphur content is 1.8%, and nitrogen content is 0.11%, and density is 0.9078g/cm ³Reaction conditions is: 375 ℃ of temperature of reaction, hydrogen dividing potential drop 8.0 MPas, volume space velocity 1.0h ^-1The hydrodenitrogenationactivity activity of catalyzer is calculated by 1 order reaction, and related calculation formula is as follows.

The nitrogen determination method is SH/T 0657-2007, and reaction result is listed in table 2-3.

Comparative Examples 2-9

This Comparative Examples explanation reference method is used for the effect of wax oil hydrogenation denitrogenation, and catalyzer is DC2-2A.

According to the method evaluation reference catalyst DC2-2A of embodiment 2-5, reaction result is listed in table 2-3, take the activity of DC2-2A catalyzer as 100.

Comparative Examples 2-10

This Comparative Examples explanation reference method is used for the effect of wax oil hydrogenation denitrogenation, and catalyzer is DC2-2B.

According to the method evaluation reference catalyst DC2-2B of embodiment 2-5, reaction result is listed in table 2-3.

Table 2-3

	Catalyzer	Relative denitrification activity
			Embodiment 2-5	C2-2	118
Comparative Examples 2-9	DC2-2A	100
			Comparative Examples 2-10	DC2-2B	111

Table 2-3 result shows that with respect to reference method, the method for the invention provides has better wax oil hydrogenation denitrification effect.

Embodiment 2-6

Present embodiment explanation the present invention is used for the effect that residual hydrogenation takes off carbon residue, and catalyzer is C2-3.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 100 milliliters of hydrogenation units, and stock oil adopts the normal slag in the Middle East, and sulphur content is 4.7%, and nitrogen content is 0.29%, carbon residue 12.6%.Reaction conditions is: 385 ℃ of temperature of reaction, hydrogen dividing potential drop 15.0 MPas, volume space velocity 0.5h ^-1The analytical procedure of carbon residue is GB/T17144-1997.Reaction result is listed in table 2-4.

Taking off carbon yield calculates according to following formula.

Comparative Examples 2-11

This Comparative Examples explanation reference method is used for the effect that residual hydrogenation takes off carbon residue, and catalyzer is DC2-3A.

According to the method evaluation reference catalyst DC2-3A of embodiment 2-6, reaction result is listed in table 2-4.

Comparative Examples 2-12

This Comparative Examples explanation reference method is used for the effect that residual hydrogenation takes off carbon residue, and catalyzer is DC2-3B.

According to the method evaluation reference catalyst DC2-3B of embodiment 2-6, reaction result is listed in table 2-4.

Table 2-4

	Catalyzer	Take off carbon yield/%
			Embodiment 2-6	C2-3	56.2
Comparative Examples 2-11	DC2-3A	55.8
			Comparative Examples 2-12	DC2-3B	54.6

Table 2-4 result shows that with respect to reference method, the method for the invention provides has better residual hydrogenation and takes off the carbon residue effect.

Embodiment 3-1,3-2, the 3-3 explanation is suitable for hydrotreating catalyst take titanium dioxide-aluminum oxide as carrier of the present invention and preparation method thereof; Comparative Examples 3-1,3-2,3-3,3-4,3-5,3-6 explanation reference hydrotreating catalyst take titanium dioxide-aluminum oxide as carrier and preparation method thereof.

Preparing catalyzer of the present invention and reference catalyst is prepared by following methods with the titanium dioxide-aluminum oxide carrier.

TA-1 titanium dioxide-aluminum oxide carrier:

(the special company of the triumphant benefit in Tianjin produces with 1000 gram Ti-contained aluminium hydroxide powder first, butt 64%) with after 30 gram sesbania powder mixes, again with 18 milliliters of nitric acid (concentration 65-68%, analytical pure, chemical plant, Gansu Province, west, Shantou) and 900 milliliters of mixing of water, it is even afterwards this mixture to be continued kneading at double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains titanium dioxide-aluminum oxide carrier TA-1 through 120 ℃ of dryings.Adopt x-ray fluorescence method to measure the composition of TA-1, in oxide compound and take described carrier as benchmark, titanium oxide content is 15 % by weight.

Adopt BET N ₂Absorption method is analyzed the TA-1 carrier, and the specific surface area of this carrier is 257 meters squared per gram, 0.66 ml/g of pore volume.

TA-2 titanium dioxide-aluminum oxide carrier:

First with the 700 gram aluminum hydroxide solid elastomer powder (pseudo-boehmites that Sinopec catalyzer Chang Ling branch office produces, butt 70%) and 300 gram pseudo-boehmites (Shandong Aluminium Industrial Corp produces, butt 69%), 35 gram sesbania powder grams mix, again with this mixture and 796 gram metatitanic acid slurries (production of the auspicious shirt in Jinan Chemical Industry Science Co., Ltd), 22 milliliters of nitric acid (concentration 65-68%, analytical pure, chemical plant, Gansu Province, west, Shantou), 700 ml waters mix, it is even to continue kneading at double screw banded extruder afterwards, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain titanium dioxide-aluminum oxide carrier TA-2.Adopt x-ray fluorescence method to measure the composition of TA-2, in oxide compound and take described carrier as benchmark, titanium oxide content is 30 % by weight.

Adopt BET N ₂Absorption method is analyzed the TA-2 carrier, and the specific surface area of this carrier is 231 meters squared per gram, 0.56 ml/g of pore volume.

