CN102161004A - Hydrotreating catalyst and application thereof - Google Patents

Abstract

The invention discloses a hydrotreating catalyst and application thereof. The catalyst contains a carrier, at least one metal component selected from VIII group and at least one metal component selected from VIB group, wherein the carrier contains silicon oxide-aluminum oxide. The catalyst is characterized in that: the silicon oxide-aluminum oxide is obtained by roasting a composite of boehmite and a silicon compound-containing composition, wherein the boehmite comprises at least one boehmite P1, wherein n is more than or equal to 1.1 and less than or equal to 2.5. n is equal to D(031)/D(120), wherein the D(031) represents the crystalline grain size of a crystal face represented by the 031 peak in an XRD spectrogram of boehmite grains; the D(120) represents the crystalline grain size of the crystal face represented by the 120 peak in the XRD spectrogram of the boehmite grains; the 031 peak is the peak of which the 2 theta is 34 to 43 degrees in the XRD spectrogram; and the 120 peak is the peak of which the 2 theta is 23 to 33 degrees in the XRD spectrogram. D is equal to K lambda/(Bcos theta), wherein K is Scherrer constant; lambda is diffraction wavelength of a target-shaped material; B is the peak breadth, at half height, of a diffraction peak; and 2 theta is the position of the diffraction peak. Compared with the prior art, the hydrotreating performance of the catalyst provided by the invention is obviously improved.

Description

A kind of hydrotreating catalyst and application thereof

Technical field

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

Background technology

The hydrofinishing of hydrocarbon raw material or hydrotreatment are a kind of technical process of generally using in the petroleum refining industry, and its effect mainly is to remove impurity such as sulphur in the hydrocarbon feed, nitrogen, metal, aromatic hydrocarbons, carbon residue.By hydrotreatment, perhaps can directly obtain the light-end products that clean, for example diesel oil is carried out can obtaining the clean diesel product after the hydrofinishing; Perhaps can improve the character of hydrocarbon feed, for example the FCC raw material be carried out preliminary treatment, the improved hydrocarbon feed of character is re-used as the charging of FCC process, to improve the efficient of FCC process.Employed hydrogenation catalyst is made of the carrier (as aluminium oxide, silica-alumina) that comprises group vib (as molybdenum or tungsten) and group VIII metal (as cobalt or nickel) component usually in the hydrotreatment process.Carrier has the effect of holding with dispersed active metal, and its pore structure and surface nature directly influence metal interactional power between dispersion, distribution and the metal-carrier of carrier surface, and therefore the activity to hydrogenation catalyst has material impact.Preparing good catalyst carrier for hydrgenating, is the effective way that improves hydrogenation catalyst performance.Silica-alumina is because of having better pore structure, specific surface, heat-resistant stability and solid acid character, and the carrier that Chang Zuowei prepares this type of catalyst uses.

In the prior art, having is the report of the hydrogenation catalyst of carrier about silica-alumina carrier and preparation method thereof with adopting silica-alumina a lot.For example:

Document (" aluminium oxide-silicon oxide is the preparation and the rare-earth-doped modification research of nano-powder ", functional material, 2004,35 the 6th phases of volume, 788 pages) reported that a kind of aluminium oxide-silicon oxide is the preparation of nano-powder, comprising that nano level active Al (OH) x that adopts the aluminium powder hydrolysis and prepare is an aluminum feedstock, is the silicon raw material with waterglass, and with Al ₂O ₃/ SiO ₂Be basic recipe at=2: 1, after introducing an amount of dispersant, fully mixes.By the control of pH value, to coat depositing technology,, thereby form the Al-Si complex at a certain temperature at surface, Al source parcel one deck Si raw material, go worker's technologies such as sodium, Solid-Liquid Separation, drying and calcining through washing, prepare Al ₂O ₃-SiO ₂Powder.

ZL95103291 discloses a kind of preparation method of silica-alumina carriers, comprise a kind of aluminium compound is mixed with a kind of silicon compound to obtain a kind of solution, wherein aluminium compound is aluminum alcoholate or aluminum carboxylate, and silicon compound is alcoholization silicon or silicone compounds; Under acid condition He under 50-150 ℃, make the solution hydrolysis, obtain gelinite after the cooling, obtain paste after removing excessive volatile matter, carry out extrusion molding afterwards, and obtain described carrier 300-700 ℃ of roasting.

