CN1072706C - Light oil products hydrogenation treatment catalyst containing moly and/or tungsten, and its prepn. method - Google Patents

Abstract

The present invention relates to a hydrogenation treatment catalyst of a light oil product containing molybdenum and/or tungsten. The hydrogenation treatment catalyst contains the following components: 4 wt% to less than 10 wt% of tungstic oxide and/or molybdenum oxide loaded on an alumina carrier, 1 to 5 wt% of nickel oxide and 0.01 to 1 wt % of cobalt oxide, wherein the ratio of the total atomic number of nickel and cobalt to the total atomic number of nickel, cobalt, tungsten and/or molybdenum is from 0.3 to 0.9. Compared with the prior art, the hydrogenation treatment catalyst has low metal content, but has high low-temperature activity. The hydrogenation treatment catalyst is especially suitable for a hydrogenation sweetening process of the light oil product.

Description

Contain light-end products hydrotreating catalyst of molybdenum and/or tungsten and preparation method thereof

The invention relates to a kind of oxide compound of chromium, molybdenum or tungsten or hydrotreating catalyst of oxyhydroxide and preparation method thereof of containing, more particularly, be about a kind of oxide compound of molybdenum and/or tungsten or light-end products hydrotreating catalyst of oxyhydroxide and preparation method thereof of containing.

The total sulfur content of light-end products, mercaptans content and acid number are important indicators, and some light-end products are qualified or approaching qualified as the total sulfur content of illuminating kerosene, aviation kerosene, FCC gasoline, only have mercaptan and acid number defective.The existence of mercaptan not only makes oil product produce stench, and the quality of oil product and stability are descended, and mercaptan itself also has corrodibility, therefore, in refining of petroleum, need remove the mercaptan in the light-end products or be converted into the less disulphide of harm.

Deodour method in industrial application can reduce three classes at present:

1. adopt soda acid electrochemical treating technology: its shortcoming is that the soda acid consumption is big, and the soda acid waste residue pollutes, equipment is had corrosion environment, and the color of product is still stable inadequately.

2. oxidation deodorizing technology: increase in China along with processing Middle East high-sulfur crude oil, the mercaptans content of middle runnings increases to some extent, and its total sulfur content of the cut that has such as Yi Chong boat coal has also surpassed index, now MEROX technologies that adopt non-hydrogen more, it adopts sulfonation titanium mountain valley with clumps of trees and bamboo cobalt catalyst and activator, mercaptan oxidation is become disulphide, product need washing, dehydration of salt, carclazyte decolouring, though be to operate at normal temperatures, but abraum salt, useless carclazyte have produced new pollution, and this technology has strict restriction to the acid number of raw material, and adaptability to raw material is poor.

3. hydrofining technology: this technology is general to adopt common hydrofining equipment and catalyzer, has flexible operation, the advantage of stable and reliable product quality.But this technology also exists investment high, the shortcoming that process cost is high.

In hydrofining technology, used hydrogenation catalyst plays an important role to hydrogenation process.At first, the cost of catalyzer is directly connected to the process cost of whole hydrogenation technique.Therefore, handling the middle distillate oil that total sulfur is qualified or exceed standard slightly, when only needing to remove mercaptan in the intermediate oil and acidic substance, the catalyzer of use should have higher mercaptan removal, depickling activity, and simultaneously, catalyzer becomes should be lower.Moreover, for reducing the investment and the process cost of hydrofining technology, the low temperature of catalyzer (150～200 ℃) activity has very important significance, and catalyzer has the energy consumption that higher activity not only can reduce hydrofining technology at low temperatures, and technical process is also had very important influence.For example, the temperature of a normal line kerosene that distills from the thermal distillation device (being a kind of reaction raw materials of the present invention) is generally about 160～180 ℃, when the temperature of reaction of hydrofining technology is below 200 ℃ the time, when this oil product is carried out hydro-sweetening, this reaction raw materials only need pass through simple heat-exchanger rig, just can reach required temperature of reaction, used heat transferring medium can be used the steam of middle pressure (15 kilograms of pressure), perhaps, reaction raw materials directly enters the hydro-sweetening device without heat exchange, carries out the hydro-sweetening reaction.And when the temperature of reaction of hydrofining technology be 240 ℃ or when higher, make reaction raw materials reach desired reaction temperature, used heat transferring medium then must just can reach with the steam of high equipressure (35 kilograms of pressure).

CN85,104,438B discloses tungsten and the nickel catalyzator that a kind of fluoro-containing alumina that is used for fraction oil hydrogenation refining supports, this catalyzer gama-alumina that to be the purity that obtained by aluminum alkoxide or alkyl aluminum hydrolysis obtain through 500～700 ℃ of roastings greater than the diaspore of 65 heavy %, make fluoro-containing alumina through the dipping fluorine cpd, re-use the technology of soaking altogether, the catalyzer that the oxide compound of tungsten and nickel makes in the load equably, it consists of nickel oxide 1～5 heavy %, Tungsten oxide 99.999 12～35 heavy %, fluorine 1～9 heavy %.Because this catalyst metal content is higher, thereby its cost is higher.This catalyzer is applicable to the hydrofining of distillate, i.e. desulfurization and denitrification process, catalyzer need prevulcanized to handle before use.

CN1,085,934A discloses a kind of catalyzer that is used for hydrorefining petroleum waxes, and this catalyzer is made up of magnesium oxide, nickel oxide, Tungsten oxide 99.999 and aluminum oxide, wherein, content of magnesia 0.1～1.9 heavy %, nickel oxide content 2.5～6.0 heavy %, tungsten oxide content 24.0～34.0 heavy %, this catalyzer is applicable to heavier petroleum fractions, is specially adapted to the unifining process of petroleum wax cut, and has higher hydrogenation activity, but its metal content is higher, and cost is higher.Catalyzer must be handled through prevulcanized before using.

CN1,105,053A discloses a kind of fraction oil Hydrobon catalyst, this catalyzer is made of the aluminum oxide precursor carrier that high-temperature roasting obtains under the gas mixture atmosphere of air and water vapour, fluorine auxiliary agent and nickel and tungsten active ingredient, each component concentration is (with the catalyzer is benchmark, weight %): fluorine 1～9%, nickel oxide 1～5%, Tungsten oxide 99.999 15～38%, all the other are carriers.This catalyzer is applicable to the hydrogenation process of heavy distillate, and has higher hydrogenation activity, but its metal content is higher, and carrier must be through air and the high-temperature roasting of water vapor mixture atmosphere, and preparation process is comparatively complicated, and therefore, cost is higher.Catalyzer must be handled through prevulcanized before using.

