CN1048651C

CN1048651C - Process for preparation of hydrogenating catalyst carrier

Info

Publication number: CN1048651C
Application number: CN94107295A
Authority: CN
Inventors: 赵琰; 佟明海; 曹光伟; 魏登凌; 王继峰
Original assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Current assignee: Sinopec Fushun Research Institute of Petroleum and Petrochemicals
Priority date: 1994-06-29
Filing date: 1994-06-29
Publication date: 2000-01-26
Anticipated expiration: 2014-06-29
Also published as: CN1141821A

Abstract

The present invention describes a preparation method for a hydrogenating catalyst carrier with an average pore diameter of 7 to 12 nm, a pore volume of 0.7 to 1.2 ml/g and a surface area of 250 to 500 m<2>/g. The method is suitable for heavy distillate oil hydrodesulphurization, hydrodenitrification, hydrodemetallization, aromatic hydrocarbon saturation catalyst carriers and hydrocracking catalyst carriers.

Description

A kind of preparation method of catalyst carrier for hydrgenating

The invention belongs to macropore, high surface area aluminum oxide or contain the preparation method of small amounts phosphorus or silica support and be used for preparing catalyzer.

The mean pore size of carrier of the present invention is 7～12nm, pore volume 0.7～1.2ml/g, surface-area 250～500M ²/ g is applicable to the carrier and the carrier of hydrocracking catalyst of heavy distillate hydrogenating desulfurization, hydrodenitrification, hydrodemetallation (HDM), aromatic hydrocarbon saturation catalyst.

Purpose of the present invention provide have macropore, high surface area, tap density be lower, is that carrier, second purpose of main ingredient provides the aqueous alumina based on pseudo-boehmite with the aqueous alumina, not only can also can be used as tackiness agent as support of the catalyst.The 3rd purpose is with macropore, high surface area aluminum oxide or contain small amounts phosphorus or silicon oxide is that the carrier heavy distillate hydrotreatment of making and hydrocracking catalyst desulfurization, denitrification activity are good, activity and middle distillates oil selectivity height during hydrocracking.

Heavy distillate is meant HAGO, VGO, CGO, CCO etc., and boiling range is 250～560 ℃, contains usually than high-sulfur, nitrogen, aromatic hydrocarbons etc.In order to reduce topsoil and to keep high activity of catalyst, need remove impurity, so that the vapour that production and transport is used, diesel oil, oil fuel, or provide the high-quality charging for downstream unit such as FCC, HC, MHC etc.The unifining process that heavy distillate removes impurity generally is referred to as hydrotreatment, and it is under certain temperature and pressure, and stock oil contacts with the catalyzer that suits with hydrogen, nitrogen transformation is ammonia, sulphur is converted into hydrogen sulfide, and polycyclic aromatic hydrocarbons is saturated.Typical hydrotreating catalyst contains oxide or the sulfide of VIII family and group vib metal, is supported on γ-Al ₂O ₃Or low SiO ₂Stable Al ₂O ₃, or P ₂O ₅-Al ₂O ₃Or SiO ₂-P ₂O ₅-Al ₂O ₃On the carrier.In order to improve catalyst activity, still needing sometimes adds auxiliary agent B, P, F etc.Think that at present the pore structure character of carrier directly affects catalyst activity, stability.

