CN105013498B - A kind of hydrotreating catalyst and its application - Google Patents

Abstract

A kind of hydrotreating catalyst and its application, the catalyst contains carrier and at least one is selected from VIII race and at least one metal component selected from group vib, the carrier contains silica alumina and aluminum oxide, on the basis of carrier, the content of silica alumina is 10 90 weight %, the content of aluminum oxide is 10 90 weight %, it is characterized in that, the carrier mixes with boehmite by silica alumina, is molded, dries and is calcined and obtains, the boehmite includes PB1, characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively greater than 1 to less than or equal to 3, wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃In peak height of the 2 θ angles for 24 30 °, 35 41 ° and 46 52 ° of three diffraction maximums respectively in PB1 x-ray diffraction spectra.Compared with prior art provides catalyst, the present invention, which provides catalyst, has more preferable hydrogenation aromatics-removing performance.

Description

A kind of hydrotreating catalyst and its application

Technical field

The present invention relates to a kind of hydrotreating catalyst and its application.

Background technology

Industry, which is hydrocracked charging, includes the 350-540 DEG C of cut such as VGO, and reaction temperature is entered typically between 350-440 DEG C High boiling component is contacted with catalyst in liquid form in reaction in material.Catalyst pore passage structure just has prior Effect, this is accomplished by increasing the aperture of carrier, improves the ability that reaction molecular touches hydrogenation active metals in catalyst.Due to Molecular sieve and metal sulfide pore volume are smaller, particularly meet the middle macropore of macromolecule hydrocarbon feed needs required by PETROLEUM PROCESSING It is less, conventional method can by introduced in carrier of hydrocracking catalyst the method for big pore volume heat-resistant inorganic oxide matrix come Realize, for example, introduce alumina host.

ZL97121663.0 discloses a kind of hydrocracking catalyst for being particularly suitable for use in producing intermediate oil, containing whetheing there is The silica-alumina component that shapes and aperture alumina adhesive, the content of amorphous silica-alumina is 30-60 weights %, at least one group vib element and at least one VIII race element are measured, hydrogenation metal oxide total content is 20-35 weight %, remaining Measure as aperture alumina adhesive, it is characterised in that 150-300 meters of catalyst specific surface²/ gram, 0.25-0.50 milliliters of pore volume/ Gram, 4-15 nano-pores are distributed in 60-90%, infrared 0.30-0.50 mMs/gram of acidity.

ZL01123765.1 discloses a kind of catalyst for hydrogenation treatment of diesel oil, and the catalyst contains a kind of carrier and is supported on Molybdenum and/or tungsten and nickel and/or cobalt on the carrier, it is characterised in that the carrier is made up of aluminum oxide and zeolite, aluminum oxide with The weight ratio of zeolite is 90：10-50：50, the aluminum oxide is according to 75 by small porous aluminum oxide and macroporous aluminium oxide：25-50：50 Weight than the aluminum oxide that is composited, wherein, small porous aluminum oxide is that diameter is less than the pore volume in 80 angstroms of holes and accounts for total pore volume More than 95% aluminum oxide, macroporous aluminium oxide accounts for the oxidation of total pore volume more than 70% for the pore volume in 60-600 angstroms of holes of diameter Aluminium.

The content of the invention

The hydrotreating catalyst being modified it is an object of the invention to provide a kind of performance and the catalyst application.

Content of the present invention includes：

1. a kind of hydrotreating catalyst, containing carrier and at least one VIII race is selected from and at least one selected from group vib Metal component, the carrier contains silica-alumina and aluminum oxide, and on the basis of carrier, the content of silica-alumina is 10-90 weight %, the content of aluminum oxide is 10-90 weight %, it is characterised in that the carrier is by silica-alumina with intending thin Diaspore mixing, shaping, dry and be calcined and obtain, the boehmite includes PB1, is characterized with X-ray diffraction, the PB1's κ₁And κ₂Respectively greater than 1 to less than or equal to 3, wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃Respectively PB1 x-ray diffraction spectra In in peak height of the 2 θ angles for 24-30 °, 35-41 ° and 46-52 ° of three diffraction maximums.

2. the catalyst according to 1, it is characterised in that on the basis of carrier, the content of silica-alumina is 20- 80 weight %, the content of aluminum oxide is 20-80 weight %；Characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively 1.02-2.4.