CN1,123, it is carrier with the gama-alumina that 310A discloses a kind of, active ingredient is the Hydrodevulcanizing catalyst for hydro-carbons of cobalt, molybdenum, described carrier modified zinc oxide, single-steeping cobalt-molybdenum, this catalyzer are formed (weight) and be: ZnO 1～15%, MoO ₃5～18%, CoO 1～10%.Before using, this catalyzer need prevulcanized to handle.

CN1,040,610A discloses a kind of Hydrodevulcanizing catalyst for hydro-carbons, and it is to contain the γ-Al of titanium oxide ₂O ₃Be carrier, active ingredient is molybdenum, cobalt and nickel.γ-Al ₂O ₃Titanium oxide content is 5～30 heavy % in the carrier, MoO in the catalyzer ₃Content is 5～20 heavy %, and best 10～15 heavy %, CoO content are 1～10 heavy %, and NiO content is 2～10 heavy %.This catalyzer can be used for the hydrogenating desulfurization of the petroleum fractions of 80～200 ℃ of boiling ranges, sulphur content 1～300ppm, though needn't carrying out prevulcanized, handles by this catalyzer, and, before the use, need at 230～300 ℃ hydrogen pressure 50 kilograms per centimeter ²Condition under reduce.

USP4880524 discloses a kind of temperature, 13.6～238 kilograms per centimeter at 149～482 ℃ ²Pressure under by hydrocarbon feed being contacted the method for hydrocarbon feed being carried out hydrotreatment with a kind of catalyzer, at least 300 meters of the specific surfaces of described catalyzer ²/ gram, and bore dia accounts at least 70% of total pore volume less than the pore volume of 70 dusts.Described catalyzer adopts special method preparation, contains the nickel (amounting to into nickel oxide is 1.27～7.62 heavy %) of 1～6 heavy %, molybdenum (amounting to into molybdenum oxide is 12～35 heavy %) or 10～40 heavy % tungsten (amounting to into Tungsten oxide 99.999 is 12.6～50.4 heavy %) or the molybdenum of 8～40 heavy % and the mixture of tungsten of 8～22 heavy % in the catalyzer.This catalyst metal content is higher and preparation process is comparatively complicated.

CN1,169,337A discloses a kind of catalyst for hydrogenation of fraction oil, and this catalyzer contains tungsten, nickel and the cobalt that loads on the gama-alumina, and in oxide compound, W content is that 10～30 heavy %, nickel content are that 1～7 heavy %, cobalt contents are 0.01～1 heavy %.This catalyzer is total to infuse fully with the aqueous solution of tungsten, nickel and cobalt compound.This catalyzer must be handled through prevulcanized before use, and there is the higher shortcoming of metal content equally in this catalyzer.

In addition, above-mentioned catalyzer all has a fatal shortcoming, is exactly that low temperature active is lower.

The purpose of this invention is to provide that a kind of metal content is lower, the cost of catalyzer is lower and have light-end products hydrotreating catalyst of higher low temperature active and preparation method thereof.

As previously mentioned, the low temperature active of hydrotreating catalyst of the prior art is all lower, and the metal content of most of catalyzer is also higher, and cost is higher.The present inventor is surprised to find that, on catalyst carrier alumina, introduce three active component nickel, cobalt and molybdenums and/or tungsten, and adjust three ratios between the component, and can make when metal content reduces in the catalyzer, significantly improve its low-temp desulfurization activity.Particularly adopt a kind of special methods to prepare this catalyzer and can further improve its low-temp desulfurization activity.

Catalyzer provided by the invention contains Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, with the catalyzer is benchmark, the content of described Tungsten oxide 99.999 and/or molybdenum oxide is that 4 heavy % are to weighing % less than 10, the content of nickel oxide is 1～5 heavy %, the content of cobalt oxide is 0.01～1 heavy %, and nickel and cobalt total atom number are 0.3～0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.

Preparation of catalysts method provided by the invention comprises with containing the aqueous solution of molybdenum and/or tungsten compound and nickel compound and the aqueous solution oxide impregnation alumina supporter of cobalt compound, and the roasting dipping is gone up molybdenum and/or tungsten, the alumina supporter of nickel and cobalt, wherein, described usefulness contains the process of the compound water solution oxide impregnation alumina supporter of cobalt and carries out with separating with the process of aqueous solution oxide impregnation alumina supporter that contains molybdenum and/or tungsten compound and nickel compound, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is with after containing the aqueous solution oxide impregnation alumina supporter and roasting of molybdenum and/or tungsten compound and nickel compound, the temperature of carrying out roasting after the described aqueous solution oxide impregnation alumina supporter with cobalt compound is 50～300 ℃, and roasting time was greater than 1 hour.

According to catalyzer provided by the invention, nickel oxide content is preferably 2～4 heavy %.The content of cobalt oxide is preferably 0.02～0.5 heavy %.The ratio that the content of Tungsten oxide 99.999 and/or molybdenum oxide is preferably 4.5～9 heavy %, described nickel and cobalt total atom number and the total atom number of nickel, cobalt, tungsten and/or molybdenum is preferably 0.4～0.7.

All right in the catalyzer provided by the invention, and preferably contain a kind of auxiliary agent, described auxiliary agent is selected from one or more in the oxide compound of fluorine or magnesium, phosphorus, and in element, the content of described auxiliary agent is 0.01～8 heavy %, preferred 0.2～5 heavy %.

Described alumina supporter is the aluminum oxide that is commonly used for catalyst carrier for hydrgenating.Preferred gama-alumina, η-aluminum oxide or its mixture.More preferred alumina supporter is gama-alumina or the aluminum oxide be made up of gama-alumina basically.

Catalyzer provided by the invention can carry out prevulcanized before use, but had better not carry out prevulcanized, and directly going into operation with oxidized catalyst gets final product.

Catalyzer provided by the invention can adopt and soak the technology preparation altogether, and promptly with the common oxide impregnation alumina supporter of the aqueous solution that contains molybdenum and/or tungsten, nickel and cobalt compound, catalyzer is prepared in roasting then.

Catalyzer preferred manufacturing procedure provided by the invention comprises with containing the aqueous solution of molybdenum and/or tungsten compound and nickel compound and the aqueous solution oxide impregnation alumina supporter of cobalt compound, and the roasting dipping is gone up molybdenum and/or tungsten, the alumina supporter of nickel and cobalt, wherein, described usefulness contains the process of the compound water solution oxide impregnation alumina supporter of cobalt and carries out with separating with the process of the aqueous solution oxide impregnation alumina supporter of tungstenic and/or molybdenum compound and nickel compound, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is with after containing the aqueous solution oxide impregnation alumina supporter and roasting of molybdenum and/or tungsten compound and nickel compound, the temperature of carrying out roasting after the described aqueous solution oxide impregnation alumina supporter with cobalt compound is 50～300 ℃, and roasting time was greater than 1 hour.Adopt this method can further improve the low temperature active of catalyzer.