Secondly, in order from heavy distillate, to produce gasoline, boat coal, diesel oil, lube base oil and ethylene raw (steam cracking is used), need deep pyrolytic (such as FCC, HC, MHC), wherein HC and the used catalyst of MHC process, except using VIII family and group vib metal as the hydrogenation component, still with the zeolite after Y type, X-type, ZSM, β zeolite and the modification thereof or the SiO of unformed different Si/Al ratios ₂-Al ₂O ₃Do outside the acidic components, also use a small amount of boehmite (AlOOH) to make the adhesive of carrier or catalyst.Be main hydrocracking catalyst for oil distillate (boat coal and light diesel fuel) in production, need to use a part of aluminium oxide to do carrier, to play dispersed metal, to reduce second pyrolysis, to improve the catalyst middle distillates oil selectivity and to improve catalyst strength, strengthen crushing strength, reduce the attrition of catalyst rate.At above-mentioned various objectives, to Al ₂O ₃Pore diameter range and ratio that pore volume, surface-area, pore distribution are mainly concentrated, Al ₂O ₃Middle impurity such as Na ⁺, Cl ^-, SO ₄ ^2-, Fe ³⁺Deng requirement and Al ₂O ₃The content of middle auxiliary agent P, Si, F, B etc. and combined composition thereof etc. all has different requirements.

As everyone knows, catalyst carrier properties such as pore volume, the pore diameter range that surface area or average pore size and pore size distribution are mainly concentrated and ratio or most probable aperture to employed catalyst activity, selectively, stability and regenerability play an important role.The heavy distillate hydrogenation is handled and the used carrier of hydrocracking catalyst, if mean pore size＜5nm, because heavy metal in the mink cell focus, colloid, asphalt content are higher, heavy metal deposition and polycyclic aromatic hydrocarbons, gum asphalt coking are deposited in the catalyst pores, and easily make catalyst deactivation, the mink cell focus macromole is low in catalyzer aperture internal diffusion speed simultaneously, speed of response is low, therefore require to enlarge the aperture, to guarantee the stability of catalyzer, if mean pore size excessive (＞12nm), the catalyst buildup density of then making is little, denitrification activity is low and intensity is low.Therefore above-mentioned hydrotreatment, the used pseudo-boehmite dry glue powder of hydrocracking catalyst is than body, suitable mean pore size is 7～12nm, it is big that this outer surface area is wanted, and because of surface-area is big, Metal Distribution is even, catalyst activity, stability and regenerability are good, general requirement carrier surface area＞300M ²/ g, following patent has been revealed carrier or Preparation of catalysts method.

EP0,201,949 have revealed narrow hole Al ₂O ₃The carrier preparation process, this Al ₂O ₃Surface area＞300N ²/ g, pore volume 0.35～0.65ml/g, at least 80% or＞90% aperture＜5nm, crushing strength＞88N, this Al ₂O ₃Contain P0.1～4.5% (w).This carrier preparation method is (such as H with the phosphorus-containing compound bialuminate aqueous solution ₃PO ₄+ AlCl ₃) and basic aluminate (NaAlO ₂Or KAlO ₂), at 20～90 ℃, PH is 5.5～10, be preferably in 50～85 ℃, PH neutralizes under 6～7.5 conditions, wears out 15 minutes at least more preferably aging 0.25～1 hour at 20～90 ℃, then filter, again cyclic washing and filtration, in removing and the time impurity that brings, 50～150 ℃ of dryings, roasting in 300～900 ℃ of scopes makes γ-Al ₂O ₃

USP4,820,679 have revealed a kind of method for preparing catalyst, its surface-area＞300M ²/ g, at least 70% pore volume concentrate on aperture＜7nm high activated catalyst.This method uses alkaline aqueous solution (such as NaAlO ₂) and one or more acid aluminium salt aqueous solution [such as Al ₂(SO ₄) ₃], at 20～90 ℃, PH is 5.5～10, is preferably in 55～65 ℃, PH6～7.5 neutralizations, is in 11～12 scopes aging 15 minutes at least at 20～90 ℃, preferably 50～85 ℃ of PH8～12, PH, in the washing and Al (OH) ₃Hydrogel, with nickel salt and molybdenum or tungsten saline solution, at 25～100 ℃, PH is 4～10 times pulps, makes metal adsorption with hydrogel, until final catalyst contains NlO1～6% and MoO ₃8～22% or WO ₃10～40%, two rear extruded mouldings, dry, roasting in 300～900 ℃ of scopes.