TA-3 titanium dioxide-aluminum oxide carrier:

(the permanent brightness chemical industry in Yantai company limited produces with the commercial pseudo-boehmite of 1000 grams, butt 69%) mixes with 22 gram sesbania powder, again with this mixture and 20 milliliters of nitric acid, 740 ml waters mix, it is even to continue kneading at double screw banded extruder afterwards, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain 690 gram alumina supporters, with containing tetrabutyl titanate (Beijing sharp fine chemicals of benefit company, chemical pure) the above-mentioned alumina supporters of 590 milliliters of ethanolic solns dipping of 122 grams through 120 ℃ of dryings 4 hours and 480 ℃ of roastings 3 hours, obtain titanium dioxide-aluminum oxide carrier TA-3 respectively.Adopt x-ray fluorescence method to measure the composition of TA-3, in oxide compound and take described carrier as benchmark, titanium oxide content is 4 % by weight.

Adopt BET N ₂Absorption method is analyzed the TA-3 carrier, and the specific surface area of this carrier is 242 meters squared per gram, 0.69 ml/g of pore volume.

The employed raw material sources of Kaolinite Preparation of Catalyst are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry company limited product, technical grade; Ammonium metawolframate, Zhuzhou diamond tungsten product company limited product, technical grade; Nickelous nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product, analytical pure; Basic nickel carbonate, Yixing Xu Chi chemical industry company limited product, chemical pure; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Beijing Yili Fine Chemicals Co., Ltd., analytical pure; Phosphoric acid, Beijing Chemical Plant's product, analytical pure, 85% concentration; Citric acid monohydrate Food grade, Beijing Chemical Plant's product, analytical pure; Neutral ammonium fluoride, chemical plant, Jinan product, analytical pure.

Embodiment 3-1

Get TA-1 carrier 150 grams, flooded 2 hours with 123 milliliters of aqueous solution that contain ammonium paramolybdate 30.3 grams, phosphatase 11 2.1 grams, in 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours make and contain the molybdenum carrier, contain the molybdenum carrier 2 hours with 87 milliliters of aqueous solution dippings that contain Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 22.3 grams afterwards, in 120 ℃ of dryings 4 hours, make catalyzer C 3-1, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Comparative Examples 3-1

Get TA-1 carrier 150 grams, contain ammonium paramolybdate 30.3 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 22.3 grams with 123 milliliters, the aqueous solution dipping of phosphatase 11 2.1 grams 2 hours, in 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours, obtain comparative catalyst DC3-1A, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Comparative Examples 3-2

Get TA-1 carrier 150 grams, contain ammonium paramolybdate 30.3 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 22.3 grams, the aqueous solution dipping of phosphatase 11 2.1 grams 2 hours with 123 milliliters, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC3-1B, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Embodiment 3-2

Get TA-2 carrier 150 grams, flooded 2 hours with 120 milliliters of aqueous solution that contain ammonium metawolframate 58.2 grams, ammonium paramolybdate 2.7 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, what make load molybdenum oxide and Tungsten oxide 99.999 contains molybdenum, tungsten carrier, contains molybdenum, tungsten carrier 2 hours with the 62 milliliters of dippings of the aqueous solution that contain nickelous nitrate 61.3 grams afterwards, in 120 ℃ of dryings 4 hours, obtain catalyzer C 3-2, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Comparative Examples 3-3

Get TA-2 carrier 150 grams, flooded described carriers 2 hours with 120 milliliters of the aqueous solution that contains ammonium metawolframate 58.2 grams, ammonium paramolybdate 2.7 grams, nickelous nitrate 61.3 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, obtain comparative catalyst DC3-2A, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Comparative Examples 3-4

Get TA-2 carrier 150 grams, with 120 milliliters of described carriers of dipping of the aqueous solution that contain ammonium metawolframate 58.2 gram, ammonium paramolybdate 2.7 grams, nickelous nitrate 61.3 grams 2 hours, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC3-2B, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Embodiment 3-3

Get TA-3 carrier 150 gram, with the aqueous solution dipping of 130 milliliters of fluorinated ammoniums, 7.6 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Flooded above-mentioned fluorine-containing carrier 2 hours with the 116 milliliters of liquid of the aqueous solution that contain ammonium metawolframate 96.1 gram, in 120 ℃ of oven dry 4 hours, 420 ℃ of roastings 4 hours made the tungstenic carrier of load Tungsten oxide 99.999.

With 64 milliliters of above-mentioned tungstenic carriers of dipping of the aqueous solution that contains basic nickel carbonate 17.2 gram, Citric acid monohydrate Food grade 19.7 grams, in 170 ℃ of dryings 4 hours, obtain catalyzer C3-3, take catalyst weight as benchmark, composition measuring the results are shown in table 3-1.

Comparative Examples 3-5

Get TA-3 carrier 150 gram, with the aqueous solution dipping of 130 milliliters of fluorinated ammoniums, 7.6 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Flooded fluorine-containing carriers 2 hours with 116 milliliters of the aqueous solution that contains ammonium metawolframate 96.1 grams, basic nickel carbonate 17.2 grams, Citric acid monohydrate Food grade 24.6 grams, in 120 ℃ of dryings 4 hours, 420 ℃ of roastings 4 hours, obtain comparative catalyst DC3-3A, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Comparative Examples 3-6

Get TA-3 carrier 150 gram, with the aqueous solution dipping of 130 milliliters of fluorinated ammoniums, 7.6 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Flooded fluorine-containing carriers 2 hours with 116 milliliters of the aqueous solution that contains ammonium metawolframate 96.1 grams, basic nickel carbonate 17.2 grams, Citric acid monohydrate Food grade 24.6 grams, in 170 ℃ of dryings 4 hours, obtain comparative catalyst DC3-3B, take catalyst weight as benchmark, 3-1 is shown in the results are shown in of composition measuring.

Table 3-1

Embodiment 3-4,3-5, the 3-6 explanation the invention provides the effect of method.

Comparative Examples 3-7,3-8,3-9,3-10,3-11, the effect of 3-12 explanation reference method.

Embodiment 3-4

Present embodiment explanation the present invention is used for the effect of vacuum residuum hydrotreatment, and catalyzer is C 3-1.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 250 milliliters of hydrogenation units, and raw materials used oil nature, reaction conditions see Table 3-2, and reaction result sees Table 3-3.