ZL03157163 discloses a kind of silica-alumina with structure of similar to thin diaspore and preparation method thereof, contains the silica of 5-60 weight % after its roasting, the aluminium oxide of 40-95 weight %.It is characterized in that the N value of described silica-alumina is 0.2-1, described N=P1/P2.P1 is that chemical shift is the peak area at 60 ± 0.1-0.2ppm place in the solid 27Al NMR spectrogram of described silica-alumina, and P2 is that chemical shift is the peak area at 5 ± 0.1-0.2ppm place in the solid 27Al NMR spectrogram of described silica-alumina.Described preparation method comprises the mixed liquor of a kind of boehmite of preparation and water, introduces a kind of solution of silicon-containing compound afterwards, and is aging and dry.

ZL200380105512 discloses a kind of cogelled Preparation of catalysts method of amorphous silica-alumina very uniformly, comprise: aqueous silicate solution is acutely mixed with the aqueous solution of acid aluminium salt, keep the pH of solution to be lower than 3.0 and guarantee that described aluminium salt and silicate solutions fully mix tempestuously, are formed on the acidifying Ludox in the aluminum salt solution simultaneously; Under the situation of the described solution of violent mixing, in described acidifying Ludox/aluminum salt solution, add alkaline precipitating agent gradually the pH of described solution is risen to greater than 3.0, produce cogelled slurries; Mix described cogelled slurries and make whole cogelled slurries keep continuing to add alkaline precipitating agent under the situation of even pH violent, make final pH in the scope of 5-9; Wash the common gelling of described precipitation; With the cogelled finished catalyst that is processed into described precipitation.

ZL200410048355 discloses a kind of silica-alumina, the silica that contains 5-60 weight % after its dehydration, the aluminium oxide of 40-95 weight %, the preparation method of this silica-alumina comprises a kind of salic water mixed liquid of preparation, introduce a kind of solution of silicon-containing compound, aging and drying afterwards, the solution of wherein said silicon-containing compound is a kind of mother liquor of synthesis of molecular sieve.

ZL96120986 discloses a kind of catalyst for hydrodesulfurizationfraction fraction oil, to contain SiO ₂The alumina globule of 5-15w% is a carrier, and catalyst contains MoO ₃12.0-18.0w%, CoO 3.0-6.0w%, pore volume 0.45-0.55ml/g, average pore size is characterized in that at 7.0-10.0nm: when catalyst granules is tightly packed, under particle diameter 1.5-2.5mm situation, the specific area 190-220m of per volume of catalyst ²/ ml.The Preparation of Catalyst main points are: in siliceous alumina globule preparation process, the drying of wet rubber ball is in containing ammonia atmosphere, carries out at a slow speed under low temperature (＜100 ℃).

ZL01815324 discloses a kind of hydrotreating catalyst that is used for heavy oil, contain at least a vib metal and/or at least a VIII family metal that is selected from cobalt, nickel, iron that is selected from molybdenum, tungsten, chromium on silica-alumina carriers, described silica-alumina carrier has ²⁹Si NMR spectrum, wherein-50ppm to the-observed maximum main peak of 100ppm be positioned at-80ppm is to-100ppm, the content of silica is 1-20% in the carrier, and mixes with alumina source with the organo-silicon compound form that is selected from alkyl silane, alkoxy silane and straight chain or modified silicon oil and sneak into carbon monoxide-olefin polymeric.

ZL02133122 discloses a kind of hydrotreating catalyst and preparation method thereof, this catalyst is loaded on a kind of siliceous alumina support by the specific process preparation by molybdenum, nickel, phosphorus and prepares, and the siliceous aluminium oxide of specific process preparation is by adding the preparation of nanometer silicon-containing compound such as nano silicon.Described catalyst has the metal enrichment surface and is uniformly dispersed and higher total acid content, particularly the middle strong acid amount of 150～250 ℃ weak acid amount and 250～400 ℃ distributes and accounts for the ratio height of total acid content, and acid strength distributes suitable, when being used for mink cell focus hydrotreatment process, have higher hydrodesulfurization and hydrodenitrogenationactivity activity.