3. the catalyst according to 2, it is characterised in that characterized with X-ray diffraction, the κ of the PB1₁For 1.2-2.3, κ₂For 1.02-1.4。

4. the catalyst according to 1, it is characterised in that the specific surface area of the PB1 is 100-350 meters²/ gram, pore volume For 0.7-1.2 mls/g.

5. the catalyst according to 4, it is characterised in that the specific surface area of the PB1 is 150-280 meters²/ gram, pore volume For 0.85-1.12 mls/g.

6. the catalyst according to 1, it is characterised in that the specific surface area of the silica-alumina is 350-750 Rice²/ gram, pore volume is 0.4-1.2 mls/g.

7. the catalyst according to 6, it is characterised in that the specific surface area of the silica-alumina is 400-650 Rice²/ gram, pore volume is 0.45-0.95 mls/g.

8. the catalyst according to 1,6 or 7 any one, it is characterised in that on the basis of the silica-alumina, The content of silica is 10-80 weight % in the silica-alumina.

9. the catalyst according to 8, it is characterised in that on the basis of the silica-alumina, the silica- The content of silica is 15-55 weight % in aluminum oxide.

10. the catalyst according to 1, it is characterised in that the metal component of VIII race is selected from nickel and/or cobalt, described The metal component of group vib is selected from molybdenum/or tungsten, is counted by oxide and on the basis of the catalyst, the content of the nickel and/or cobalt For 1-15 weight %, the content of the molybdenum/or tungsten is 5-40 weight %.

11. the catalyst according to 10, it is characterised in that counted by oxide and on the basis of the catalyst, described The content of nickel and/or cobalt is 2.0-10 weight %, and the content of the molybdenum/or tungsten is 10-35 weight %.

12. the catalyst according to 1, it is characterised in that the boehmite is PB1 and PB2 mixture, with dry Base meter and on the basis of carrier, PB1 content is that 10-90 weight %, PB2 content are 5-60 weight %, with infrared spectrum characterization, PB2 δ values are 1.5-4.5, wherein, δ=I₁/（I₂+I₃）, I₁For 3665- in the infrared hydroxyl spectrum of the boehmite 3680cm^-1Locate the peak height of absworption peak, I₂For 3720-3730cm^-1Locate the peak height of absworption peak, I₃For 3760-3780cm^-1Locate absworption peak Peak height.

13. the catalyst according to 12, it is characterised in that counted by butt and on the basis of carrier, PB1 content is 20-80 weight %, PB2 content are that 10-50 weight %, the PB2 δ values are 1.8-3.8.

14. the catalyst according to 1, it is characterised in that described drying condition includes：Temperature is 50-350 DEG C, when Between be 1-24 hours；Described roasting condition includes：Temperature is 400-700 DEG C, and the time is 0.5-6 hours.

15. the catalyst according to 14, it is characterised in that described drying condition includes：Temperature is 80-200 DEG C, when Between be 1-6 hours；Described roasting condition includes：Temperature is 550-650 DEG C, and the time is 1-3 hours.

16. the catalyst according to 12, it is characterised in that the PB2 is that PB1 is dry 0.5-14 hours in 70-400 DEG C Modifier.

17. the catalyst according to 16, it is characterised in that the PB2 be PB1 in 220-330 DEG C dry 1-6 hours Modifier.

18. application of the catalyst in hydrocarbon ils processing according to any one of 1-17.

In the present invention, described silicaalumina carrier can be commercially available commodity or use any one existing skill It is prepared by art.It is preferred that specific surface area is 350-750 meters²/ gram, pore volume is 0.4-1.2 mls/g of silica-alumina, further Preferably specific surface area is 400-650 meters²/ gram, pore volume is 0.45-0.95 mls/g of silica-alumina.

The shaping is carried out according to a conventional method, such as extruded moulding.Can be added in extrusion molding appropriate extrusion aid and/ Or adhesive, then extrusion molding.The extrusion aid, the species of peptizing agent and consumption are known to those skilled in the art, This is not repeated.

The method of the drying and roasting is conventional method, for example, being done using baking oven, guipure, converter heating means Dry, drying condition includes 50-350 DEG C of temperature, preferably 70-200 DEG C, time 1-24 hour, preferably 2-6 hour；Using baking oven, net Band, converter heating means are calcined, and roasting condition includes 350-800 DEG C of temperature, and preferably 400-700 DEG C, the time, 0.5-6 was small When, preferably 1-4 hours.