The preferred manufacturing procedure of the catalyzer that provides according to invention, its concrete steps are as follows:

(1) with the precursor of aluminum oxide through moulding, drying, have following 500～700 ℃ of roasting 1～6h in air or water vapour again, make alumina supporter;

(2) alumina supporter that obtains with compound water solution dipping (1) step that contains molybdenum and/or tungsten and nickel.Dry also roasting.The consumption of molybdenum and/or tungsten and nickel compound should make and contain 4 heavy % in the final catalyzer to less than 10 heavy %, preferred 4.5～9 heavy % Tungsten oxide 99.999 and/or molybdenum oxide, 1～5 heavy %, the nickel oxide of preferred 2～4 heavy %.

(3) product that obtains with the compound water solution of cobalt dipping (2) step, and at 50～300 ℃, preferred 150～250 ℃ of roastings, roasting time is greater than 1 hour, preferred 2～4 hours.Wherein, the consumption of cobalt compound should make in the final catalyzer and contain 0.01～1, the cobalt oxide of preferred 0.02～0.5 heavy %.

The precursor of described aluminum oxide is selected from the various hydrated aluminum oxides that can generate gama-alumina and/or η-aluminum oxide after the roasting, as pseudo-boehmite, gibbsite etc.The preferred pseudo-boehmite of the precursor of described aluminum oxide or based in the hydrated aluminum oxide of pseudo-boehmite one or more.

Wherein, the dry and roasting that contains behind the aqueous solution oxide impregnation alumina supporter of molybdenum and/or tungsten and nickel compound of described usefulness is carried out under normal condition.As drying temperature can be normal temperature to 200 ℃, and maturing temperature can be 400～600 ℃, and roasting time was preferably 2～5 hours more than 1 hour.

Described dipping can adopt general pickling process or saturated pickling process, preferred saturated pickling process.

It is 150～250 ℃ that described usefulness contains the temperature of carrying out roasting after the compound water solution dipping of cobalt, and roasting time is 2～4 hours.

Described tungsten and/or molybdenum compound are selected from one or more in its water-soluble cpds, preferred ammonium tungstate, ammonium metawolframate and/or ammonium molybdate.Nickel compound can be selected from its water-soluble nitrate, acetate, carbonate, subcarbonate, preferred nickelous nitrate and/or nickel acetate.Cobalt compound can be selected from its water-soluble nitrate, acetate, carbonate, subcarbonate, preferred Xiao Suangu and/or Cobaltous diacetate.

Preparation of catalysts method provided by the invention can also comprise the step of flooding described alumina supporter with one or more the aqueous solution that contains in magnesium, phosphorus and the fluorine cpd, described being immersed in before containing molybdenum and/or tungsten compound and nickeliferous compound water solution oxide impregnation alumina supporter carried out, and dipping is after super-dry and roasting.The condition of dry and roasting with flood molybdenum and/or tungsten after drying and roasting condition identical.The consumption of described magnesium, phosphorus and fluorine cpd and the aqueous solution thereof should make in the final catalyzer and contain, in element, and 0.01～8 heavy %, magnesium, phosphorus and/or the fluorine of preferred 0.2～5 heavy %.

Magnesium, phosphorus and fluorine cpd are selected from one or more in its water-soluble cpds.Wherein, the preferred magnesium nitrate of magnesium compound, fluorine cpd preferred fluorinated ammonium and/or hydrofluoric acid, one or more in phosphorus compound preferably phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, the primary ammonium phosphate.

Catalyzer provided by the invention can be used for the hydrofining of gasoline fraction and middle distillate wet goods light-end products, be specially adapted to hydro-sweetening, the deacidification of the kerosene(oil)fraction of 130～290 ℃ of the catalytically cracked gasoline of 35～210 ℃ of boiling ranges and boiling ranges, its operational condition can be adjusted in following ranges according to the raw material oil properties with to the requirement of oil quality: 149～315 ℃ of temperature of reaction, volume space velocity 2～8h ^-1, hydrogen dividing potential drop 0.3～2.0 MPa, hydrogen to oil volume ratio be greater than 5.The used hydrogen of hydrofining can be the new hydrogen (hydrogen purity 85～100%) of industry, industrial discharge hydrogen (hydrogen purity 50～85%), discharge gas in ammonia synthesis etc.In a word, hydrogen purity is had no particular limits, only limit oxygen level≤5ppm in the hydrogen, H ₂S content≤2.0 weigh %, so just can enlarge the source of hydrogen greatly, improve the utilization ratio of hydrogen.Because catalyzer provided by the invention has good low temperature active, therefore, is particularly useful for hydro-sweetening, the deacidification of the above-mentioned catalytically cracked gasoline and the kerosene(oil)fraction of 150～200 ℃ of temperature of reaction.

Under the prerequisite that catalyzer provided by the invention reduces greatly at active metallic content, the catalyzer cost reduces greatly, under higher temperature of reaction (greater than 200 ℃), kept existing hydrogenation catalyst suitable mercaptan removal to light-end products, the depickling performance higher with metal content.

Beat allly especially be, under the condition of temperature of reaction lower (149～200 ℃), compare that catalyzer provided by the invention has higher catalytic activity with the catalyzer that existing metal content is higher.For example adopt cobalt oxide 0.05～0.25 heavy % that contains provided by the invention, the catalyzer of nickel oxide 2.05～3.51 heavy %, Tungsten oxide 99.999 or molybdenum oxide 6.06～8.50 heavy %, to boiling range is 161～220 ℃, sulphur content 2170ppm, the aviation kerosene of mercaptan sulfur content 128ppm, 0.039 milligram of potassium hydroxide/gram of acid number carried out hydro-sweetening, hydrogen dividing potential drop 0.7 MPa, liquid hourly space velocity 4 hours ^-1, hydrogen to oil volume ratio 25 condition under, when temperature of reaction was 180 ℃, mercaptan sulfur content dropped to 8～16ppm in the reaction product, acid number drops to zero, total sulfur content drops to 1977～1995ppm; When temperature of reaction was 200 ℃, mercaptan sulfur content dropped to 6～15ppm in the reaction product, and acid number drops to zero, and sulphur content drops to 1962～1980ppm; When temperature of reaction is 220 ℃, mercaptan sulfur content drops to 4～9ppm in the reaction product, acid number drops to zero, sulphur content drops to 1950～1968ppm, the specification of quality that all meets No. 3 aviation fuel, particularly, the low temperature active of catalyzer that soaks cobalt method preparation after the employing wherein is higher, and the method for soaking cobalt after adopting prepares, the catalyzer that contains auxiliary agent magnesium, phosphorus or fluorine simultaneously is wherein active the highest.