USP3,864,461 have revealed that heap is than little Al ₂O ₃The carrier preparation method is: contain Al ₂O ₃2～7.5%Na ₃AlO ₂The aqueous solution is added in 12～35 ℃ or 45～70 ℃ of scopes and contains Al ₂O ₃2～6%Al ₂(SO ₄) ₃In the aqueous solution, make earlier Al ₂(SO ₄) ₃Surplus 10%, most of Al (OH) under acid condition ₃Precipitation then adds superfluous 10%NaAlO ₂Solution in PH7.3～10 scopes, makes it precipitation fully, Al in the slurries ₂O ₃Content 2～7w%, filtration, washing, filter cake are dry under＜100 ℃, and 300～400 ℃ of roastings.

Find out from above patent, pore distribution mainly concentrate on aperture＜5nm or＜7nm, account for more than 70%, have even＞80% or＞90%, pore volume is also little, is 0.35～0.65ml/g, and is not too suitable as the carrier of catalyst for hydro-processing heavy distillate.

Speak of in the above-mentioned patent with Al (OH) ₃Hydrogel directly adds aqueous metal salt, makes catalyst, and following drawback is arranged: the catalyst crushing strength is low, rate of wear is big; Extrusion is shaped and does not more add the Al of metal ₂O ₃The powder difficulty; Generate easily NlAl ₂O ₄Or CoAl ₂O ₄Spinelle is difficult for during sulfuration being reduced to sulfide and affects activity, because Al (OH) ₃Hydrogel and aqueous metal salt direct effect are combined with the aluminium of various structures, have lost Al ₂O ₃Support modification measure or add a small amount of auxiliary agent and can improve activity and control metal in the surface uniform peptizaiton, thus coprecipitation method, kneading method to add the catalyst activity of metal lower than infusion process.

A kind of rickle that above-mentioned patent is revealed compares Al ₂O ₃The carrier preparation method, reality is the soda acid swing method, its repeatability is relatively poor.

Emphasis of the present invention provide a kind of acidity a little less than, surface-area 250～500M ²/ g, pore volume 0.7～1.2ml/g, mean pore size is 7～12nm, based on the aqueous alumina of pseudo-boehmite, or contains the preparation method of the aqueous alumina of small amounts phosphorus and/or silicon oxide.Can be as the carrier of heavy distillate hydrotreatment and hydrocracking catalyst, also can be as the used pseudo-boehmite of the tackiness agent of catalyzer or carrier (AlOOH).This method can according to the different requirements of catalyst, add different oxides, to adjust Al ₂O ₃Acidity and pore structure and surface nature are suitably adjusted neutrality condition in addition, still can prepare the boehmite of medium pore volume and surface area, use for adhesive or carrier.

Aqueous alumina or the aqueous alumina hydrogel preparation that contains a small amount of phosphorous oxide and/or silica are with suitable acidity or alkaline matter or solution one or more aluminum saline solutions that go to neutralize, and generate Al (OH) ₃Hydrogel precipitation, the technology of the present invention key are with alkaline precipitating agent such as NaOH or NH ₄OH or composite alkali aluminum saline solution such as KAlO ₂Or NaAlO ₂Acid aluminum saline solution such as Al go to neutralize ₂(SO ₄) ₃, Al (NO ₃) ₃, AlCl ₃Deng, if with alkalescence composite alkali aluminum saline solution such as KAlO ₂Or NaAlO ₂, not only can use the acid aluminium salt aqueous solution such as Al ₂(SO ₄) ₃, Al (NO ₃) ₃, AlCl ₃, also usable acid precipitating reagent is such as HCl, HNO ₃, CO ₂Deng.One of the technology of the present invention key is to regulate to contain aluminum solutions to make its pH value be 6.0～10, could produce Al (OH) ₃Or AlOOH precipitation.Next is that to regulate the temperature contain aluminum solutions be 30～85 ℃.