Inventors of the present invention have surprisingly found that, characterized with X-ray diffraction, κ is met using including one kind₁Value is 1 to small In equal to 3 and κ₂Value is 1 to the boehmite PB1 less than or equal to 3 and silica-alumina component, oxygen preferably wherein The specific surface area of SiClx-alumina component is 400-650 meters²/ gram, pore volume is 0.45-0.95 mls/g, the content of silica Carrier is prepared into for 15-55 weight, when preparing hydrotreating catalyst by the carrier, catalyst has higher aromatic hydrocarbons convertibility Energy.

Wherein, κ₁=h₂/h₁、κ₂=h₃/h₂, h₁、h₂And h₃Respectively in PB1 x-ray diffraction spectra 2 θ angles be 24-30, The peak height of 35-41 and 46-52 three diffraction maximums.

According to the present invention, further preferred PB1 κ₁And κ₂Value be respectively 1.02-2.3, the more preferred PB1 κ₁Value be 1.2-2.3, κ₂Value be 1.02-1.4.

On the premise of application claims are sufficient for, PB1 source is not particularly limited the present invention, for example, can be with It is commercially available commodity or is prepared using arbitrary existing method.Such as disclosed in a CN100999328B class is using aluminum sulfate and partially Boehmite prepared by boehmite method prepared by sodium aluminate neutralisation can meet the requirement of the present invention, here as join Examine reference.

In the present invention, the PB1 is in κ₁And κ₂Value meet require on the premise of, preferably wherein specific surface area be 100-350 Rice²/ gram, pore volume is 0.7-1.2 mls/g, and further preferred specific surface area is 150-280 meters²/ gram, pore volume is 0.85-1.12 Ml/g boehmite.

In the present invention, pore volume, specific surface area of the boehmite etc. are in 600 DEG C of roastings by the boehmite After burning 4 hours, characterized and obtained by BET N2 adsorptions.

Inventor further study show that, in the boehmite by aforementioned claim is met in 70-400 DEG C of dry 0.5-14 Hour, 220-330 DEG C is preferable over after dry 1-6 hours, is obtained PB1 modifier PB2, is characterized using infrared absorption spectroscopy, PB2 δ values be 1.5-4.5, preferably 1.8-3.8.Mixed using it with PB1 and silica-alumina, be molded the carrier prepared When preparing hydrotreating catalyst, the performance of catalyst is further enhanced.Wherein, δ=I₁/（I₂+I₃）, I₁Intend thin to be described 3665-3680cm in the infrared hydroxyl spectrum of diaspore^-1Locate the peak height of absworption peak, I₂For 3720-3730cm^-1Locate the peak of absworption peak Height, I₃For 3760-3780cm^-1Locate the peak height of absworption peak.

The catalyst provided according to the present invention, the content for being selected from VIII race and the metal component selected from group vib is hydrogenation The usual content of catalyst is handled, for example, on the basis of catalyst and in terms of oxide, the catalyst contains 1-10 weight %'s VIII race's metal component, 5-40 weight % VI B races metal component；Preferably comprise 1.5-7 weight % VIII race's metal component, 7-35 Weight % VI B races metal component.One or more of the group vib metal in Cr, Mo or W, preferably Mo and/or W, institute State one or more of the group VIII metal component in Fe, Co or Ni, preferably Co and/or Ni.

It is being enough at least one to be selected from VIII race and at least one metal component selected from group vib is carried on the oxygen by described On the premise of changing on alumina supporter, specific carrying method is not particularly limited.It is preferred that method be infusion process.Including respectively or same When prepare the dipping solution containing the metal component compound selected from VIII and group vib, described dipping is according to maceration extract consumption Difference can be excessive immersion stain, hole saturation dipping, and the mode difference realized according to dipping can be that infusion method is soaked, spray impregnates Deng.By the regulation and control to the concentration of dipping solution, consumption or carrier consumption, the described of specified content can be prepared and urged Agent, this is that those skilled in the art are readily appreciated by, and is not repeated here.

The method for preparing catalyst provided according to the present invention, described vib metals compound is selected from these metals One or more in soluble compound, for example, it may be silico-tungstic acid, silicotungstate, phosphomolybdic acid, phosphomolybdate, molybdate, One or more in paramolybdate, tungstates, metatungstate, ethyl metatungstate.