And adopt cobalt oxide content 0.05 to weigh %, nickel oxide content 2.4 heavy %, tungsten oxide content 20 heavy %, auxiliary agent Mg content 0.8 heavy %, nickel and cobalt atom number and nickel, the ratio of cobalt and tungsten total atom number is 0.27 commercial catalysts, cobalt oxide content 0.09 heavy %, nickel oxide content 2.5 heavy %, tungsten oxide content 22.6 heavy %, auxiliary agent Mg content 1 heavy %, nickel and cobalt atom number and nickel, the ratio of cobalt and tungsten total atom number is 0.27 commercial catalysts and CN1,169, the nickel oxide content 6.5 heavy % that the disclosed activity of 337A is the highest, molybdenum oxide content 19.5 heavy %, auxiliary agent potassium content 0.49 heavy %, nickel and cobalt atom number and nickel, the ratio of cobalt and tungsten total atom number is 0.26 catalyzer, under the identical situation of other reaction conditionss, when temperature of reaction is 180 ℃, mercaptan sulfur content in the product, acid number and total sulfur content are respectively up to 28～31ppm, 0.017～0.019 milligram of potassium hydroxide/gram and 2043～2062ppm; When temperature of reaction was 200 ℃, mercaptans content was up to 23～25ppm in the product, and sulphur content all can not reach the specification of quality of No. 3 aviation fuel up to 2020～2023ppm.And adopt nickel oxide content 3.62 to weigh %, tungsten oxide content 8.53 heavy %, nickel and nickel and tungsten total atom are during than the two-pack reference catalyst that is 0.6, under the identical situation of other reaction conditionss, when temperature of reaction is 180 ℃, mercaptan sulfur content in the product, acid number and sulphur content are respectively up to 38ppm, 0.025 milligram of potassium hydroxide/gram and 2100ppm; When temperature of reaction was 200 ℃, mercaptan sulfur content was up to 28ppm in the product, and sulphur content all can not reach the specification of quality of No. 3 aviation fuel up to 2059ppm.

The following examples will the present invention will be further described.

Example 1

This example illustrates the preparation of support of the catalyst provided by the invention.

Take by weighing 5000 gram aluminium hydrate powder A (solid content 70 heavy %, pseudo-boehmite content 85 heavy %, Shandong Aluminum Plant produces), add a small amount of extrusion aid and water, be extruded into the trilobal bar that circumscribed circle diameter is 1.6mm with banded extruder, 120 ℃ of oven dry 2 hours, 600 ℃ of roasts 4 hours, the length of the cloverleaf pattern bar that obtains is cut into 2～3 millimeters, makes carrier Z ₁Carrier Z ₁Specific surface, pore volume list in the table 1.Described specific surface and pore volume adopt cryogenic nitrogen absorption BET method to measure (down together).

Example 2

This example illustrates the preparation of support of the catalyst provided by the invention.

Take by weighing 500 gram examples, 1 described aluminium hydrate powder A (solid content 70 heavy %, pseudo-boehmite content 85 heavy %, Shandong Aluminum Plant produces) and 500 gram aluminium hydrate powder B (solid content 70 heavy %, pseudo-boehmite content 70 heavy %, Chang Ling refinery catalyst plant is produced), thorough mixing, add a small amount of extrusion aid and water, be extruded into the cloverleaf pattern bar that circumscribed circle diameter is 1.6mm with banded extruder, dried 2 hours for 120 ℃, 600 ℃ of roasts 4 hours are cut into 2～3 millimeters with the length of the cloverleaf pattern bar that obtains, make carrier Z ₂Carrier Z ₂Specific surface, pore volume list in the table 1.

Example 3～5

The following example explanation preparation that contains the support of the catalyst of auxiliary component provided by the invention.

Get magnesium nitrate [Mg (NO ₃) 2.6H ₂O] 49.0 grams, add deionized water and be made into the 325ml magnesium nitrate aqueous solution, with the magnesium nitrate aqueous solution dipping 500 gram carrier Z that prepare ₁, then in 120 ℃ dry 2 hours down, 550 ℃ of following roastings 4 hours make magnesium-containing carrier Z ₃

Adopt and use the same method, take by weighing Neutral ammonium fluoride (NH respectively ₄F) 37.5 grams, phosphoric acid (concentration 85.6 heavy %) are 75 milliliters, add deionized water respectively and are made into 325 milliliters and 330 milliliters of ammonium fluoride aqueous solutions and phosphate aqueous solution, flood 500 respectively with the ammonium fluoride aqueous solution, the phosphate aqueous solution that prepare and restrain carrier Z ₁Then in 120 ℃ dry 2 hours down, 550 ℃ of following roastings 4 hours make fluorine-containing carrier Z ₄With phosphorous carrier Z ₅Carrier Z ₃～Z ₅Middle auxiliary agent content (in element) and specific surface, pore volume are listed in the table 1.The content of phosphorus, magnesium, fluorine all adopts x-ray fluorescence spectrometry.

Table 1

Example number	1	2	3	4	5
						Bearer number	Z 1	Z 2	Z 3	Z 4	Z 5
The auxiliary agent kind	/	/	Mg	F	P
						The heavy % of auxiliary agent content	0	0	0.93	3.5	2.0
Specific surface, rice 2/ gram	278	283	275	270	272
						Pore volume, milliliter/gram	0.40	0.45	0.38	0.37	0.38

Example 6～12

Catalyzer provided by the invention and preparation thereof.

(1) takes by weighing quantitative nickelous nitrate [Ni (NO respectively ₃) ₂.6H ₂O] and ammonium molybdate [(NH ₄) ₆Mo ₇O ₂₄.4H ₂O] or ammonium metatungstate aqueous solution (be called for short AMT solution, concentration is 77.6 gram WO ₃/ 100 ml solns), add deionized water after the mixing, be made into 96 milliliters of aqueous solution that contain nickelous nitrate and ammonium molybdate or ammonium metawolframate.Respectively with the above-mentioned solution impregnation for preparing 150 gram carrier Z ₁～Z ₅4 hours, 120 ℃ of dryings 2 hours, 450 ℃ of roastings 4 hours.Used each material consumption is listed in the table 2.

(2) take by weighing quantitative Xiao Suangu [Co (NO respectively ₃) ₂.6H ₂O] add deionized water, be made into 94 milliliters of cobalt nitrate aqueous solutions, the product with the cobalt nitrate aqueous solution dipping (1) that is made into obtains respectively 180～230 ℃ of roastings 3 hours, gets catalyzer C provided by the invention ₁～C ₇The consumption of Xiao Suangu, maturing temperature and catalyzer C ₁～C ₇In each component concentration list in the table 2.Wherein the content of cobalt, nickel, molybdenum, tungsten, magnesium, fluorine, phosphorus all adopts x-ray fluorescence spectrometry.