Suitable preparation method is with the acid aluminium salt aqueous solution and the neutralization of composite alkali aluminum saline solution, generates Al ₂O ₃The hydrogel precipitation.Suitable acid aluminium salt comprises Al ₂(SO ₄) ₃, Al (NO ₃) ₃, AlCl ₃, Al preferably ₂(SO ₄) ₃And AlCl ₃Suitable composite alkali aluminum salt is NaAlO ₂, suitable basic solution is NH ₄OH.With in composite alkali aluminum salt brine solution and the acid aluminium salt aqueous solution and the stream and some hrs, in and the selection of time, should add speed, neutralization tank capacity and neutralization reaction effects according to two kinds of solution and determine.

After neutralization is finished, can add as required or not add silicate solutions, SiO ₂Content accounts for carrier 0.1～5.0w%, because SiO ₂Ratio is little, improves Al ₂O ₃Surface acidity improves the interaction of metal and aluminium, and adding method of the present invention is in advance the proper amount of silicon hydrochlorate to be sneaked into composite alkali aluminum salt or alkaline solution then neutralizes.

Add or do not add aqueous silicate solution, do not need to adjust again temperature and PH, wear out, the aging temperature typical range is 30～85 ℃, and suitable is 40～80 ℃, the suitableeest is 50～70 ℃, aging typical PH is 6～10, and suitable PH is 7～9.5, and optimal pH is 7.5～9.0, aging temperature and PH and neutral temperature, PH is basic identical.If in and the time alkaline solution adopt NH ₄OH considers NH in the ageing process ₃Volatilization, and PH is reduced, can add a small amount of weak aqua ammonia this moment, to keep required pH value.Digestion time typical range 0.25～8 hour, suitable is 0.5～5 hour, the suitableeest is 1～3 hour.

Behind aging the end, slurries filter in the usual way, and solubilizer making beating washing refilters then, and repeatedly several times, to remove the water soluble salt that generates in most of N-process, the suitableeest solvent of washing is water purification, certainly also available lower alcohol solvent.

Aluminium hydroxide hydrogel after the washing is pressed conventional method 50～150 ℃ of dryings, or adds the water making beating before the drying as required, adds the phosphorus-containing compound aqueous solution in situation about stirring, and phosphorus content accounts for 0.5～5w% of carrier.

Preparing the aluminum hydroxide solid elastomer process by the present invention may further comprise the steps:

A) the preparation bialuminate aqueous solution, Al ₂O ₃Concentration is 2～10g/100ml.

B) the preparation basic aluminate aqueous solution, Al ₂O ₃Concentration is 10～30g/100ml, or the preparation dilute ammonia solution, NH ₃Content is 9～15g/100ml.

C) the acid aluminium salt aqueous solution and basic aluminium salt (or NH ₄OH) aqueous solution adds simultaneously continuously and stirs in lower certain water gaging, 30～85 ℃ of neutral temperatures, suitable 40～80 ℃ the suitableeest be 50～70 ℃, in and PH typical range 6～10, fitting is 7～9.5, the suitableeest is 7.5～9.0.25～4 hour neutralization reaction time, suitable 0.5～3 hour, the suitableeest was 1～2 hour, in and Al in the slurries ₂O ₃Content is 2～10g/100ml, and suitable is 5～9g/100ml.

D) at 30～85 ℃, suitable 40～80 ℃, the suitableeest is that 50～70 ℃ of temperature and PH are 6～10, and suitable is 7～9.5, and the suitableeest is aging under 7.5～9 conditions, digestion time 0.25～8 hour, and suitable is 0.5～5 hour, the suitableeest is 1～3 hour.

When e) needing at d) before the step, add aqueous silicate solution, make SiO ₂Content is 0.1～5w%, wears out again.The suitableeest aqueous silicate solution is Na ₂SiO ₃Solution, its SiO ₂Content is 1～10g/100ml.Behind aging the end, filter, isolate water-soluble salt.