It is the preparation method of the hydrogenation catalyst of containing phosphor of carrier with the silica-alumina that ZL200510064753 discloses a kind of, this method comprises in described silica-alumina carrier introduces phosphorus, molybdenum, nickel and tungsten, the preparation method of described silica-alumina carrier comprises the precursor of aluminium oxide and/or aluminium oxide is mixed with the precursor of silica and/or silica and roasting, obtain the silica-alumina carrier, this carrier contains the silica of 2-45% and the aluminium oxide of 55-98%.

ZL200510109496 discloses a kind of Highly Actived Petrolatum Hydrobon Catalyst And Preparation Method And Use.The carrier of this catalyst is siliceous aluminium oxide, and active component is WO ₃And NiO, adjuvant component is P ₂O ₅, by each components contents of weight percent meter of catalyst be respectively: WO ₃Be 25%～35%, NiO is 2.0%～7.0%, P ₂O ₅With P count 2.0%～5.5%, SiO ₂Be 1%～10%, all the other are aluminium oxide.

(" different silica sources is to NiW/Al for document ₂O ₃-SiO ₂The influence of catalyst hydrogenation desulfurization performance ", petroleum journal＜PETROLEUM PROCESSING 〉, 2009,25 the 3rd phases of volume, 307 pages) reported NiW/Al ₂O ₃-SiO ₂The preparation method, comprise Ludox or SiO ₂Powder and Al ₂O ₃The powder extruded moulding is made silica-alumina supports after high-temperature roasting; Or ethyl orthosilicate flooded Al ₂O ₃Carrier floods back 100 ℃ of oven dry, after the hydrolysis in air atmosphere with higher temperature roasting 3h, prepare silica-alumina supports.Adopt the saturated infusion process in hole afterwards, the silica-alumina supports dipping NiW solution with above-mentioned preparation obtains NiW/Al after drying and the activation ₂O ₃-SiO ₂Catalyst.

Wherein, adopt hydrated alumina such as boehmite directly mixes with silicon-containing compound, the method for roasting prepares silica-alumina, be used more and more because of it is simple to operate.

Boehmite of the prior art generally is prepared by following method: (1) alkaline precipitation, i.e. acidifying aluminium salt and alkali neutralization.Be settled out monohydrate alumina with alkali from the acidifying aluminum salt solution, obtain the boehmite product by processes such as aging, washing, dryings again, this method often is called as alkali precipitation (acid system), as in the ammoniacal liquor and the method for alchlor; (2) acid precipitation method is promptly in the aluminium salt of strong acid or strong acid and aluminate.Be settled out monohydrate alumina with acid from aluminate solution earlier, obtain the boehmite product by processes such as aging, washing, dryings again, often be called as acid precipitation (alkaline process), common method comprises the most at present: CO ₂In the gas and in the method for sodium metaaluminate, aluminum sulfate and the method for sodium metaaluminate; (3) aluminum alkoxide Hydrolyze method generates monohydrate alumina with aluminum alkoxide and water generation hydrolysis, obtains the boehmite product through aging, filtration, drying again.Preparation process at boehmite generally all is made up of processes such as crystal grain generation (neutralization precipitation or hydrolytic process), grain growth (ageing process), washing, dryings.Therefore, crystal grain generates, the process conditions of grain growth can exert an influence to the quantity and the speed of growth that crystal grain generates, the preparation technology of various boehmites has proposed process conditions separately, grain size, the degree of crystallinity of control product are to reach the purpose of physical propertys such as control product pore volume and specific area.For example:

ZL200410024185 discloses a kind of preparation method of boehmite, this method comprises that sodium aluminate solution is carried out carbonating to be decomposed, reacting slurry is separated, fractional crystallization is obtained product through washing, dry post processing, what described sodium aluminate solution carbonating was decomposed is controlled to be: add sodium aluminate solution in the water that feeds carbon dioxide, the pH value of controlling solution by the throughput of control carbon dioxide is 10-13, after interpolation finishes, increase the throughput of carbon dioxide rapidly, make the pH value of solution be reduced to 9.5-10.5 rapidly, obtain reacting slurry.