Described group VIII metal compound is selected from the salt of these metals, includes their inorganic acid salt or organic salt.Example Such as, the inorganic salts be selected from nitrate, carbonate, subcarbonate, hypophosphites, phosphate, sulfate, chloride and this One or more in the partially decomposed product of a little salts, it is preferable that one in nitrate, carbonate or subcarbonate Plant or several.The organic salt is the salt or soluble complexes that organic matter is combined generation with VIII race's metal, the organic matter Can be organic base, organic carboxyl acid, amine, ketone, ethers, alkyls, preferably organic carboxylate.

The catalyst provided according to the present invention, can also contain organic additive, on the basis of the catalyst, and with carbon Element meter, the content of the organic additive is no more than 10 weight %, is further preferably no more than 6 weight %.

One or more of the described organic additive in oxygen-containing and/or nitrogenous organic matter.The oxygen-containing chemical combination One or more of the thing in Organic Alcohol, organic acid, one kind in organic amine, organic ammonium salt of organic compounds containing nitrogen or It is several.Specifically, ethylene glycol, glycerine, polyethylene glycol are selected from selected from oxygen containing organic matter（Molecular weight is 200~1500）, two Ethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, winestone One or more in acid, malic acid, wherein it is preferred that ethylene glycol, glycerine, polyethylene glycol and citric acid；Nitrogenous organic matter choosing One from ethylenediamine, diethylenetriamines, 1,2-diaminocyclohexane tetraacetic acid, amion acetic acid, NTA, EDTA and its ammonium salt Plant or several, wherein it is preferred that EDTA and NTA.Described organic additive can also include simultaneously containing Organic Alcohol and Organic acid.

The preparation method provided according to the present invention, when the catalyst of the present invention further contains organic compound, is also wrapped The step of including introducing organic compound, the organic compound can be concomitantly introduced into group VIII metal, can also introduced Introduce, and be dried after group VIII metal, organic matter and group VIII metal preferably are configured into mixed solution passes through The mode of dipping is introduced simultaneously, is dried afterwards.The selection of the drying temperature and time are except being insufficient to allow VIII gold Belong to salt or complex compound decomposes outer, should also allow to retain most of introduced organic matter in the catalyst, for example, retain more than 50% Organic matter, it is highly preferred that retain more than 70% organic matter.Its method can be that any one can be realized in the prior art The method for stating purpose.For example, heat drying, it is dried under reduced pressure and heats with reference to the method such as being dried under reduced pressure.When the drying means During for heat drying, drying temperature preferably is no more than 250 DEG C, is further preferably no more than 200 DEG C, more preferably not more than 180℃.For example, in one preferred embodiment, the drying temperature is 70 DEG C~180 DEG C.

According to the present invention, when preparing the catalyst containing organic compound, in terms of carbon and with the catalysis On the basis of agent, preferably by selecting the introduction volume of the organic compound to cause in final catalyst, the organic additive Content is no more than 10 weight %, is further preferably no more than 6 weight %.

According to the conventional method in this area, the hydrotreating catalyst before the use, can generally exist in hydrogen Under, presulfurization is carried out with sulphur, hydrogen sulfide or containing sulfur feedstock at a temperature of 140-370 DEG C, this presulfurization can be carried out outside device Also can be In-situ sulphiding in device, the active metal component that it is loaded is converted into metal sulfide component.

The catalyst that the present invention is provided can be used for hydrotreating or the hydro-upgrading of all kinds of hydrocarbon oil crude materials.For hydrotreating Or the reaction condition of hydro-upgrading is usual hydrotreating or hydro-upgrading reaction condition, such as reacts Wen Weidu 200-420 DEG C, more preferably 220-400 DEG C, pressure be 2-18 MPas, more preferably 2-15 MPas, liquid hourly space velocity (LHSV) is 0.3-10 Hour^{- 1}, more preferably 0.3-5 hours^{- 1}, hydrogen to oil volume ratio is 50-5000, more preferably 50-4000.

The device of the hydrotreating or the reaction of hydro-upgrading can be enough to make the feedstock oil at hydrogenation any Manage with being carried out in the catalytic reaction dress device of the catalyst under reaction condition, for example, in the fixed bed reactors, it is mobile Carried out in bed reactor or fluidized bed reactor.

Compared with prior art provides catalyst, the present invention, which provides catalyst, has more preferable hydrogenation aromatics-removing performance.Example Such as, the catalyst provided using the present invention processes catalytic cracking tail oil, tail oil balance arene content under the conditions of being pressed in 6.4MPa Relative reduction is up to 10-55%.