F) with water purification or lower alcohol washing aluminium hydroxide hydrogel, wash temperature is identical with neutral temperature, washing PH9.0-8.3, and PH successively decreases along with washing times, regulates the solution of PH in the washing process, can be NH ₄OH, NH ₄HCO ₃, also can use Na ₂CO ₃The aqueous solution.The washing purpose is to remove SO ₄ ^2-Or Cl ^-, Na ⁺Deng, make crystalline aluminum hydroxide complete or grow up simultaneously.Need to filter after each washing.

G) aluminium hydroxide hydrogel after the washing can add an amount of phosphoric acid or ammonium phosphate salt when needing, and making phosphorus content is 0.5～5w%.

H) aluminum hydroxide filter cake or slurries after the washing, or the aluminum hydroxide filter cake after phosphorating or slurries 50～150 ℃ of lower dryings, make dry glue powder Al ₂O ₃Content＞70w%.

L) dried dry glue powder is converted into γ-Al 300～700 ℃ of roastings ₂O ₃Or low SiO ₂Stable γ-Al ₂O ₃Or P ₂O ₅-Al ₂O ₃Or SiO ₂-P ₂O ₅-Al ₂O ₃

J) dry back dry glue powder add/or do not add zeolite after Y type, X type, ZSM, β zeolite and the modification thereof, add tackiness agent, extrusion aid etc. again, grind to mix to pinch and roll, extruded moulding floods with VIII family and group vib metal salt solution behind the drying and roasting and makes catalyzer.

K) dried dry glue powder also can directly add or not add j) described zeolite, VIII family and group vib metal-salt add tackiness agent, extrusion aid etc. again, grind, mix and pinch, roll, again extruded moulding, drying, the bakes to burn the article catalyzer that gets product.

Macropore of the present invention, high surface area aluminum oxide or contain the preparation method and the use thereof of small amounts phosphorus and/or silica support further specify with following example, but these examples can not limit the present invention.

Example one

To contain the 4.1l aqueous solution and the 8l aqueous solution that contains 2613g Tai-Ace S 150 of 2320g sodium metaaluminate, be respectively charged in the tubualted bottle of high level, and connect the under meter inflow down and be equipped with in the stainless cylinder of steel of 2l water purifying belt stirrer and heating jacket, be heated to 68～72 ℃.Under the uniform stirring condition, two kinds of solution are added in the tank simultaneously by certain speed, make PH remain on 8～8.5, in and 1 hour, slurries 60～65 ℃ lower aging 1 hour, filter to isolate mother liquor, add Al ₂O ₃30 times of water purification washings of inventory refilter, and repeatedly several times, wash temperature is identical with aging temperature, available 10% NH ₄OH or 20g/100ml Na ₂CO ₃The aqueous solution is regulated washing PH9.0～8.3, and PH successively decreases with washing times, washes rear wet cake and is divided into two parts, a direct 110 ± 10 ℃ of dryings 8 hours, and again 500～550 ℃ of roastings 4 hours, i.e. sample (1).Another part is added to 13ml83%H ₃PO ₄With making beating in the 2.5l water 1 hour, filter, by above-mentioned condition drying, roasting, i.e. sample (1A).Character sees Table 1.

Example two

Take 400～440l/h flow velocity with the NaAlO of proportion as 1.34～1.364 ₂Solution and take 640～660l/h flow velocity with the Al of proportion as 1.154～1.162 ₂(SO ₄) ₃Solution, be added to simultaneously in the 200l water purification in the stirring 58～64 ℃ of holding temperatures, PH7.9～8.6, neutralization reaction 1.5 hours, slurries wore out 1 hour in above-mentioned condition, filtered, and washed 5 times in 60～65 ℃ of PH9.0～8.3, wet cake adds in the 1000l water purification and pulls an oar, spray-drying, the sampling roasting, character sees Table 1 (2).

Example three

Condition is with example one, and the just aging preceding 338ml that adds contains SiO ₂6.75g/100ml Na ₂SiO ₃, the results are shown in Table 1 (3).