Table 2

Example number		6	7	8	9	10	11	12
									The catalyzer numbering		C 1	C 2	C 3	C 4	C 5	C 6	C 7
The used carrier numbering		Z 1	Z 1	Z 2	Z 3	Z 4	Z 5	Z 1
									Preparation of Catalyst	The nickelous nitrate consumption, gram	15.60	13.25	15.90	17.80	16.50	16.60	23.40
The ammonium molybdate consumption, gram			20.50
								The AMT solution usage, milliliter		16.40	13.50		13.00	16.70	16.50	18.70
The Xiao Suangu consumption, gram	0.40	0.65	0.95	0.98	1.58	1.15	0.69
								Maturing temperature, ℃		180	200	230	200	210	180	230
The catalyzer compositional analysis	CoO, heavy %	0.05	0.10	0.15	0.16	0.25	0.18										0.10
								NiO, heavy %	2.40	2.05	3.25	2.79	2.50	2.57	3.51
	WO 3, heavy %	7.65	6.34		6.06	7.68	7.63									8.50
								MoO 3, heavy %			7.38
	Ni+Co and Ni+Co+W or Mo atomic ratio	0.50	0.51	0.46	0.60	0.53	0.53									0.56
								Auxiliary agent	Kind				Mg	F	P
Content, heavy %				0.76	2.67	1.53

Comparative Examples 1

Take by weighing 24.25 gram nickelous nitrate [Ni (NO ₃) ₂.6H ₂O], measure 18.80 milliliters of examples, 6～12 described AMT solution, the two mixing and adding deionized water are made into 94 milliliters of aqueous solution that contain nickelous nitrate and ammonium metawolframate.With the above-mentioned solution impregnation for preparing 150 gram carrier Z ₁4 hours, 120 ℃ of dryings 2 hours, 450 ℃ of roasts 4 hours obtain reference catalyst, and it is numbered C ₈C ₈Contain nickel oxide 3.62 heavy %, Tungsten oxide 99.999 8.53 heavy %, nickel is 0.56 with nickel and tungsten atom ratio.

Example 13

Prepare catalyzer by example 9 each material consumption and method, different is with containing nickelous nitrate, Xiao Suangu and the common oxide impregnation alumina supporter of 95 milliliters of mixed aqueous solutions of AMT solution, and the dipping back obtains catalyzer in 450 ℃ of roastings 4 hours, and it is numbered C ₉C ₉Contain cobalt oxide 0.16 heavy %, nickel oxide 2.79 heavy %, Tungsten oxide 99.999 6.06 heavy %, magnesium 0.76 heavy %, the atomic ratio of nickel and cobalt and nickel, cobalt and tungsten is 0.60.

Example 14～21

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

Adopting boiling range as shown in table 3 is that 161～220 ℃ 1# aviation kerosene is raw material evaluate catalysts C ₁～C ₇And C ₉Mercaptan removal and depickling activity.Be reflected on 100 milliliters of hydrogenation units and carry out.50 milliliters of catalyzer loading amounts, reaction conditions is: 180 ℃ of temperature of reaction, hydrogen dividing potential drop 0.7 MPa, liquid hourly space velocity 4.0 hours ^-1, hydrogen to oil volume ratio 25.Reaction product character is listed in the table 5.Wherein, sulphur content adopts micro-coulometric determination (SH/T 0253-9) mensuration, mercaptans content to adopt potentiometric determination, acid number employing SH/T0163-92 method mensuration, colourity to adopt GB 6540-86 method mensuration (down together).

Comparative Examples 2～6

Below the Comparative Examples explanation metal content existing catalyzer that is much higher than catalyzer provided by the invention be used for the activity of light-end products hydro-sweetening and depickling.

Press the activity of the method evaluate catalysts of example 14～21, different is that catalyst system therefor is reference catalyst C ₈, the industrial trade mark is that catalyzer, the industrial trade mark of CH-17 (Chang Ling refinery catalyst plant product) is catalyzer, the CN1 of CH-18 (Chang Ling refinery catalyst plant product), 169, the CH-18 catalyzer of inactivation (described reformed pre-hydrogenated temperature of reaction is 300 ℃, reaction pressure 2 MPas) on catalyzer D of 337A example 7 preparation (catalyzer D is a highest wherein active catalyzer) and the reformed pre-hydrogenated device.CH-17, CH-18, CN1,169, on the catalyzer D of 337A example 7 preparation and the reformed pre-hydrogenated device the numbering of the CH-18 catalyzer of inactivation be followed successively by C ₁₀, C ₁₁, C ₁₂And C ₁₃, their composition, atoms metal ratio, specific surface and pore volume are listed in the table 4, and the character of product is listed in the table 6.

Table 3

The stock oil title	Aviation kerosene	Aviation kerosene	Aviation kerosene	Aviation kerosene
					The stock oil numbering	1#	2#	3#	4#
d 20 4, gram per centimeter 3	0.7916	0.7864	0.7818	0.7990
					Sulphur content, ppm	2170	1470	1490	250
Mercaptan sulfur content, ppm	128	105	114	37
					Acid number, the milligram potassium hydroxide/gram	0.039	0.031	0.031	0.029
Colourity, number	19	20	22	18
					Boiling range ℃ initial boiling point 10% 50% 90% is done	161 173 186 207 220	162 171 184 209 228	162 171 185 211 220	147 163 187 225 242

Table 4

The catalyzer numbering	Specific surface, rice 2/ gram	Pore volume, milliliter/gram	Metal is formed, heavy %	Nickel (cobalt) and nickel (cobalt), tungsten (molybdenum) atomic ratio
					C 10	230	0.40	NiO:6.5 MO 3:19.5 K:0.49	0.39
C 11	174	0.31	CoO:0.05 NiO:2.40 WO 3:20.0 Mg:0.80	0.27
					C 12	170	0.30	CoO:0.09 NiO:2.50 WO 3:22.6 Mg:1.0	0.26
C 13	160	0.28	CoO:0.04 NiO:2.10 WO 3:19.5 Mg:0.53	0.26

Table 5

Example number	14	15	16	17	18	19	20	21
									The catalyzer numbering	C 1	C 2	C 3	C 4	C 5	C 6	C 7	C 9
Product mercaptan sulphur content, ppm	13	12	12	9	8	9	13	16
									The product total sulfur content, ppm	1985	1978	1979	1977	1978	1981	1990	1995
The product acid number, the milligram potassium hydroxide/gram	0	0	0	0	0	0	0	0
									Colourity, number	27	27	27	27	27	27	27	27

Table 6

Example number	Comparative Examples 2	Comparative Examples 3	Comparative Examples 4	To this example 5	Comparative Examples 6
						The catalyzer numbering	C 8	C 10	C 11	C 12	C 13
Product mercaptan sulphur content, ppm	38	31	29	28	35
						The product total sulfur content, ppm	2100	2062	2048	2043	2068
The product acid number, the milligram potassium hydroxide/gram	0.025	0.019	0.018	0.017	0.019
						Colourity, number	27	27	27	27	27

Example 22～29

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

Press the method evaluate catalysts C of example 14～21 ₁～C ₇And C ₉Mercaptan removal and depickling activity, different just temperature of reaction are 200 ℃.Reaction product character is listed in the table 7.