Table 3-2

Stock oil character	Vacuum residuum
		Density (20 ℃), g/cm 3	0.9668
S，ppm	33000
		N，ppm	2400
MCR，m％	10.7
		Metal content, ppm
Ni	15.6

V	38.2
		Reaction conditions
The hydrogen dividing potential drop, MPa	14.0
		Catalyst volume, mL	100
Temperature, ℃	380
		Volume space velocity, h -1	0.5
Hydrogen-oil ratio, v/v	700

The measuring method of sulphur is GB/T 17040-2008, and the nitrogen determination method is SH/T 0704-2001.

The hydrodesulfurization activity of catalyzer calculates by 2.0 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related calculation formula is as follows.

Reaction result sees Table 3-3.

Comparative Examples 3-7

This Comparative Examples explanation reference method is used for the effect of vacuum residuum hydrotreatment, and catalyzer is DC3-1A.

According to the method evaluation comparative catalyst DC3-1A of embodiment 3-4, reaction result sees Table 3, take the activity of DC3-1A catalyzer as 100.

Comparative Examples 3-8

This Comparative Examples explanation reference method is used for the effect of vacuum residuum hydrotreatment, and catalyzer is DC3-1B.

According to the method evaluation comparative catalyst DC3-1B of embodiment 3-4, reaction result sees Table 3-3.

Table 3-3

Table 3-3 result shows that with respect to reference method, the method for the invention provides has better residual hydrocracking performance.

Embodiment 3-5

Present embodiment explanation the present invention is used for the effect of liquefied coal coil hydrotreatment, and catalyzer is C3-2.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 100 milliliters of hydrogenation units, and raw materials used oil nature, reaction conditions see Table 3-4, and reaction result sees Table 3-5.The hydrodesulfurization activity of catalyzer calculates by 1.65 order reactions, and related calculation formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and calculation formula is seen embodiment 3-4.

The measuring method of sulphur is SH/T 0689-2000, and the nitrogen determination method is SH/T 0657-2007.

Table 3-4

Stock oil character	Liquefied coal coil
		Density (20 ℃), g/cm 3	0.9934
S，ppm	133
		N，ppm	3500
Colloid, m%	8.0
		Reaction conditions
The hydrogen dividing potential drop, MPa	12.0
		Catalyst volume, mL	100

Temperature, ℃	380
		Volume space velocity, h -1	1.4
Hydrogen-oil ratio, v/v	600

Comparative Examples 3-9

This Comparative Examples explanation reference method is used for the effect of liquefied coal coil hydrotreatment, and catalyzer is reference catalyst DC3-2A.

According to the method evaluation reference catalyst DC3-2A of embodiment 3-5, reaction result is listed in table 3-5, take the activity of DC3-2A catalyzer as 100.

Comparative Examples 3-10

This Comparative Examples explanation reference method is used for the effect of liquefied coal coil hydrotreatment, and catalyzer is DC3-2B.

According to the method evaluation reference catalyst DC3-2B of embodiment 3-5, reaction result is listed in table 3-5.

Table 3-5

Table 3-5 result shows that with respect to reference method, the method for the invention provides has better liquefied coal coil hydrotreatment effect.

Embodiment 3-6

Present embodiment explanation the present invention is used for the hydrorefined effect of straight-run diesel oil, and catalyzer is C3-3.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 30 milliliters of hydrogenation units, and raw materials used oil nature, reaction conditions see Table 3-6, and reaction result sees Table 3-7.The hydrodesulfurization activity of catalyzer calculates by 1.65 order reactions, and related calculation formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and calculation formula is seen embodiment 3-5.The measuring method of sulphur is SH/T 0689-2000, and the nitrogen determination method is SH/T 0657-2007.

Reaction result is listed in table 3-7.

Table 3-6

Stock oil character	Straight-run diesel oil
		Density (20 ℃), g/cm 3	0.8440
S，ppm	8300
		N，ppm	150
Refractive index (20 ℃)	1.4721
		Reaction conditions
The hydrogen dividing potential drop, MPa	3.2
		Catalyst volume, mL	30
Temperature, ℃	350
		Volume space velocity, h -1	2.0
Hydrogen-oil ratio, v/v	300

Comparative Examples 3-11

This Comparative Examples explanation reference method is used for the hydrorefined effect of straight-run diesel oil, and catalyzer is DC3-3A.

According to the method evaluation reference catalyst DC3-3A of embodiment 3-6, reaction result is listed in table 3-7, take the activity of DC3-3A catalyzer as 100.

Comparative Examples 3-12

This Comparative Examples explanation reference method is used for the hydrorefined effect of straight-run diesel oil, and catalyzer is DC3-3B.

According to the method evaluation reference catalyst DC3-3B of embodiment 3-6, reaction result is listed in table 3-7.

Table 3-7

Table 3-7 result shows that with respect to reference method, the method for the invention provides has better straight-run diesel oil hydrofining effect.

Embodiment 4-1,4-2, the 4-3 explanation is suitable for hydrotreating catalyst take Zirconia-alumina as carrier of the present invention and preparation method thereof; Comparative Examples 4-1,4-2,4-3,4-4,4-5,4-6 explanation reference hydrotreating catalyst take Zirconia-alumina as carrier and preparation method thereof.

Preparing catalyzer of the present invention and reference catalyst is prepared by following methods with the Zirconia-alumina carrier.

ZA-1 Zirconia-alumina carrier:

(the special company of the triumphant benefit in Tianjin produces with 1000 gram aluminium hydrate powders, butt 68%) with after 28 gram sesbania powder mixes, again with 20 milliliters of nitric acid (concentration 65-68%, analytical pure, chemical plant, Gansu Province, west, Shantou) and 910 milliliters of mixing of water, it is even afterwards this mixture to be continued kneading at double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains alumina supporter through 120 ℃ of dryings.