ZL200510068393 discloses a kind of preparation method of boehmite, it is that precipitating reagent is produced in the process of boehmite that this method comprises with acid or aluminate, adds 6-18 gram melamine (CA) for become glue behind the expanding agent dissolution filter with the acidifying aluminum salt solution of trioxygen-containing aluminium 20-40 grams per liter in the sodium aluminate solution of trioxygen-containing aluminium 60-180 grams per liter; Becoming the glue temperature is 50-90 ℃, and becoming glue pH value is 6.5-8.5, Separation of Solid and Liquid, and filtration washing obtains filter cake, and the water that oven dry is adhered to changeed brilliant 4-10 hour 320-350 ℃ of following roasting, pulverized promptly to get the boehmite finished product.

ZL02120772 discloses a kind of preparation method of gama-alumina, this method comprises sodium metaaluminate or sodium aluminate solution is contacted with carbonated gas, intermittence or continuous mode to become glue, the aging boehmite that obtains, isolate solid product, washing is also dry, the terminal point pH of described one-tenth glue or process pH are controlled in the scope of 6-9.5, become the time or the time of staying of glue reaction to be less than 40 minutes, become 10-100 ℃ of glue reaction temperature, become the glue reaction to finish the back and add alkaline matter rapidly, make the pH value of slurries rise to 9.5-11.5 or carry out Separation of Solid and Liquid rapidly and washing.

USP4019978 discloses a kind of production method of alumina, and this method is by pressing Al ₂O ₃Meter concentration is at least in 2% the aluminum sulfate solution introduces sodium aluminate solution, concentration by control sodium aluminate and aluminum sulfate solution, the control sodium aluminate joins speed and the mixing speed in the aluminum sulfate solution, to guarantee that big extremely portion hydrated alumina precipitates generation under acid condition, the control mixture temperature is 12-35 ℃ or 45-70 ℃, controls alkaline ageing time, to produce the low-density aluminium oxide that boehmite is formed.Hydrated alumina after filtration, washing, dry then.Low-density aluminium oxide useful as catalysts carrier, particularly hydrodesulfurization catalyst support.

Although prior art has the multiple different method for preparing boehmite, and the performance of the boehmite that obtains is more excellent in some aspects, yet, they and silicon-containing compound are being mixed with the silica-alumina carrier, again these carriers are used to prepare catalyst, when particularly preparing hydrogenation class catalyst, the performance of catalyst is as the saturated performance of aromatic hydrocarbons, hydrodesulfurization activity is still on the low side.

Summary of the invention

The technical problem to be solved in the present invention provide a kind of new, be the hydrotreating catalyst and the application thereof of carrier with the silica-alumina.

The present inventor finds under study for action, when adopting the silica-alumina preparing carriers hydrotreating catalyst that boehmite directly mixes with silicon-containing compound, the method for roasting prepares, the character of boehmite directly exerts an influence to catalyst performance.And the n value of the boehmite that prior art provides (being generally 0.85-1.05) on the low side is to cause this type of boehmite and silicon-containing compound composition being used to prepare hydrogenation catalyst, one of reason that catalyst performance is low.

The invention provides a kind of hydrotreating catalyst, this catalyst contains carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, described carrier contains silica-alumina, it is characterized in that, described silica-alumina is obtained through roasting by the composition of boehmite and silicon-containing compound, wherein, described boehmite is the boehmite P1 that comprises at least a 1.1≤n≤2.5; N=D (031)/D (120) wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.

The present invention also provides a kind of method for hydrotreating hydrocarbon oil, is included under the hydrotreatment reaction condition, with hydrocarbon oil crude material oil and catalyst haptoreaction, it is characterized in that described catalyst is aforesaid catalyst provided by the invention.