Brief description of the drawings

Accompanying drawing is used to a further understanding of the present invention, and constitutes a part for specification, with following specific implementation Mode is used to illustrate the present invention together, but is not construed as limiting the invention.In the accompanying drawings：

Fig. 1（The XRD of boehmite）In PB1-1 be the boehmite for meeting application claims XRD spectra； PB2-2 is a kind of PB1-1 modifier；SB（The boehmite of Sasol companies production, trade name SB powder）It is that one kind can not Meet the XRD spectra of the boehmite of application claims.

Fig. 2（The IR-OH figures of boehmite）In PB2-1 be a kind of IR-OH spectrograms of PB1-1 modifier；PB2-2 For the IR-OH spectrograms of another PB1-1 modifier；PB2-3 is PB1-1 in the IR-OH spectrograms of 600 DEG C of product of roastings.

Embodiment

The invention will be further described by the following examples.

In experiment, XRD is carried out on the D5005 type X-ray diffractometers of Siemens, Cu targets, Ka radiation, solid Detector, 40kV, 40mA, step-scan, 0.02 ° of stride, 5~70 ° of scanning range.

IR-OH spectrograms are measured in U.S.'s BIO-RAD companies FT3000 type Fourier transformation infrared spectrometers, 15mm's Self-supporting piece, and vacuum is to 10^-3Pa, keeps 1h, is cooled to 1000~4000cm of scanning after room temperature^-1Wave-number range.

Boehmite, preparation method or source used in embodiment and comparative example：

PB1-1

The sodium metaaluminate that the aluminum sulfate and concentration for being 93g/L by the 500mL concentration of clear are 195g/L（Causticity coefficient For 1.6）It is slowly added to simultaneously in reactors of the 2L with stirring, controlling reaction temperature is 40 DEG C, pH value 7.3.After reaction completely, stir It is 9.7 to mix and add sodium carbonate to the solution ph that concentration is 0.5mol/L.After the reaction 1 hour of 50 DEG C of constant temperature, filtering, deionized water Washing three times, 120 DEG C of temperature of being divulged information in baking oven dry 3hr, obtain boehmite PB1-1.PB1-1 h1, h2, h3, k₁, k₂ And its pore volume is listed in table 1.

PB1-2

It is that 48g/L aluminum sulfate and the ammoniacal liquor of concentration 8% are slowly added to 2L bands simultaneously and stirred by the 600mL concentration of clear In the reactor mixed, reaction filtering, it is 35 DEG C, pH value 6.0 to add ammoniacal liquor controlling reaction temperature.After reaction completely, filter, will Filter cake is beaten, and it is 9.5 that stirring, which adds ammonium hydrogen carbonate to solution ph,.After the reaction 12 hours of 35 DEG C of constant temperature, filtering, deionization washing Wash three times, 120 DEG C of temperature of being divulged information in baking oven dry 3hr, obtain boehmite PB1-2.PB1-2 h1, h2, h3, k₁, k₂With And its pore volume is listed in table 1.

PB1-3

It is that 93g/L aluminum sulfate and the ammoniacal liquor of concentration 8% are slowly added to 2L bands simultaneously and stirred by the 600mL concentration of clear In the reactor mixed, controlling reaction temperature is 50 DEG C, pH value 4.6.After reaction completely, filter cake is beaten by filtering, and stirring adds carbon Sour sodium to solution ph is 8.4.After the reaction 0.5 hour of 35 DEG C of constant temperature, filtering, deionized water is washed three times, divulges information 120 in baking oven DEG C temperature dries 3hr, obtains boehmite PB1-3.PB1-3 h1, h2, h3, k₁, k₂And its pore volume is listed in table 1.

SB

The boehmite of Sasol companies production, trade name SB powder.SB h1, h2, h3, k₁, k₂And its pore volume row In table 1.

Table 1

	h1	h2	h3	k1	k2	Pore volume
							PB1-1	1300	2400	2913	1.85	1.21	1.0
PB1-2	1223	2721	3730	2.22	1.37	0.85
							PB1-3	1860	2984	3211	1.60	1.08	1.10
PB2-1	424	540	581	1.27	1.08	0.98
							PB2-2	514	615	674	1.20	1.10	0.98
SB	5740	4278	6089	0.74	1.42	0.55

Wherein, SB can not meet application claims.

Boehmite modifier used in embodiment and comparative example and preparation method thereof：

PB2-1

300 grams of PB1-1 are placed in Muffle furnace, 250 DEG C and at such a temperature constant temperature 3 hours is heated to, obtains PB2-1. PB2-1 I1, I2, I3 and δ value is listed in table 2.