Comparative Examples 7～11

Below the Comparative Examples explanation metal content commercial catalysts that is much higher than catalyzer provided by the invention be used for the activity of light-end products hydro-sweetening and depickling.

Press the activity of the method evaluate catalysts of example 22～29, different is that catalyst system therefor is reference catalyst C ₈, C ₁₀, C ₁₁, C ₁₂And C ₁₃, the character of reaction product is listed in the table 8.

Table 7

Example number	22	23	24	25	26	27	28	29
									The catalyzer numbering	C 1	C 2	C 3	C 4	C 5	C 6	C 7	C 9
Product mercaptan sulphur content, ppm	10	10	11	6	6	6	11	15
									The product total sulfur content, ppm	1965	1968	1970	1963	1964	1962	1973	1980
The product acid number, the milligram potassium hydroxide/gram	0	0	0	0	0	0	0	0
									Colourity, number	28	28	28	28	28	28	28	28

Table 8

Example number	Comparative Examples 7	Comparative Examples 8	Comparative Examples 9	Comparative Examples 10	Comparative Examples 11
						The catalyzer numbering	C 8	C 10	C 11	C 12	C 13
Product mercaptan sulphur content, ppm	28	25	24	23	25
						The product total sulfur content, ppm	2059	2023	2020	2020	2020
The product acid number, the milligram potassium hydroxide/gram	0	0	0	0	0
						Colourity, number	27	27	27	27	27

Example 30～37

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

Press the method evaluate catalysts C of example 14～21 ₁～C ₇And C ₉Mercaptan removal and depickling activity, different just temperature of reaction are 220 ℃.Reaction product character is listed in the table 9.

Comparative Examples 12～16

Below the Comparative Examples explanation metal content commercial catalysts that is much higher than catalyzer provided by the invention be used for the activity of light-end products hydro-sweetening and depickling.

Press the activity of the method evaluate catalysts of example 30～37, different is that catalyst system therefor is reference catalyst C ₈, C ₁₀, C ₁₁, C ₁₂And C ₁₃, the character of reaction product is listed in the table 10.

Table 9

Example number	30	31	32	33	34	35	36	37
									The catalyzer numbering	C 1	C 2	C 3	C 4	C 5	C 6	C 7	C 9
Product mercaptan sulphur content, ppm	8	8	8	4	4	4	8	9
									The product total sulfur content, ppm	1959	1961	1960	1953	1950	1950	1957	1968
The product acid number, the milligram potassium hydroxide/gram	0	0	0	0	0	0	0	0
									Colourity, number	28	28	28	28	28	28	28	28

Table 10

Example number	Comparative Examples 12	Comparative Examples 13	Comparative Examples 14	Comparative Examples 15	Comparative Examples 16
						The catalyzer numbering	C 8	C 10	C 11	C 12	C 13
Product mercaptan sulphur content, ppm	13	9	8	8	9
						The product total sulfur content, ppm	2033	2010	2008	2005	2020
The product acid number, the milligram potassium hydroxide/gram	0	0	0	0	0
						Colourity, number	27	28	28	28	27

From the result of table 5～10 as can be seen, (1) when 220 ℃ of temperature of reaction, adopt metal content to be significantly less than comparative catalyst's catalyzer provided by the invention, under situation identical under other processing condition, mercaptan in the product and acid number and be on close level during with the comparative catalyst, product meets the specification of quality of No. 3 rocket engine fuels, and (mercaptan sulfur content is not more than 20ppm, acid number is not more than 0.015 milligram of potassium hydroxide/gram, total sulfur content is not more than 2000ppm), the color of product is greatly improved.And when adopting reference catalyst, total sulfur content is high slightly in the product.(2) temperature of reaction be 180 ℃ with 200 ℃ of situations identical with other processing condition under, adopt catalyzer provided by the invention, product meets the specification of quality of No. 3 rocket engine fuels, the color of product is greatly improved, its mercaptan removal activity and depickling activity are all apparently higher than the comparative catalyst, and when adopting the comparative catalyst, at least a specification of quality that does not meet No. 3 rocket engine fuels in its product in mercaptan, acid number and the sulphur.(3) with the reduction of temperature of reaction, the active decline of catalyst desulfurizing alcohol provided by the invention is very slow, and the active decline of comparative catalyst's mercaptan removal is very obvious.Above presentation of results, catalyzer provided by the invention has good low temperature active, and this is that prior art is incomparable.

Example 38～40

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

With identical stock oil, press the method and the condition evaluating catalyzer C of example 22 ₁Activity, different just reaction pressure and hydrogen-oil ratio differences.Hydrogen to oil volume ratio is 30 o'clock, and the character of reaction product is listed in the table 11 under the different pressures.

Table 11

Example number	38	39	40
				Reaction pressure, MPa	0.3	0.7	1.5
Hydrogen to oil volume ratio	30	30	30
				Mercaptan sulfur content in the product, ppm	7	9	13
The product acid number, the milligram potassium hydroxide/gram	0	0	0

Example 41～43

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

With identical stock oil, press the method and the condition evaluating catalyzer C of example 22 ₁Activity, different just air speed and hydrogen-oil ratio differences.Hydrogen to oil volume ratio is 30 o'clock, and the character of reaction product is listed in the table 12 under the different air speeds.

Table 12

Example number	41	42	43
				Liquid hourly space velocity, hour -1	2	4	6
Hydrogen to oil volume ratio	30	30	30
				Mercaptan sulfur content in the product, ppm	7	9	8
The product acid number, the milligram potassium hydroxide/gram	0	0	0

Example 44～47

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

With identical stock oil, press the method and the condition evaluating catalyzer C of example 22 ₁Activity, different just hydrogen-oil ratio differences.The character of reaction product is listed in the table 13 under the different hydro oil ratio.