Compared with prior art, the carrier that the invention provides catalyst is obtained through roasting by the composition of boehmite and silicon-containing compound, wherein, described boehmite comprises the boehmite P1 of at least a 1.1≤n≤2.5, said composition obtains the silica-alumina carrier through roasting, when adopting this preparing carriers hydrogenation catalyst, catalyst performance be improved significantly.For example, hydrogenation active metals content at catalyst, under the identical situation of preparation condition, employing the invention provides the silica-alumina carrier, and (precursor is boehmite and the silicon-containing compound of a kind of n=1.8, in oxide, the content of aluminium oxide is 70 weight % in the described composition, the content of silica is 30 weight %) preparation hydrogenation catalyst, (precursor is boehmite and the silicon-containing compound of a kind of n=0.98 than reference silica-alumina carrier, in oxide, the content of aluminium oxide is 70 weight % in the described composition, and the content of silica is 30 weight %) the relative arene saturating activity of the hydrogenation catalyst of preparation improves 30%.

The specific embodiment

According to catalyst provided by the invention, in the composition of wherein said boehmite and silicon-containing compound, described P1 is preferably the boehmite of 1.2≤n≤2.2.Described n=D (031)/D (120), the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, the D value is obtained by following formula, D=K λ/(Bcos θ), K is the Scherrer constant, and λ is the diffraction wavelength of target section bar material, and B is the half-peak breadth of this diffraction maximum, 2 θ are the position of this diffraction maximum, for different diffraction maximums, the value that B and 2 θ all get peak correspondingly, for example, when calculating D (031), D (031)=K λ/(Bcos θ), wherein B is the half-peak breadth of 031 diffraction maximum, 2 θ are the position of 031 diffraction maximum; When calculating D (120), D (120)=K λ/(Bcos θ), wherein B is the half-peak breadth of 120 diffraction maximums, 2 θ are the position of 120 diffraction maximums.

Described silicon-containing compound, it can be organic silicon-containing compound, as in esters of silicon acis, silanol, silicon ether, silicone and the silicone oil one or more, also can be inorganic silicon-containing compound, for example be selected from a kind of in silica gel (hydrated SiO 2), Ludox, silicic acid, waterglass, amorphous aluminum silicide, the zeolite molecular sieve.Preferred silica gel, silicic acid and the Ludox that adopts in the inorganic silicon-containing compound.

According to catalyst provided by the invention, wherein, content to boehmite and silicon-containing compound in the composition of described boehmite and silicon-containing compound is not particularly limited, and promptly they can be usual content, in oxide, the content of preferred boehmite is 65-99 weight %, more preferably 75-97 weight % is more preferably 80-95% weight, and the content of silicon-containing compound is 1-35% weight %, more preferably 3-25% weight % is more preferably 5-20% weight.

The preparation method of the boehmite P1 of described 1.1≤n≤2.5 comprises: aluminum contained compound solution is contacted with acid or alkali carry out precipitation reaction, perhaps organic aluminum contained compound is contacted the reaction that is hydrolyzed with water, obtain hydrated alumina; The above-mentioned hydrated alumina that obtains is worn out, wherein, described aluminum contained compound solution and acid or alkali contact or described organic aluminum contained compound and water contact and hydrated alumina aging in any one process in the presence of the grain growth conditioning agent, carry out, described grain growth conditioning agent is for can regulate the material of the speed of growth of crystal grain on different crystal faces.

As long as although make hydrolysis or precipitation reaction and aging in one of arbitrary process in the presence of the grain growth conditioning agent, carry out realizing purpose of the present invention, but under the preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out in the presence of the grain growth conditioning agent, and the n that can make the gained boehmite like this is in preferred 1.2≤n≤2.2 scopes.