PB2-2

300 grams of PB1-1 are placed in Muffle furnace, 300 DEG C and at such a temperature constant temperature 3 hours is heated to, obtains PB2-2. PB2-2 I1, I2, I3 and δ value is listed in table 2.

PB2-3

300 grams of PB1-1 are placed in Muffle furnace, 600 DEG C and at such a temperature constant temperature 3 hours is heated to, obtains PB2-3. PB2-3 I1, I2, I3 and δ value is listed in table 2.

PB2-4

300 grams of PB1-2 are placed in Muffle furnace, 230 DEG C and at such a temperature constant temperature 5 hours is heated to, obtains PB2-4. PB2-4 I1, I2, I3 and δ value is listed in table 2.

PB2-5

300 grams of PB1-3 are placed in Muffle furnace, 330 DEG C and at such a temperature constant temperature 2 hours is heated to, obtains PB2-5. PB2-5 I1, I2, I3 and δ value is listed in table 2.

Table 2

	I1	I2	I3	δ
					PB1-1	0.226	0.547	0.641	0.8
PB2-1	0.041	0.314	0.807	2.3
					PB2-2	0.014	0.126	0.512	3.7
PB2-3	0.056	0.204	0.2961	1.1
					PB2-4	0.081	0.351	0.792	1.8
PB2-5	0.022	0.116	0.489	3.5

Comparative example 1

By 267 grams of boehmite SB（Butt 0.75, butt assay method is that a certain amount of former powder is inserted into crucible with cover It is put into Muffle furnace, is warming up to after 700 DEG C of constant temperature 1hr, calculates ratio of the residue with former powder, similarly hereinafter）With 395 grams of silica- Aluminum oxide（German Condea companies production, trade name Sira-40, pore volume 0.88ml/g, than surface 468m²/ g, silica weight Measure content 40%, butt 0.76）, the mixing of 16 grams of sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of bakings Dry 3 hours, 600 DEG C of roasting temperatures 3 hours obtained carrier, catalyst carrier composition is shown in Table 3.

It is cooled to after room temperature, takes 100 grams of carriers to use and contain ammonium metatungstate（Zigong, Sichuan cemented carbide workses, tungsten oxide content is 82 weight %）50 grams, basic nickel carbonate（Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content is 51 weight %）8.7 grams, The 10.5g citric acid 78ml aqueous solution is impregnated, and 180 DEG C are dried 10 hours, obtain catalyst R-1.On the basis of catalyst total amount, in R1 The mass fraction of metal component（For calculated value, similarly hereinafter）It is listed in table 3.

Example 1

By 267 grams of boehmite powder PB1-1（Butt 0.75）With 3695 grams of silica-aluminas（With comparative example 1）, field The 16 grams of mixing of cyanines powder, are extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, and 120 DEG C dry 3 hours, 600 DEG C of roasting temperatures 3 hours, carrier is obtained, catalyst carrier composition is shown in Table 3.

It is cooled to after room temperature, takes 100 grams of carriers to use and contain ammonium metatungstate（Zigong, Sichuan cemented carbide workses, tungsten oxide content is 82 weight %）51 grams, basic nickel carbonate（Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content is 51 weight %）8.7 grams, The 10.5g citric acid 87ml aqueous solution is impregnated, and 180 DEG C are dried 10 hours, obtain catalyst C-1.On the basis of catalyst total amount, C-1 The mass fraction of middle metal component is listed in table 3.

Example 2

By 133 grams of boehmite powder PB1-1 with 109 grams of PB2-2（Butt 0.92）, 394g silica-aluminas（With real Example 1）, the mixing of 16 grams of sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of drying are roasted at a temperature of 600 DEG C Burn 3 hours, obtain carrier, catalyst carrier composition is shown in Table 3.

It is cooled to after room temperature, takes 100g carriers to use and contain ammonium metatungstate（Zigong, Sichuan cemented carbide workses, tungsten oxide content is 82 Weight %）51 grams, basic nickel carbonate（Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content is 51 weight %）8.7 grams, The 10.5g citric acid 94ml aqueous solution is impregnated, and 180 DEG C are dried 10 hours, obtain catalyst C-2.On the basis of catalyst total amount, C-2 The mass fraction of middle metal component is listed in table 3.

Comparative example 2

Be the same as Example 2, except that replacing PB-2-2 with 100g PB2-3, obtains catalyst R-2.With catalyst total amount On the basis of, the mass fraction of metal component is listed in table 3 in R-2.