Example four

Contain Al with 1000l/h ₂O ₃AlCl for 34.8g/l ₃Solution replaces Al ₂(SO ₄) ₃Solution contains NH with 280l/h ₃The NH of 114g/l ₄OH replaces NaAlO ₂, neutralization, aging, wash conditions is constant, the results are shown in Table 1 (4).

Example five

Press EP0, the reference carrier of 201,949 examples, 1 preparation is with 740gNaAlO ₂Be added in the 1l water purification, be heated to 60 ℃, 542gAlCl ₃H ₂O adds in the 876g water, and adds 112g85%H ₃PO ₄Be heated to 60 ℃, two kinds of solution pass through under meter, are added to simultaneously by certain flow rate and are equipped with in the white cylinder of steel of 0.5l water purifying, and keeping PH is 7, use NaAlO before wearing out ₂PH adjusts to 10 with slurries, wears out 1 hour at 60 ℃, and roasting in filtration, washing, 8 hours, 565 ℃ airflows of 110 ± 10 ℃ of dryings the results are shown in Table 1 (5).

Example six

Identical with example five conditionally completes, only at AlCl ₃Do not add 85%H in the solution ₃PO ₄, see Table 1 (6).

Found out that by table 1 example 1～4 is by the Al of the technology of the present invention preparation ₂O ₃, contain P ₂O ₅Al ₂O ₃And SiO ₂-P ₂O ₅-Al ₂O ₃, average pore size is all at 8～12nm, pore volume 0.8～1.0ml/g, surface area 300～460M ²/ g, pore distribution concentration and is pressed EP0 in 5～15nm scope, the examples 5,6 of 201,949 preparations, average pore size 5～7.2nm, pore volume be less than 0.5ml/g, pore size distribution mainly concentrates on＜5nm or＜the 10nm scope in.

Example seven

Catalyst A is the boehmite dry glue powder (Al of the technology of the present invention example 2 described process preparations in the example 7 ₂O ₃Content 71.50%), add proper inorganic acid, water squeezes for helping, kneading rolls, by φ 1.6mm bunge bedstraw herb orifice plate extrusion, carrier bar after the roasting, drying, roasting, is made catalyst property and is seen Table 2 by general infusion process dipping 1 hour, the superfluous liquid of elimination with Mo-Nl-P solution.Catalyst B is industrially to use, with Al ₂O ₃Be the heavy oil hydrogenating treatment catalyst of carrier, at the 6.4MPa hydrogen pressure, during LHSV1.0 ^-1, 380 ℃ of following hydrotreatment wax tailings, its HDN performance sees Table 2.

Example eight

Catalyzer C is pseudo-boehmite dry glue powder and the overstable gamma zeolite with the 4 described process preparations of the technology of the present invention example in the example 8, aluminum oxide, nickelous nitrate, tackiness agent mix to pinch and roll, by φ 1.8mm orifice plate extrusion, make hydrocracking catalyst, catalyzer D uses reference hydrocracking catalyst, two kinds of catalyzer for industry and all adopts two doses of series connection of single hop once to be VGO and CGO mixing oil by flow process, stock oil, and character sees Table 3, under the 14.7MPa hydrogen pressure, treated oil nitrogen 3～5ppm is during LHSV1.5 ^-1, hydrogen/oil is 1500 to carry out hydrocracking, generates oil＜when 320 ℃ of yields are 60w%, the 320 hours desired reaction temperatures of turning round see Table 4 as the initial activity of catalyzer.

Find out Al of the present invention from table 2, table 4 ₂O ₃Or P ₂O ₅-Al ₂O ₃Has higher hydrodenitrogeneration Deng the hydrotreatment of making or hydrocracking catalyst, hydrogenation cracking activity.