Wherein, there is no particular limitation to the consumption of grain growth conditioning agent, the consumption of grain growth conditioning agent is the 0.5-10 weight % that treats organic aluminum contained compound weight of hydrolysis in the selective hydrolysis reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; The consumption of grain growth conditioning agent is the inorganic 0.5-10 weight % that contains al reactant weight in the described precipitation reaction, 1-8.5 weight % more preferably, further preferred 5-8.5 weight %; In the described ageing process, the consumption of grain growth conditioning agent can be preferably 1-8.5 weight % for the 0.5-10 weight % of hydrated alumina weight, further preferred 5-8.5 weight %.Unless stated otherwise, among the present invention, the consumption of described grain growth conditioning agent is that benchmark calculates with the weight of aluminium oxide corresponding in organic aluminum contained compound, inorganic aluminum contained compound and the hydrated alumina respectively.Also be, in aluminium oxide, in the described precipitation reaction, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of inorganic aluminum contained compound weight, in the described hydrolysis, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of organic aluminum contained compound weight, and in the described ageing process, the consumption of described grain growth conditioning agent is the 0.5-10 weight % of hydrated alumina weight.

Among the present invention, described grain growth conditioning agent can be the various materials that can regulate the speed of growth of crystal grain on different crystal faces, particularly can regulate the material of crystal grain in the speed of growth of 120 crystal faces and 031 crystal face, be preferably alditol and carboxylate thereof, be specifically as follows in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, the ribose hydrochlorate one or more.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be in sylvite, sodium salt and the lithium salts one or more.

In boehmite preparation process of the present invention, adding mode to described grain growth conditioning agent is not particularly limited, the grain growth conditioning agent can be added separately, also can be in advance the grain growth conditioning agent be mixed with wherein one or more raw materials, and then the raw material that will contain the grain growth conditioning agent reacts.

Wherein, described inorganic aluminum contained compound solution can be various aluminum salt solutions and/or aluminate solution, and described aluminum salt solution can be various aluminum salt solutions, for example can be one or more the aqueous solution in aluminum sulfate, aluminium chloride, the aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use two kinds or more of mixing back.Described aluminate solution is an aluminate solution arbitrarily, as sodium aluminate solution and/or potassium aluminate.Because its acquisition is easy and price is low, preferred sodium aluminate solution.Aluminate solution also can be used alone or as a mixture.

Concentration to described aluminum salt solution and/or aluminate solution is not particularly limited, and preferably counts the 0.2-1.1 mol with aluminium oxide.

Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetate, citric acid, the oxalic acid one or more, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, the hydrochloric acid.Described carbonic acid can original position produces by feed carbon dioxide in aluminum salt solution and/or aluminate solution.Concentration to described acid solution is not particularly limited, preferred H ⁺Concentration be the 0.2-2 mol.

Described aqueous slkali can for hydroxide or in aqueous medium hydrolysis make the aqueous solution be the salt of alkalescence, preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, the potassium hydroxide; Preferred salt is selected from one or more in sodium metaaluminate, potassium metaaluminate, carbonic hydroammonium, ammonium carbonate, sodium acid carbonate, sodium carbonate, saleratus, the potash.Concentration to described aqueous slkali is not particularly limited, preferred 0H ^-Concentration be the 0.2-4 mol.When during as alkali, when calculating the consumption of described grain growth conditioning agent, also considering the amount of corresponding aluminium oxide in sodium metaaluminate and/or the potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.

Described organic aluminum contained compound can be various can with water generation hydrolysis, producing in the aluminum alkoxide of aqua oxidation aluminum precipitation one or more, for example can be in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and the isooctanol aluminium one or more.Described organic aluminum contained compound and water consumption ratio are not particularly limited, and the preferred water yield is greater than the required amount of stoichiometry.

In boehmite preparation process of the present invention, the described condition of precipitation reaction that makes is not particularly limited, preferred pH value is 3-11, more preferably 6-10; Temperature can be 30-90 ℃, is preferably 40-80 ℃.

Wherein, it is conventionally known to one of skill in the art making the method for aluminum precipitation by the control of consumption to alkali in the reactant or acid.

Condition to described hydrolysis is not particularly limited, as long as water contacts with aluminum alkoxide hydrolysis generation hydrated alumina takes place, and the condition that hydrolysis specifically takes place is conventionally known to one of skill in the art.

Wherein, can in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, add the compound of crystal grain growth regulating effect, also can add aqueous slkali or acid solution and suitably regulate the pH value, under suitable temperature, wear out then to 7-10.Separate then, washing, drying.