Example 3

By 131.6g grams of boehmite powder PB1-3（Butt 0.76）With 224.7g PB2-1（Butt 0.89）, 267g oxygen SiClx-aluminum oxide（German Condea companies production, trade name Sira-20, pore volume 0.49ml/g, than surface 590m²/ g, dioxy SiClx weight content 20%, butt 0.75）, the mixing of 16 grams of sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of drying, 600 DEG C of roasting temperatures 3 hours obtain carrier, and catalyst carrier composition is shown in Table 3.

It is cooled to after room temperature, takes 100g carriers to use and contain ammonium metatungstate（Zigong, Sichuan cemented carbide workses, tungsten oxide content is 82 Weight %）51 grams, basic nickel carbonate（Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content is 51 weight %）8.7 grams, The 10.5g citric acid 92ml aqueous solution is impregnated, and 140 DEG C are dried 3 hours, obtain catalyst C-3.On the basis of catalyst total amount, in C-3 The mass fraction of metal component is listed in table 3.

Example 4

By 460g grams of boehmite powder PB1-3（Butt 0.76）With 56g PB2-1（Butt 0.89）, 267g silica- Aluminum oxide（German Condea companies production, trade name Sira-30, pore volume 0.78ml/g, than surface 455m²/ g, silica weight Measure content 30%, butt 0.75）, the mixing of 16 grams of sesbania powder, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, 120 DEG C of bakings Dry, 480 DEG C of roasting temperatures 8 hours obtain carrier, catalyst carrier composition is shown in Table 3.

It is cooled to after room temperature, takes 100g carriers to use and contain ammonium metatungstate（Zigong, Sichuan cemented carbide workses, tungsten oxide content is 82 Weight %）30 grams, basic nickel carbonate（Xu Chi Chemical Co., Ltd.s of Jiangsu, nickel oxide content is 51 weight %）18 grams, 25g The citric acid 94ml aqueous solution is impregnated, and 110 DEG C are dried 20 hours, obtain catalyst C-4.On the basis of catalyst total amount, metal in C-4 The mass fraction of component is listed in table 3.

Table 3

Example 7

This example illustrates that the present invention provides the performance of catalyst.

Raw materials used oil is the husky light vacuum gas oil (VGO) that subtracts two, and its physico-chemical property is shown in Table 4.

In this example, the evaluation method of catalyst is：By catalyst breakage into 2-3 millimeters of diameter particle, at 30 milliliters In fixed bed reactors load 20 milliliters of catalyst, reaction before first under a hydrogen atmosphere with containing 2 heavy % carbon disulfide kerosene according to Following program is vulcanized, and then switches reaction raw materials reaction.

Vulcanization program：150 DEG C are warming up to, sulfurized oil is introduced, constant temperature 1hr Wen Bo to be adsorbed are by two reactors, with 60 DEG C/hr is warming up to 230 DEG C, stable 2hr is warming up to 360 DEG C, stable 6hr with 60 DEG C/hr.Reaction oil is replaced, reaction temperature is adjusted To 355 DEG C, at least stablize 20hr.It is 6.4 MPas, liquid hourly space velocity (LHSV) to react hydrogen dividing potential drop（LHSV）1 hour^-1, hydrogen-oil ratio（Volume） 800, the catalyst of evaluation and its results are shown in Table 5.

Table 4

	Feedstock oil
		Density（20℃）, g/cm3	0.8885
S, weight %	16000
		N, mg/l	352
Simulation distillation（ASTM D-2887）
		IBP	291
50	391
		90	421

By products obtained therefrom by 350 DEG C of progress vacuum distillations after reaction, products obtained therefrom carries out mass spectrum PONA analysis, as a result It is shown in Table 5.

Table 5,

Catalyst	Tail oil aromatic hydrocarbons	Aromatic hydrocarbons is reduced
			R-1	14.6	Benchmark, %
C-1	13.2	10
			C-2	7.8	53
R-2	15.8	Aromatic hydrocarbons increase about 8%

Because evaluating catalyst reaction pressure is relatively low so that tail oil aromatic hydrocarbons is used close to so-called thermodynamical equilibrium region Tail oil arene content relative reduction 10-55% after this method.