Contain Zircosol ZN (chemical industry company limited far away product in the permanent industry in Beijing with 516 milliliters, analytical pure) aqueous solution dipping 600 of 70 grams restrains alumina supporters 2 hours, in 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours, make Zirconia-alumina carrier ZA-1, in oxide compound and take described carrier as benchmark, zirconia content is 5 % by weight.

Adopt BET N ₂Absorption method is analyzed the ZA-1 carrier, and the specific surface area of this carrier is 244 meters squared per gram, 0.71 ml/g of pore volume.

ZA-2 Zirconia-alumina carrier:

First with the 1000 gram aluminum hydroxide solid elastomer powder (pseudo-boehmites that Sinopec catalyzer Chang Ling branch office produces, butt 70%) mixes with 33 gram sesbania powder, again with this mixture with contain basic zirconium chloride (the special reagent of Chengdu bass company limited, analytical pure) 465 aqueous solution that restrain are 870 milliliters, 19 milliliters of nitric acid (concentration 65-68%, analytical pure, chemical plant, Gansu Province, west, Shantou) mixes, it is even to continue kneading at double screw banded extruder, be extruded into afterwards the butterfly bar of 1.3 millimeters of ф, wet bar is through 120 ℃ of dryings after 4 hours, in 600 ℃ of roastings 3 hours, obtain Zirconia-alumina carrier ZA-2.In oxide compound and take described carrier as benchmark, zirconia content is 20 % by weight.

Adopt BET N ₂Absorption method is analyzed the ZA-2 carrier, and the specific surface area of this carrier is 267 meters squared per gram, 0.60 ml/g of pore volume.

The employed raw material sources of Kaolinite Preparation of Catalyst are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry company limited product, technical grade; Ammonium metawolframate, Zhuzhou diamond tungsten product company limited product, technical grade; Nickelous nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product, analytical pure; Basic nickel carbonate, Yixing Xu Chi chemical industry company limited product, chemical pure; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Beijing Yili Fine Chemicals Co., Ltd., analytical pure; Phosphoric acid, Beijing Chemical Plant's product, analytical pure, 85% concentration; Citric acid monohydrate Food grade, Beijing Chemical Plant's product, analytical pure; Neutral ammonium fluoride, chemical plant, Jinan product, analytical pure.

Embodiment 4-1

Get ZA-1 carrier 150 grams, flooded 2 hours with 117 milliliters of aqueous solution that contain ammonium paramolybdate 66.5 grams, phosphatase 11 4.5 grams, in 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contains the molybdenum carrier 2 hours with 70 milliliters of aqueous solution dippings that contain Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 42.5 grams afterwards, in 120 ℃ of dryings 4 hours, make catalyzer C4-1, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Comparative Examples 4-1

Get ZA-1 carrier 150 grams, contain ammonium paramolybdate 66.5 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 42.5 grams with 117 milliliters, the aqueous solution dipping of phosphatase 11 4.5 grams 2 hours, in 120 ℃ of dryings 4 hours, 480 ℃ of roastings 4 hours, obtain comparative catalyst DC4-1A, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Comparative Examples 4-2

Get ZA-1 carrier 150 grams, contain ammonium paramolybdate 66.5 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 42.5 grams, the aqueous solution dipping of phosphatase 11 4.5 grams 2 hours with 117 milliliters, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC4-1B, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Embodiment 4-2

Get ZA-2 carrier 150 grams, flooded 2 hours with 109 milliliters of aqueous solution that contain ammonium paramolybdate 32.4 grams, phosphatase 79 .1 gram, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, what make the load molybdenum oxide contains the molybdenum carrier, contains the molybdenum carrier 2 hours with the 71 milliliters of dippings of the aqueous solution that contain nickelous nitrate 19.3 grams afterwards, in 120 ℃ of dryings 4 hours, obtain catalyzer C4-2, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Comparative Examples 4-3

Get ZA-2 carrier 150 grams, flooded described carriers 2 hours with 109 milliliters of the aqueous solution that contains ammonium paramolybdate 32.4 grams, nickelous nitrate 19.3 grams and phosphatase 79 .1 gram, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, obtain comparative catalyst DC4-2A, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Comparative Examples 4-4

Get ZA-2 carrier 150 grams, with 109 milliliters of described carriers of dipping of the aqueous solution that contains ammonium paramolybdate 32.4 gram, nickelous nitrate 19.3 grams and phosphatase 79 .1 gram 2 hours, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC4-2B, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Embodiment 4-3

Get ZA-1 carrier 150 gram, with the aqueous solution dipping of 109 milliliters of fluorinated ammoniums, 4.8 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

The 105 milliliters of above-mentioned fluorine-containing carriers of dipping of the aqueous solution 2 hours that contain ammonium metawolframate 83.1 gram, in 120 ℃ of oven dry 2 hours, 450 ℃ of roastings 3 hours made the tungstenic carrier of load Tungsten oxide 99.999.

With 61 milliliters of above-mentioned tungstenic carriers of dipping of the aqueous solution that contains basic nickel carbonate 16.2 gram, Citric acid monohydrate Food grade 20.9 grams, in 170 ℃ of dryings 4 hours, obtain catalyzer C4-3, take catalyst weight as benchmark, composition measuring the results are shown in table 4-1.

Comparative Examples 4-5

Get ZA-1 carrier 150 gram, with the aqueous solution dipping of 109 milliliters of fluorinated ammoniums, 4.8 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Flooded above-mentioned fluorine-containing carriers 2 hours with 105 milliliters of the aqueous solution that contains ammonium metawolframate 83.1 grams, basic nickel carbonate 16.2 grams, Citric acid monohydrate Food grade 20.9 grams, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours, obtain comparative catalyst DC4-3A, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Comparative Examples 4-6

Get ZA-1 carrier 150 gram, with the aqueous solution dipping of 109 milliliters of fluorinated ammoniums, 4.8 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain fluorine-containing carrier.