Table 13

Example number	44	45	46	47
					Hydrogen to oil volume ratio	5	10	15	20
Mercaptan sulfur content in the product, ppm	17	15	13	11
					The product acid number, the milligram potassium hydroxide/gram	0.009	0.008	0	0

Example 48～50

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

With identical stock oil, press the method and the condition evaluating catalyzer C of example 22 ₁Activity, different just hydrogen source and hydrogen-oil ratio differences.Hydrogen to oil volume ratio is 30 o'clock, and the character of reaction product is listed in the table 14 under the different hydrogen sources.

Table 14

Example number	48	49	50
				Hydrogen source	The hydrogen that contains 0.5 heavy % hydrogen sulfide	The hydrogen that contains 1.5 heavy % hydrogen sulfide	The hydrogen that contains 25 body % nitrogen
Hydrogen to oil volume ratio	30	30	30
				Mercaptan sulfur content in the product, ppm	8	9	9
The product acid number, the milligram potassium hydroxide/gram	0	0	0

Example 51～52

Following example illustrates that catalyzer provided by the invention is used for the activity of light-end products hydro-sweetening and depickling.

With identical stock oil, press the method and the condition evaluating catalyzer C of example 22 ₁Activity, different just temperature of reaction differences, the character of reaction product is listed in the table 15 under the differential responses temperature.

Table 15

Example number	51	52
			Temperature of reaction ℃	160	170
Mercaptan sulfur content in the product, ppm	14	13
			The product acid number, the milligram potassium hydroxide/gram	0	0

From the result of table 11～15 as can be seen; (1) uses catalyzer of the present invention; under different processing condition; (temperature is lower than 200 ℃ even under unusual demulcent hydroconversion condition; even be low to moderate 160 ℃, and hydrogen-oil ratio is not more than 30) mercaptan of product and the specification of quality that acid number all reaches No. 3 rocket engine fuels.(2) when temperature of reaction is lower than 200 ℃, catalyst desulfurizing alcohol provided by the invention is active little with the variation of temperature of reaction, found that of associative list 5～10, though the prior art catalyzer at high temperature has the catalytic activity suitable with catalyzer provided by the invention, but, when temperature of reaction is lower than 200 ℃, with the reduction of temperature of reaction, its mercaptan removal and depickling are active significantly to be reduced, and product can not reach the specification of quality of No. 3 rocket engine fuels.

Example 53～55

Following example illustrates that catalyzer provided by the invention is used for light-end products hydro-sweetening and depickling activity.

Press the method evaluate catalysts C of example 22 ₁Activity, 2#, 3# and the 4# aviation kerosene of different is raw materials used oil the is respectively listed boiling range of table 3 is 162～228 ℃, 162～220 ℃ and 147～242 ℃, reaction conditions is also different.Reaction conditions and product characteristics are listed in the table 16.

Table 16

Example number	53	54	55
				The reaction raw materials numbering	2#	3#	4#
Reaction pressure, MPa	0.7	0.7	0.7
				Temperature of reaction ℃	180	180	180
Liquid hourly space velocity hour -1	6.0	4.0	4.0
				Hydrogen to oil volume ratio	30	30	30
Product mercaptan sulphur content, ppm	12	8	4
				The product acid number, the milligram potassium hydroxide/gram	0	0	0

From the result of table 16 as can be seen, catalyzer provided by the invention has adaptability widely to different oil products.

Example 56

Following example illustrates that catalyzer provided by the invention is used for the activity stability of light-end products hydro-sweetening and depickling.

The employing boiling range is that 161～220 ℃ 1# aviation kerosene is raw material evaluate catalysts C ₁Mercaptan removal and the activity stability of depickling, be reflected on 100 milliliters of hydrogenation units and carry out.100 milliliters of catalyzer loading amounts, reaction conditions is: 240 ℃ of temperature of reaction, hydrogen dividing potential drop 0.7 MPa, liquid hourly space velocity 4.0 hours ^-1, hydrogen to oil volume ratio 30.The mercaptan sulfur content and the acid number of reaction product are listed in the table 17 with the variation in reaction times.Sampling when reacting to 500,1000 and 2000 hours is carried out multiple performance analysis to product, and the results are shown in Table 18.Stop test after the reaction to 2006 hour, catalyzer is poured out carefully, catalyzer is divided into three equal parts by the position of upper, middle and lower layer in reactor, get each 3 gram of catalyzer of upper, middle and lower layer respectively, with the carbon deposit of the infrared determination of carbon and sulfur instrument of CS-344 analysis of catalyst, the results are shown in Table 21.

Table 17

Reaction times hour	Generate oily mercaptan sulfur content ppm	Generate oleic acid value milligram potassium hydroxide/gram
			175	3	0
366	5	0
			558	4	0
840	7	0
			1034	6	0
1337	7	0
			1673	5	0
1961	5	0
			2006	5	0

Table 18

Project	The GB6537-94 quality standard	1# stock oil	Reaction times, hour
						500	1000	2000
			Colourity, number	Report	19				26	27	27
Acid number, the milligram potassium hydroxide/gram	Be not more than 0.015	0.039				0	0	0
			Total sulfur content, heavy %	Be not more than 0.20	0.217				0.188	0.180	0.168
Mercaptan sulfur content, ppm	Be not more than 20	128				5	7	5
			The doctor test	By	Sun				By	By	By
Silver slice corrosion (50 ℃, 4h), level	Be not more than 1	0				0	0	0
			Copper corrosion (100 ℃, 4h), level	Be not more than 1	1a				1a	1a	1a
Boiling range, ℃ initial boiling point 10% 50% 90% is done	The report be not higher than 205 be not higher than 232 the report be not higher than 300	161 173 186 207 220				160 173 186 205 220	160 172 187 205 221	159 172 186 204 220

Example 57

Following example illustrates that catalyzer provided by the invention is used for the activity stability of light-end products hydro-sweetening and depickling.

Method according to example 56 is carried out activity rating to identical stock oil, and different is that temperature of reaction is 180 ℃.Mercaptan sulfur content and acid number are listed in the table 19 with the variation in reaction times in the reaction product.Sampling when reacting to 500,1000 and 2000 hours is carried out multiple performance analysis to product, and the results are shown in Table 20.By example 55 same methods catalyst carbon deposit is analyzed, the results are shown in Table 21.