Described acid solution or aqueous slkali can be with above-described identical or different.

Described aging temperature is preferably 35-98 ℃, and ageing time is preferably 0.2-6 hour.

According to method provided by the invention, the described known technology that is separated into this area is as the method for filtration or centrifugation or evaporation.

In boehmite preparation process of the present invention, after aging, also comprise the washing and the dry step that often comprise in the preparation boehmite process, described washing and dry method are preparation boehmite conventional process.For example, can use oven dry, forced air drying or spray-dired method.Generally speaking, baking temperature can be 100-350 ℃, is preferably 120-300 ℃.

According to the preparation method of boehmite of the present invention, an embodiment preferred may further comprise the steps:

(1) will contain the aluminum contained compound solution of grain growth conditioning agent and aqueous slkali or acid solution and stream or batch (-type) and join and carry out precipitation reaction in the reaction vessel, obtain the hydrated alumina slurries; Perhaps in deionized water, add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide, obtain the hydrated alumina slurries;

(2) filter cake behind the hydrated alumina dope filtration that step (1) is obtained adds in the aluminium oxide slurries that water making beating obtains again again, adds the grain growth conditioning agent, after regulating pH and being 7-10, in 35-98 ℃ of aging 0.2-6 hour; Also the hydrated alumina slurries that above-mentioned steps (1) can be obtained without filter the grain growth conditioning agent exist or not in the presence of be under the 7-10 at pH, in 35-98 ℃ of aging 0.2-6 hour;

(3) product that filter, washing step (2) obtains;

(4) product that obtains of drying steps (3) obtains the boehmite of 1.1≤n provided by the invention≤2.5.

According to catalyst provided by the invention, wherein, the composition of described boehmite and silicon-containing compound can also comprise the boehmite P2 except that the boehmite of 1.1≤n≤2.5, described P2 is the boehmite of n＜1.1, preferred P2 is the boehmite of 0.8＜n＜1.1, and further preferred P2 is the boehmite of 0.85≤n≤1.05.When described composition contains P2, be benchmark in oxide and with the boehmite total amount, the content of described P2 is not more than 70 weight %, further preferably is not more than 50 weight %, more preferably is not more than 30 weight %.

Described composition can adopt any prior art that described boehmite is mixed with described silicon-containing compound and obtain.Wherein, described mixing can be the simple accumulation that described boehmite and described silicon-containing compound are placed a place, also can be to adopt any one prior art, for example, can in mixer, grinder, directly boehmite be mixed by the mode that stirs with silicon-containing compound, can boehmite, silicon-containing compound and water be mixed being enough under the condition of pulp, filter afterwards, dry or moist method mixes.When adopting any one prior art to mix, those skilled in the art optionally can to described mix the uniformity that should reach control, to this present invention to being not particularly limited.

The consumption of each component makes in the final composition in described mixed process, in oxide, the content of preferred boehmite is 65-99 weight %, 75-97 weight % more preferably, be more preferably 80-95% weight, the content of silicon-containing compound is 1-35% weight %, and more preferably 3-25% weight % is more preferably 5-20% weight.Said composition obtains silica-alumina provided by the invention through roasting.

According to catalyst provided by the invention, wherein said method of roasting and condition can be that this area prepares examples of such carriers customary way and condition.Preferred roasting condition comprises: temperature is carried out for 400～900 ℃, and further preferred 500～750 ℃, roasting time is 1-12 hour, more preferably 2-8 hour.

According to catalyst provided by the invention, wherein said silica-alumina carrier optionally can be made into is convenient to the article shaped of operating arbitrarily, as spherical, compressing tablet and bar shaped.Described moulding can be carried out according to a conventional method, all can as methods such as compressing tablet, spin, extrusions.

One preferred embodiment in, the article shaped preparation method of described silica-alumina comprises:

(1) the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1, silicon-containing compound and water are mixed being enough under the condition of pulp, filter afterwards, dry or moist, obtain described composition;

(2) with the extrusion molding on banded extruder of step (1) resulting composition;

(3) the dry and roasting with step (2) gained extrusion molding thing.