Flooded above-mentioned fluorine-containing carriers 2 hours with 109 milliliters of the aqueous solution that contains ammonium metawolframate 81.8 grams, basic nickel carbonate 16.0 grams, Citric acid monohydrate Food grade 20.6 grams, in 170 ℃ of dryings 4 hours, obtain comparative catalyst DC4-3B, take catalyst weight as benchmark, 4-1 is shown in the results are shown in of composition measuring.

Table 4-1

Embodiment 4-4,4-5, the 4-6 explanation the invention provides the effect of method.

Comparative Examples 4-7,4-8,4-9,4-10,4-11, the effect of 4-12 explanation reference method.

Embodiment 4-4

Present embodiment explanation the present invention is used for the effect of wax tailings hydrotreatment, and catalyzer is C4-1.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 100 milliliters of hydrogenation units, and raw materials used oil nature, reaction conditions see Table 4-2, and reaction result sees Table 4-3.

Table 4-2

The measuring method of sulphur is SH/T 0689-2000, and the nitrogen determination method is SH/T 0704-2001.

The hydrodesulfurization activity of catalyzer calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related calculation formula is as follows.

Comparative Examples 4-7

This Comparative Examples explanation reference method is used for the effect of wax tailings hydrotreatment, and catalyzer is DC4-1A.

According to the method evaluation comparative catalyst DC4-1A of embodiment 4-4, reaction result sees Table 4-3, take the activity of DC4-1A catalyzer as 100.

Comparative Examples 4-8

This Comparative Examples explanation reference method is used for the effect of wax tailings hydrotreatment, and catalyzer is DC4-1B.

According to the method evaluation comparative catalyst DC4-1B of embodiment 4-4, reaction result sees Table 4-3.

Table 4-3

Table 4-3 result shows that with respect to reference method, the method for the invention provides has better wax tailings hydrotreatment effect.

Embodiment 4-5

Present embodiment explanation the present invention is used for the hydrorefined effect of coker gas oil, and catalyzer is C4-2.

Catalyst breakage is become the 2-4 mm granules, and reaction is carried out at 100 milliliters of hydrogenation units, and raw materials used oil nature, reaction conditions see Table 4-4, and reaction result sees Table 4-5.The hydrodesulfurization activity of catalyzer calculates by 1.65 order reactions, and related calculation formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and calculation formula is seen embodiment 4-4.

The measuring method of sulphur is SH/T 0689-2000, and the nitrogen determination method is SH/T 0657-2007.

Table 4-4

Stock oil character	Coker gas oil
		Density (20 ℃), g/cm 3	0.8426
S，ppm	8100
		N，ppm	1620
Refractive index (20 ℃)	1.4723
		Reaction conditions
The hydrogen dividing potential drop, MPa	6.4
		Catalyst volume, mL	100
Temperature, ℃	350
		Volume space velocity, h -1	2.5
Hydrogen-oil ratio, v/v	400

Comparative Examples 4-9

This Comparative Examples explanation reference method is used for the hydrorefined effect of coker gas oil, and catalyzer is DC4-2A.

According to the method evaluation reference catalyst DC4-2A of embodiment 4-5, reaction result is listed in table 4-5, take the activity of DC4-2A catalyzer as 100.

Comparative Examples 4-10

This Comparative Examples explanation reference method is used for the hydrorefined effect of coker gas oil, and catalyzer is DC4-2B.

According to the method evaluation reference catalyst DC4-2B of embodiment 4-5, reaction result is listed in table 4-5.

Embodiment 4-6

Present embodiment explanation the present invention is used for the hydrorefined effect of coker gas oil, and catalyzer is C4-3.

Evaluation method is with embodiment 4-5, and reaction result sees Table 4-5.

Comparative Examples 4-11

This Comparative Examples explanation reference method is used for the hydrorefined effect of coker gas oil, and catalyzer is DC4-3A.

According to the method evaluation reference catalyst DC4-3A of embodiment 4-5, reaction result is listed in table 4-5.

Comparative Examples 4-12

This Comparative Examples explanation reference method is used for the hydrorefined effect of coker gas oil, and catalyzer is DC4-3B.

According to the method evaluation reference catalyst DC4-3B of embodiment 4-5, reaction result is listed in table 4-5.

Table 4-5

Table 4-5 result shows that with respect to reference method, the method for the invention provides has better coker gas oil hydrofining effect.

Embodiment 5-1,5-2, the 5-3 explanation is suitable for hydrotreating catalyst that contains molecular sieve of the present invention and preparation method thereof; Comparative Examples 4-1,4-2,4-3,4-4,4-5, the 4-6 explanation contains reference hydrotreating catalyst of molecular sieve and preparation method thereof.

Preparing catalyzer of the present invention and reference catalyst is prepared by following methods with containing molecular sieve carrier:

The used preparation that contains molecular sieve complex carrier S-1 of catalyzer of the present invention:

With 1000 gram pseudo-boehmite (Sinopec catalyzer Chang Ling branch office products, butt is 72%) and 108 gram USY type molecular sieve (Sinopec catalyzer Chang Ling branch office products, lattice constant 24.55 dusts, butt 74 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, and 600 ℃ of roastings obtained carrier S 1 in 4 hours, the content of aluminum oxide is that the content of 90%, USY type molecular sieve is 10% among the S1.