Table 1

Example	(1)	(1A)	(2)	(3)	(4)	(5)	(6)
Example	(1)	(1A)	(2)	(3)	(4)	(5)	(6)	Raw material
Acidic solution	Al ₂(SO ₄) ₃	Al ₂(SO ₄) ₃	Al ₂(SO ₄) ₃	Al ₂(SO ₄) ₃	AlCl ₃	AlCl ₃+H ₃PO ₄	AlCl ₃	Raw material
Acidic solution	Al ₂(SO ₄) ₃	Al ₂(SO ₄) ₃	Al ₂(SO ₄) ₃	Al ₂(SO ₄) ₃	AlCl ₃	AlCl ₃+H ₃PO ₄	AlCl ₃	Basic solution	NaAlO ₂	NaAlO ₂	NaAlO ₂	NH ₄OH	NH ₄OH	NaAlO ₂	NaAlO ₂
Carrier A l ₂O ₃Middle P, w% SiO ₂，w％	0 0	1.73 0	0 0	1.95 3.34	0 0	2 0	0 0	Basic solution	NaAlO ₂	NaAlO ₂	NaAlO ₂	NH ₄OH	NH ₄OH	NaAlO ₂	NaAlO ₂
Carrier A l ₂O ₃Middle P, w% SiO ₂，w％	0 0	1.73 0	0 0	1.95 3.34	0 0	2 0	0 0	* pore volume, ml/g	0.803	0.996	0.851	1.03	0.917	0.49	0.45
Surface-area, M ²/g	359	433	389	460	303	365	251	* pore volume, ml/g	0.803	0.996	0.851	1.03	0.917	0.49	0.45
Surface-area, M ²/g	359	433	389	460	303	365	251	Mean pore size, nm	8.9	9.2	8.7	8.9	12.1	5.4	7.2
Pore distribution, %＜5nm 5～10nm 10～15nm＞15nm	27.3 42.9 13 16.8	24.6 51.6 10.9 12.9	33.4 51.2 6.5 8.7	31.6 42.1 12.3 14	4.2 48.7 17.9 29.2	92.5 3.9 1.7 1.9	30.1 64.0 1.7 2.4	Mean pore size, nm	8.9	9.2	8.7	8.9	12.1	5.4	7.2

* the listed pore volume of table 1.Surface-area.Pore distribution is the N determination of adsorption method.

Table 2

	CatA	CatB
	CatA	CatB	MoO ₃, w%	24.6	9.9
WO ₃, w%	-	20.9	MoO ₃, w%	24.6	9.9
WO ₃, w%	-	20.9	NlO, w%	3.72	6.31
Auxiliary agent, w%	2.83	4.77	NlO, w%	3.72	6.31
Auxiliary agent, w%	2.83	4.77	Pore volume, ml/g	0.323	0.247
Average pore size, nm	8.3	5.8	Pore volume, ml/g	0.323	0.247
Average pore size, nm	8.3	5.8	The 500 hours HDN that turn round, %	80.2	69.2
The 500 hours HDS that turn round, %	95.4	92.2	The 500 hours HDN that turn round, %	80.2	69.2

Table 3

Raw material	CGO	VGO-CGO
Raw material	CGO	VGO-CGO	Density, g/cm ²	0.8836	0.8778
Boiling range, ℃	227～486	307～521	Density, g/cm ²	0.8836	0.8778
Boiling range, ℃	227～486	307～521	Sulphur, w%	0.81	0.42
Nitrogen, w%	0.42	0.145	Sulphur, w%	0.81	0.42
Nitrogen, w%	0.42	0.145	Carbon, w%	86.9	85.86
Hydrogen, w%	12.97	12.92	Carbon, w%	86.9	85.86

Table 4

CatC CatDMoO ₃, w% 18.8 25.1gNlO, w% 5.76 8.73SiO ₃, w% 12.56 3.0Al ₂O ₃, w% surplus surplus pore volume, ml/g 0.355 0.36 tap density, g/ml 0.88 0.91 crushing strength, N/mm 24.7 23 average reaction temperature, ℃ 381 394