Table 19

Reaction times hour	Generate oily mercaptan sulfur content ppm	Generate oleic acid value milligram potassium hydroxide/gram
			128	12	0
246	13	0
			300	11	0
508	12	0
			705	11	0
1506	11	0
			1750	11	0
2006	11	0

Table 20

Project	The GB6537-94 quality standard	1# stock oil	Reaction times, hour
						500	1000	2000
			Colourity, number	Report	19				26	27	27
Acid number, the milligram potassium hydroxide/gram	Be not more than 0.015	0.039				0	0	0
			Total sulfur content, heavy %	Be not more than 0.20	0.217				0.185	0.183	0.175
Mercaptan sulfur content, ppm	Be not more than 20	128				13	11	11
			The doctor test	By	Sun
Silver slice corrosion (50 ℃, 4h), level	Be not more than 1	0				0	0	0
			Copper corrosion (100 ℃, 4h), level	Be not more than 1	1a				1a	1a	1a
Boiling range, ℃ initial boiling point 10% 50% 90% is done	The report be not higher than 205 be not higher than 232 the report be not higher than 300	161 173 186 207 220				160 173 186 205 220	160 172 185 206 220	161 172 186 206 221

Table 21

The position of catalyzer in reactor	On	In	Down	On average
					Example 56 catalyzer coke contents, heavy %	6.58	5.87	5.03	5.83
Example 57 catalyzer coke contents, heavy %	6.15	5.63	4.87	5.55

The result of table 17～21 shows that catalyzer provided by the invention not only has good active, and has good active stability, and the character of the reaction product that obtains all meets the quality standard of No. 3 aviation fuel.More beat allly be, the catalyzer provided by the invention active stability of mercaptan removal at low temperatures is also very high, and, from the catalyst carbon deposit component analysis, catalyzer provided by the invention at low temperatures carbon deposit than lower under the high temperature, therefore, catalyzer provided by the invention will have longer running period at low temperatures.

Claims (16)

1. light-end products hydrotreating catalyst that contains molybdenum and/or tungsten, this catalyzer contains Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and the cobalt oxide that loads on the alumina supporter, it is characterized in that, with the catalyzer is benchmark, the content of described Tungsten oxide 99.999 and/or molybdenum oxide is that 4 heavy % are to weighing % less than 10, the content of nickel oxide is 1～5 heavy %, and the content of cobalt oxide is 0.01～1 heavy %, and nickel and cobalt total atom number are 0.3～0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum.

2. catalyzer according to claim 1 is characterized in that described nickel oxide content is 2～4 heavy %.

3. catalyzer according to claim 2, the content that it is characterized in that described cobalt oxide are 0.02～0.5 heavy %.

4. catalyzer according to claim 1, the content that it is characterized in that described Tungsten oxide 99.999 and/or molybdenum oxide be 4.5～9 heavy %,

5. catalyzer according to claim 2 is characterized in that described nickel and cobalt total atom number and the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum are 0.4～0.7.

6. according to each the described catalyzer in the claim 1～5, it is characterized in that also containing a kind of auxiliary agent in the described catalyzer, described auxiliary agent is selected from magnesium, fluorine or phosphorus, and in element, the content of described auxiliary agent is 0.01～8 heavy %.

7. catalyzer according to claim 6 is characterized in that described auxiliary agent content is 0.2～5 heavy %.

8. catalyzer according to claim 1 is characterized in that described alumina supporter is gama-alumina, η-aluminum oxide or its mixture.

9. catalyzer according to claim 1 is characterized in that described alumina supporter is gama-alumina or the aluminum oxide be made up of gama-alumina basically.

10. claim 1 Preparation of catalysts method comprises with containing the aqueous solution of molybdenum and/or tungsten compound and nickel compound and the aqueous solution oxide impregnation alumina supporter of cobalt compound, and the roasting dipping is gone up molybdenum and/or tungsten, the alumina supporter of nickel and cobalt, it is characterized in that, described usefulness contains the process of the compound water solution oxide impregnation alumina supporter of cobalt and carries out with separating with the process of aqueous solution oxide impregnation alumina supporter that contains molybdenum and/or tungsten compound and nickel compound, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is with after containing the aqueous solution oxide impregnation alumina supporter and roasting of molybdenum and/or tungsten compound and nickel compound, the temperature of carrying out roasting after the described aqueous solution oxide impregnation alumina supporter with cobalt compound is 50～300 ℃, and roasting time was greater than 1 hour.

11. method according to claim 10 is characterized in that described tungsten compound refers to ammonium tungstate and/or ammonium metawolframate; Described molybdenum compound refers to ammonium molybdate; Described nickel compound refers to nickelous nitrate and/or nickel acetate; Described cobalt compound refers to Xiao Suangu and/or Cobaltous diacetate.

12. method according to claim 10 is characterized in that the temperature that described aqueous solution oxide impregnation alumina supporter with cobalt compound carries out roasting afterwards is 150～250 ℃, roasting time is 2～4 hours.

13. method according to claim 10, it is characterized in that this method also comprises the step of flooding described alumina supporter with one or more the aqueous solution in magnesium-containing compound, P contained compound and the fluorochemicals, carry out before the described aqueous solution oxide impregnation alumina supporter that is immersed in molybdenum and/or tungsten compound and nickel compound.

14. method according to claim 13 is characterized in that described magnesium compound refers to magnesium nitrate; Fluorine cpd refer to Neutral ammonium fluoride and/or hydrofluoric acid; Phosphorus compound is selected from one or more in phosphoric acid, ammonium phosphate, ammonium hydrogen phosphate, the primary ammonium phosphate.

15. light-end products hydrotreating catalyst that contains molybdenum and/or tungsten, this catalyzer contains Tungsten oxide 99.999 and/or molybdenum oxide, nickel oxide and cobalt oxide, it is characterized in that, with the catalyzer is benchmark, the content of described Tungsten oxide 99.999 and/or molybdenum oxide is that 4 heavy % are to weighing % less than 10, the content of nickel oxide is 1～5 heavy %, and the content of cobalt oxide is 0.01～1 heavy %, and nickel and cobalt total atom number are 0.3～0.9 with the ratio of the total atom number of nickel, cobalt, tungsten and/or molybdenum; This Preparation of catalysts method comprises with containing the aqueous solution of molybdenum and/or tungsten compound and nickel compound and the aqueous solution oxide impregnation alumina supporter of cobalt compound, and the roasting dipping is gone up molybdenum and/or tungsten, the alumina supporter of nickel and cobalt, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is carried out with separating with the process of the aqueous solution oxide impregnation alumina supporter of tungstenic and/or molybdenum compound and nickel compound, the process of described aqueous solution oxide impregnation alumina supporter with cobalt compound is with after containing the aqueous solution oxide impregnation alumina supporter and roasting of molybdenum and/or tungsten compound and nickel compound, the temperature of carrying out roasting after the described aqueous solution oxide impregnation alumina supporter with cobalt compound is 50～300 ℃, and roasting time was greater than 1 hour.

16. catalyzer according to claim 15 is characterized in that it is 150～250 ℃ that described usefulness contains the temperature of carrying out roasting after the compound water solution oxide impregnation alumina supporter of cobalt, roasting time is 2～4 hours.