The used preparation that contains molecular sieve complex carrier S-2 of catalyzer of the present invention:

(Beijing flying dragon horse company produces, SiO with 200 gram alkaline silica sols ₂Content is 30%), 83 gram pseudo-boehmite (Sinopec catalyzer Chang Ling branch office products, butt 72%) with 108.1 gram HY type molecular sieve (Sinopec catalyzer Chang Ling branch office product, lattice constant 24.62 dusts, butt 74 heavy %) mix, be extruded into circumscribed circle diameter and be 1.6 millimeters trilobal bar, wet bar was in 120 ℃ of oven dry 4 hours, and 480 ℃ of roastings obtained carrier S-2 in 4 hours.The content of silicon oxide is 30% among the S-2, and the content of aluminum oxide is that the content of 30%, HY type molecular sieve is 40%.

The used preparation that contains molecular sieve complex carrier S-3 of catalyzer of the present invention:

With 133 gram alkaline silica sol (Beijing flying dragon horse company product, SiO ₂Content is 30% weight), 125 gram pseudo-boehmites (Sinopec catalyzer Chang Ling branch office product), 25.6 gram Siral40 powder (Condea company product) and 118 gram USY (Sinopec catalyzer Chang Ling branch officies, lattice constant 2.450 nanometers, butt 76 % by weight) and 11.5 gram β zeolite (Sinopec catalyzer Chang Ling branch office products, silica alumina ratio 120, butt 87 % by 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, 580 ℃ of roastings obtained carrier S-3 in 4 hours, the content of silicon oxide is 20% among the S-3, the content of aluminum oxide is 45%, silica-alumina content is that the content of 10%, USY type molecular sieve is 20%, and the content of beta molecular sieve is 5%.

The employed raw material sources of Kaolinite Preparation of Catalyst are as follows: ammonium paramolybdate, Anqing moon metallurgy of copper chemical industry company limited product, technical grade; Ammonium metawolframate, Zhuzhou diamond tungsten product company limited product, technical grade; Nickelous nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product, analytical pure; Basic nickel carbonate, Yixing Xu Chi chemical industry company limited product, chemical pure; Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, Beijing Yili Fine Chemicals Co., Ltd., analytical pure; Phosphoric acid, Beijing Chemical Plant's product, analytical pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product, analytical pure; Citric acid monohydrate Food grade, Beijing Chemical Plant's product, analytical pure; Glycerol, Beijing Chemical Plant's product, analytical pure.

Embodiment 5-1

Get S-1 carrier 150 grams, flooded 2 hours with 124 milliliters of the aqueous solution that contains ammonium paramolybdate 26.2 grams, ammoniacal liquor 5.5 grams, through 120 ℃ of dryings 4 hours and 420 ℃ of roastings after 4 hours, be cooled to room temperature, make the carrier of load molybdenum oxide, again flooded 2 hours with 85 milliliters of the aqueous solution that contains Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 17.4 grams, in 120 ℃ of oven dry 6 hours, obtain catalyzer C-1 afterwards.Take catalyst weight as benchmark, adopt the chemical constitution among the x-ray fluorescence method mensuration catalyzer C5-1, measurement result is listed in table 5-1 (following herewith example).

Comparative Examples 5-1

Get S-1 carrier 150 gram, flooded 2 hours with 124 milliliters of aqueous solution that contain ammonium paramolybdate 26.2 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 17.4 grams, ammoniacal liquor 5.5 grams, in 120 ℃ of dryings 4 hours, 420 ℃ of roastings 4 hours obtained comparative catalyst DC5-1A.

Comparative Examples 5-2

Get S-1 carrier 150 gram, flooded 2 hours with 124 milliliters of aqueous solution that contain ammonium paramolybdate 26.2 grams, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES 17.4 grams, ammoniacal liquor 5.5 grams, in 120 ℃ of dryings 4 hours, obtain comparative catalyst DC5-1B.

Embodiment 5-2

Get S-2 carrier 150 grams, flooded 2 hours with 126 milliliters of the aqueous solution that contains ammonium metawolframate 97.8 grams, through 120 ℃ of dryings 4 hours and 450 ℃ of roastings after 4 hours, be cooled to room temperature, make the carrier of load Tungsten oxide 99.999, again flooded 2 hours with 63 milliliters of the aqueous solution that contains nickelous nitrate 30.3 grams, 9.6 gram glycerol, in 120 ℃ of oven dry 2 hours, obtain catalyzer C5-2 afterwards.

Comparative Examples 5-3

Get S-2 carrier 150 gram, with 126 milliliters of dippings of the aqueous solution that contain ammonium metawolframate 97.8 grams, nickelous nitrate 30.3 grams, glycerol 9.6 grams 2 hours, after 4 hours, obtain comparative catalyst DC5-2A through 120 ℃ of dryings 2 hours and 450 ℃ of roastings.

Comparative Examples 5-4

Get S-2 carrier 150 gram, with 126 milliliters of dippings of the aqueous solution that contain ammonium metawolframate 97.8 grams, nickelous nitrate 17.4 grams, glycerol 9.6 grams 2 hours, through 120 ℃ of dryings 2 hours, obtain comparative catalyst DC5-2B.

Embodiment 5-3

Get S-3 carrier 150 grams, flooded 2 hours with 128 milliliters of the aqueous solution that contains ammonium paramolybdate 44.4 grams, phosphatase 79 .7 gram, through 120 ℃ of dryings 4 hours and 480 ℃ of roastings after 4 hours, be cooled to room temperature, make the carrier of load molybdenum oxide, again flooded 2 hours with containing 72 milliliters of basic nickel carbonate 13.6 grams, 29.3 gram lemon aqueous acids, in 175 ℃ of oven dry 4 hours, obtain catalyzer C5-3 afterwards.

Comparative Examples 5-5

Get S-3 carrier 150 grams, flooded 2 hours with 128 milliliters of the aqueous solution that contains ammonium paramolybdate 44.4 grams, basic nickel carbonate 13.6 grams, phosphatase 79 .7 gram and citric acid 29.3 grams, after 4 hours, obtain comparative catalyst DC5-3A through 120 ℃ of dryings 4 hours and 480 ℃ of roastings.