Claims

1, a kind of have mean pore size 7～12nm, pore volume 0.7～1.2ml/g, surface-area a 250～500m ²The aluminum oxide of/g, or contain the carrying alumina preparation of small amounts phosphorus and/or silicon oxide, it is characterized in that may further comprise the steps:

A) contain aluminum ions acidic aqueous solution and contain or do not contain aluminum ions alkaline aqueous solution and add simultaneously in the water purification under stirring, carry out neutralization reaction, 0.25～4 hour neutralization reaction time;

B) neutral temperature 30-85 ℃, in and PH6～10, in and slurries in Al ₂O ₃Content is 2～10g/100ml;

C) at 30-85 ℃, the aluminium hydroxide hydrogel that the aging neutralization of PH6～10 conditions generates, digestion time 0.25～8 hour is filtered then;

Before aging, add aqueous silicate solution when d) needing, make Si-Al in conjunction with wearing out again and filtering;

E) washing aluminium hydroxide hydrogel, wash temperature is identical with neutral temperature, and control PH is so that remove impurity SO ₄ ⁼(or Cl ^-), Na ⁺

F) washing back aluminium hydroxide hydrogel can add an amount of P contained compound when needing;

G) aluminum hydroxide filter cake or slurries after the washing, or the aluminum hydroxide filter cake after phosphorating or slurries 50～150 ℃ of lower dryings, make dry glue powder Al ₂O ₃Content＞70w%;

H) dried dried glue 300～700 ℃ of roastings, is converted into γ-Al ₂O ₃Or low SiO ₂Stable γ-Al ₂O ₃, or P ₂O ₅-Al ₂O ₃Or SiO ₂-P ₂O ₅-Al ₂O ₃

2, in accordance with the method for claim 1, it is characterized in that the described aluminium ion acidic aqueous solution that contains is Al ₂(SO ₄) ₃, AlCl ₃Or Al (NO ₃) ₃The aqueous solution is with Al ₂O ₃Meter concentration is 2～10g/100ml.

3, in accordance with the method for claim 1, it is characterized in that the described aluminium ion alkaline aqueous solution that contains is NaAlO ₂Or KAlO ₂, with Al ₂O ₃Meter concentration is 10～30g/100ml.

4, in accordance with the method for claim 1, it is characterized in that described not contain aluminum ions alkaline aqueous solution be NH ₄OH or NaOH are with NH ₃Meter concentration is 9～15g/100ml.

5, in accordance with the method for claim 1, add aqueous silicate solution when needing before it is characterized in that wearing out, be Na ₂SiO ₃The aqueous solution, SiO ₂Content is 1～10g/100ml.

6, in accordance with the method for claim 1, the gel aluminum hydroxide after it is characterized in that washing, adding an amount of phosphorus-containing compound when needing is phosphoric acid or ammonium phosphate salt.

7, in accordance with the method for claim 1, it is characterized in that neutral temperature is 40～80 ℃.

8, in accordance with the method for claim 1, it is characterized in that neutral temperature is 50～70 ℃.

9, in accordance with the method for claim 1, it is characterized in that in and PH be 7～9.5.

10, in accordance with the method for claim 1, it is characterized in that in and PH be 7.5～9.0.

11, in accordance with the method for claim 1, it is characterized in that ageing time is 0.5～3 hour, Al in the slurries ₂O ₃Content is 5～9g/100ml.

12,, it is characterized in that digestion time is 0.5～5 hour according to the described method of claim 1.

13, in accordance with the method for claim 1, it is characterized in that adding aqueous silicate solution is Na ₂SiO ₃The aqueous solution, SiO ₂Content is 1～10g/100ml, SiO ₂Add-on accounts for carrier 0.1～5w%.

14, in accordance with the method for claim 1, it is characterized in that adding P contained compound is phosphoric acid or ammonium phosphate salt, and the P add-on is 0.5～5w% of carrier.