Claims (18)

1. a kind of hydrotreating catalyst, containing carrier and at least one VIII race and at least one metal selected from group vib are selected from Component, the carrier contains silica-alumina and aluminum oxide, on the basis of carrier, and the content of silica-alumina is 10- 90 weight %, the content of aluminum oxide is 10-90 weight %, it is characterised in that the carrier is by silica-alumina with intending thin water aluminium Stone mixing, shaping, dry and be calcined and obtain, the boehmite includes PB1, is characterized with X-ray diffraction, the κ of the PB1₁And κ₂ Respectively greater than 1 to less than or equal to 3, wherein, κ₁=h₂/h₁、κ₂= h₃/h₂, h₁、h₂And h₃Respectively in PB1 x-ray diffraction spectra It is 24-30 at 2 θ angles^o、35-41^oAnd 46-52^oThree diffraction maximums peak height.

2. catalyst according to claim 1, it is characterised in that on the basis of carrier, the content of silica-alumina is 20-80 weight %, the content of aluminum oxide is 20-80 weight %；Characterized with X-ray diffraction, the κ of the PB1₁And κ₂Respectively 1.02- 2.4。

3. catalyst according to claim 2, it is characterised in that characterized with X-ray diffraction, the κ of the PB1₁For 1.2-2.3, κ₂For 1.02-1.4.

4. catalyst according to claim 1, it is characterised in that the specific surface area of the PB1 is 100-350 meters²/ gram, hole Hold for 0.7-1.2 mls/g.

5. catalyst according to claim 4, it is characterised in that the specific surface area of the PB1 is 150-280 meters²/ gram, hole Hold for 0.85-1.12 mls/g.

6. catalyst according to claim 1, it is characterised in that the specific surface area of the silica-alumina is 350- 750 meters²/ gram, pore volume is 0.4-1.2 mls/g.

7. catalyst according to claim 6, it is characterised in that the specific surface area of the silica-alumina is 400- 650 meters²/ gram, pore volume is 0.45-0.95 mls/g.

8. the catalyst according to claim 1,6 or 7 any one, it is characterised in that using the silica-alumina as base The content of silica is 10-80 weight % in standard, the silica-alumina.

9. catalyst according to claim 8, it is characterised in that on the basis of the silica-alumina, the oxidation The content of silica is 15-55 weight % in silicon-aluminum oxide.

10. catalyst according to claim 1, it is characterised in that the metal component of VIII race is selected from nickel and/or cobalt, The metal component of the group vib is selected from molybdenum/or tungsten, is counted by oxide and on the basis of the catalyst, the nickel and/or cobalt Content is 1-15 weight %, and the content of the molybdenum/or tungsten is 5-40 weight %.

11. catalyst according to claim 10, it is characterised in that counted by oxide and on the basis of the catalyst, The content of the nickel and/or cobalt is 2.0-10 weight %, and the content of the molybdenum/or tungsten is 10-35 weight %.

12. catalyst according to claim 1, it is characterised in that the boehmite is PB1 and PB2 mixture, Counted by butt and on the basis of carrier, PB1 content is that 10-90 weight %, PB2 content are 5-60 weight %, with infrared spectrum Characterize, PB2 δ values are 1.5-4.5, wherein, δ=I₁/（I₂+I₃）, I₁For 3665- in the infrared hydroxyl spectrum of the boehmite 3680 cm^-1Locate the peak height of absworption peak, I₂For 3720-3730 cm^-1Locate the peak height of absworption peak, I₃For 3760-3780cm^-1Place absorbs The peak height at peak.

13. catalyst according to claim 12, it is characterised in that counted by butt and on the basis of carrier, PB1 content It is that 10-50 weight %, PB2 δ values are 1.8-3.8 for 20-80 weight %, PB2 content.

14. catalyst according to claim 1, it is characterised in that described drying condition includes：Temperature is 50-350 DEG C, the time is 1-24 hours；Described roasting condition includes：Temperature is 400-700 DEG C, and the time is 0.5-6 hours.

15. catalyst according to claim 14, it is characterised in that described drying condition includes：Temperature is 80-200 DEG C, the time is 1-6 hours；Described roasting condition includes：Temperature is 550-650 DEG C, and the time is 1-3 hours.

16. catalyst according to claim 12, it is characterised in that the PB2 is PB1 in 70-400 DEG C of dry 0.5-14 The modifier of hour.

17. catalyst according to claim 16, it is characterised in that the PB2 is that PB1 is small in 220-330 DEG C of dry 1-6 When modifier.

18. application of the catalyst in hydrocarbon ils processing according to claim any one of 1-17.