Comparative Examples 5-6

Get S-3 carrier 150 gram, with 128 milliliters of dippings of the aqueous solution that contain ammonium paramolybdate 44.4 grams, basic nickel carbonate 13.6 grams, phosphatase 79 .7 gram and citric acid 29.3 grams 2 hours, after 4 hours, obtain comparative catalyst DC5-3B through 180 ℃ of dryings.

Table 5-1

Embodiment 5-4,5-5, the 5-6 explanation the invention provides the effect of method.

Comparative Examples 5-7,5-8,5-9,5-10,5-11, the effect of 5-12 explanation reference method.

Embodiment 5-4

Present embodiment explanation the present invention is used for the effect of diesel oil hydrofining, and catalyzer is C5-1.

Catalyst breakage is become the 2-4 mm granules, and evaluate catalysts C5-1 on 30 milliliters of hydrogenation units, raw materials used oil are the mixing raw material of straight-run diesel oil and catalytic cracking diesel oil, and sulphur content is 7800ppm, and nitrogen content is 403ppm, and density is 0.8640g/cm ³Reaction conditions is: 360 ℃ of temperature, volume space velocity 1.2h ^-1, hydrogen dividing potential drop 4.8MPa, hydrogen to oil volume ratio 300.Reaction result is provided by table 5-2.The measuring method of sulphur is SH/T 0689-2000, and the nitrogen determination method is SH/T 0657-2007.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.

Comparative Examples 5-7,5-8

The diesel oil hydrofining effect of reference method is described, catalyzer is respectively DC5-1A and DC5-1B.

According to method evaluation reference catalyst DC5-1A and the DC5-1B of embodiment 5-4, reaction result is listed in table 5-2, take the activity of DC5-1A catalyzer as 100.

Table 5-2

From the table 5-2 the result as can be known, the diesel oil hydrofining effect that the invention provides method is better than reference method.

Embodiment 5-5

Present embodiment explanation the present invention is used for the effect that aromatic hydrogenation transforms, and catalyzer is C5-2.

Hydroconversion reactions is carried out at fixed-bed micro-devices.Catalyst breakage is the particle of 0.3-0.45 millimeter, and the catalyzer loading amount is 0.2 milliliter.Reaction raw materials oil is for containing the octane solution of naphthane 5.0% weight.Reaction conditions is: 390 ℃ of temperature, pressure 4.1MPa, volume space velocity 30h ^-1, hydrogen oil (mole) is than being 25.Vulcanize before the catalyst reaction, cure conditions is: 300 ℃ of constant temperature 4 hours, and pressure 2.0MPa, vulcanizing agent adopts the hexane solution of 5%DMDS.

Adopt the aromatic hydrogenation transformation efficiency to describe the hydrocracking performance of catalyzer.The aromatic hydrogenation transformation efficiency calculates by following formula.Reaction result is listed in table 5-3.

Comparative Examples 5-9,5-10

The hydrocracking effect of reference method is described, catalyzer is respectively DC5-2A and DC5-2B.

Adopt method evaluation reference catalyst DC5-2A and the DC5-2B of embodiment 5-5, reaction result is listed in table 5-3.

Table 5-3

	Catalyzer	Aromatic hydrogenation transformation efficiency %
			Embodiment 5-8	C5-2	67.2
Comparative Examples 5-9	DC5-2A	51.0
			Comparative Examples 5-10	DC5-2B	61.3

Table 5-3 result shows that the aromatic hydrogenation activity of conversion that the invention provides method is higher than reference method.

Embodiment 5-6

Present embodiment explanation the present invention is used for the effect of diesel oil hydrogenation modification, and catalyzer is C5-3.

Take density as 0.9258 gram per centimeter ³Sulphur content is that 2700ppm, nitrogen content are 1800ppm, cetane value is that 27.3 catalytic cracking diesel oil is raw material, estimate the performance of catalyzer C-3 provided by the invention at 30 milliliters of fixed bed devices, the catalyzer loading amount is 20 milliliters, and reaction conditions is: 360 ℃ of temperature, pressure 6.4MPa, volume space velocity 1.0 hours ^-1, hydrogen to oil volume ratio 600, the results are shown in the table 5-4.The measuring method of sulphur is SH/T 0689-2000, and the nitrogen determination method is SH/T 0657-2007, and the measuring method of cetane value is GB/T 386-91.

Comparative Examples 5-11,5-12

Illustrate that reference method is used for the effect of diesel oil hydrogenation modification, catalyzer is respectively DC5-3A, DC5-3B.

According to method evaluation reference catalyst DC5-3A and the DC5-3B of embodiment 5-6, reaction result is listed in table 5-4.

Table 5-4

	Embodiment 5-6	Comparative Examples 5-11	Comparative Examples 5-12
				Catalyzer	C5-3	DC5-3A	DC5-3B
Product density, gram per centimeter 3	0.8824	0.8848	0.8832
				Desulfurization degree, % by weight	93.9	92.3	93.2
Denitrification percent, % by weight	99.3	98.4	98.9
				The product cetane value	38.2	36.7	37.7
The cetane value increased value	10.9	9.4	10.4
				Density reduction value, gram per centimeter 3	0.0434	0.0410	0.0426
Diesel yield, V%	＞95	＞95	＞95

5-4 result can find out from table, and the method that the invention provides is used for diesel oil hydrogenation modification and not only has desulfurization, the nitrogen removal performance that is better than reference method, and can more effectively reduce diesel oil density, improves diesel cetane-number.

Claims (30)

1. method for hydrotreating hydrocarbon oil, be included under hydrogen existence and the hydrogenation conditions, hydrocarbon oil feed is contacted with hydrotreating catalyst, described hydrotreating catalyst contains carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, it is characterized in that, described group vib metal component exists with the form of metal oxide, and described VIII family metal component exists with the form of metal-salt.

2. according to 1 described method, it is characterized in that take described hydrotreating catalyst as benchmark and with oxide compound, the content of described VIII family metal component is the 1-10 % by weight, the content of group vib metal component is the 5-40 % by weight.

3. according to 2 described methods, it is characterized in that take described hydrotreating catalyst as benchmark and with oxide compound, the content of described VIII family metal component is the 1.5-7 % by weight, the content of group vib metal component is the 7-35 % by weight.

4. according to 1 described method, it is characterized in that described group vib metal component is selected from one or more among Cr, Mo, the W, described VI I I family metal component is selected from one or more among Fe, Co, the Ni.

5. according to 4 described methods, it is characterized in that described group vib metal is Mo and/or W, described VIII family metal component is Co and/or Ni.

6. according to 1 described method, it is characterized in that described metal-salt is selected from the inorganic salt of VIII family metal component or one or more in the organic salt.

7. according to 6 described methods, it is characterized in that described inorganic salt are selected from one or more in carbonate, subcarbonate, the nitrate; Described organic salt is organic carboxylate.

8. according to 1 described method, it is characterized in that the carrier in the described hydrotreating catalyst is selected from one or more in aluminum oxide, silicon oxide, silica-alumina, titanium oxide, titanium dioxide-aluminum oxide, Zirconia-alumina, the molecular sieve.

9. according to 8 described methods, it is characterized in that described aluminum oxide is selected from one or more among γ, η, θ, δ and the χ; Perhaps be selected from and contain one or more and be selected from fluorine, phosphorus, silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth and dose among γ, η, θ, δ and the χ of component one or more.

10. according to 9 described methods, it is characterized in that described aluminum oxide is gama-alumina or contains one or more and be selected from the gama-alumina that fluorine, phosphorus, silicon, titanium, magnesium, boron, zirconium, thorium, niobium, rare earth are dosed component.

11., it is characterized in that take described carrier as benchmark, the silica content in the described silica-alumina is the 2-45 % by weight according to 8 described methods, the content of aluminum oxide is the 55-98 % by weight.

12., it is characterized in that the content of silicon oxide is the 5-40 % by weight in the described silica-alumina according to 11 described methods, the content of aluminum oxide is the 60-95 % by weight.

13., it is characterized in that described molecular screening is from the zeolite molecular sieve of Chang Zuowei catalytic cracking activity component, one or more in the non-zeolitic molecular sieves according to 8 described methods, take described carrier as benchmark, the content of described molecular sieve is the 0.5-85 % by weight.

14. according to 13 described methods, it is characterized in that, one or more in Y zeolite, beta zeolite, mordenite, ZSM-5 of described molecular screening, take described carrier as benchmark, the content of described molecular sieve is the 1-55 % by weight.

15. according to 14 described methods, it is characterized in that, one or more the mixture of described molecular screening in Y zeolite, beta zeolite, ZSM-5, take described carrier as benchmark, the content of described molecular sieve is the 5-50 % by weight.

16., it is characterized in that take described carrier as benchmark, the content of titanium oxide is the 1-50 % by weight in the described titanium dioxide-aluminum oxide carrier according to 8 described methods, the content of aluminum oxide is the 50-99 % by weight.

17., it is characterized in that take described carrier as benchmark, the content of titanium oxide is the 2-40 % by weight in the described titanium dioxide-aluminum oxide carrier according to 8 described methods, the content of aluminum oxide is the 60-98 % by weight.

18., it is characterized in that in oxide compound, the content of titanium oxide is the 3-35 % by weight in the described titanium dioxide-aluminum oxide carrier according to 8 described methods, the content of aluminum oxide is the 65-97 % by weight.

19., it is characterized in that take described carrier as benchmark, zirconic content is the 1-40 % by weight in the described Zirconia-alumina carrier according to 8 described methods, the content of aluminum oxide is the 60-99 % by weight.

20., it is characterized in that take described carrier as benchmark, zirconic content is the 2-35 % by weight in the described Zirconia-alumina carrier according to 8 described methods, the content of aluminum oxide is the 65-98 % by weight.

21., it is characterized in that take described carrier as benchmark, zirconic content is the 3-30 % by weight in the described Zirconia-alumina carrier according to 8 described methods, the content of aluminum oxide is the 70-97 % by weight.

22. according to 8 described methods, it is characterized in that, it is characterized in that take described carrier as benchmark, the content of boron oxide is the 0.5-10 % by weight in the described boron-containing alumina carrier.

23. according to 8 described methods, it is characterized in that, it is characterized in that take described carrier as benchmark, the content of boron oxide is the 1-7 % by weight in the described boron-containing alumina carrier.

24., it is characterized in that described hydrotreating catalyst also contains one or more auxiliary agents that are selected from phosphorus, fluorine, boron, the silicon according to 1 described method, in element and take catalyzer as benchmark, the content of described auxiliary agent is no more than 10 % by weight.

25., it is characterized in that described hydrotreating catalyst also contains organic additive according to 1 to 24 described method, take described catalyzer as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight.

26. according to 1 described method, it is characterized in that, before described hydrotreating catalyst, comprise the hydrogenation activity guard catalyst, by volume and take the catalyzer total amount as benchmark, the content of described hydrogenation activity guard catalyst is below 30%.

27., it is characterized in that by volume and take the catalyzer total amount as benchmark, the content of described hydrogenation activity guard catalyst is 5-20% according to 26 described methods.

28., it is characterized in that described hydrogenation conditions comprises according to 1 described method: temperature of reaction 200-420 ℃, hydrogen dividing potential drop 2-18 MPa, liquid hourly space velocity 0.3-10 hour ^-1, hydrogen to oil volume ratio 50-5000.

29., it is characterized in that described hydrogenation conditions comprises according to 28 described methods: 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.

30., it 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 according to 1 described method.