Wherein, be to guarantee carrying out smoothly of extruded moulding, in step (2), comprise the step of an amount of water of in described composition introducings, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the cellulose one or more) and mixing.Described drying is a conventional method, carries out drying as adopting baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter to carry out roasting, the condition of described roasting is preferably, at 400-900 ℃ roasting temperature 1-12 hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.

Another preferred embodiment in, the article shaped preparation method of described silica-alumina comprises:

(1) on kneading machine or grinder, the boehmite P1 of described 1.1≤n≤2.5, the boehmite P2 that contains or do not contain n＜1.1 are mixed with silicon-containing compound, obtain described composition;

(2) with the extrusion molding on banded extruder of step (1) resulting composition;

(3) the dry and roasting with step (2) gained extrusion molding thing.

Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (1) and introduce an amount of water, peptizing agent (as be selected from nitric acid, acetic acid and the citric acid one or more), extrusion aid (as being in sesbania powder, the cellulose one or more).Described drying is a conventional method, carries out drying as adopting baking oven, mesh-belt kiln, converter and fluid bed, when adopting heating means to carry out drying, preferred baking temperature is 50-200 ℃, 0.3-12 hour drying time, further preferred baking temperature is 60-150 ℃, and be 0.5-8 hour drying time.The method of described roasting and condition are conventional method and the condition that the catalyst carrier preparation is adopted, as adopt mesh-belt kiln, vertical heater, horizontal chamber furnace (oven) and converter to carry out roasting, the condition of described roasting is preferably, at 400-900 ℃ roasting temperature 1-12 hour, further preferably 500-750 ℃ roasting temperature 2-8 hour.

When extrusion molding, the kind of the consumption of described water and described extrusion aid, peptizing agent and consumption are conventionally known to one of skill in the art, do not repeat them here.

Described silica-alumina carrier has following physico-chemical property, and pore volume is 0.5-1.1 milliliter/gram, and specific surface is a 100-400 rice ²/ gram can several bore dias be the 5-20 nanometer, and the pore volume of bore dia 4-10 nanometer is greater than 70% of total pore volume.Further preferred, the pore volume of described silica-alumina carrier is 0.55-0.90 milliliter/gram, and specific surface is a 150-350 rice ²/ gram can several bore dias be the 6-15 nanometer, and the pore volume of bore dia 4-10 nanometer is greater than 75% of total pore volume.

According to catalyst provided by the invention, be benchmark in oxide and with described catalyst, described catalyst preferably contains the VIII family metal component of 1-10 weight %, the group vib metal component of 5-35 weight %; Further preferred catalyst contains the VIII family metal component of 1.5-5 weight %, the group vib metal component of 6-30 weight %.

Catalyst provided by the invention can adopt the usual method preparation in present technique field, and for example, described preparation method comprises: the preparation carrier, and to this carrier at least a VIII of being selected from family of introducing and at least a metal component that is selected from group vib.

The method of at least a group VIII of described introducing and at least a group vib metal component, can be to contact with described carrier after the group vib metallic compound is mixed with mixed solution with at least a being selected from, as method by dipping with containing at least a group VIII; Can be to contact with described carrier after being selected from the independent obtain solution of group vib metallic compound with at least a containing at least a group VIII, described contact procedure can realize by any method, for example infusion process.Described dipping method can adopt conventional method.According to the present invention, by adjusting and control, can prepare the described catalyst of specifying content to concentration, consumption or the carrier consumption of the solution of metallic components, this is the understanding easily of those skilled in the art institute.

According to the present invention, after described impregnation steps is finished, optionally can carry out steps such as drying, roasting or not roasting.The condition of described drying and roasting all is conventional, and for example, baking temperature is 100-300 ℃, is preferably 100-280 ℃, and be 1-12 hour drying time, is preferably 2-8 hour; Sintering temperature is 350-550 ℃, is preferably 400-500 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.

Described group VIII metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals one or more.

Said group vib metallic compound is selected from one or more in the soluble compound of these metals, for example, can be in molybdate, paramolybdate, tungstates, metatungstate, the ethyl metatungstate one or more.

Can also contain organic additive in the catalyst provided by the invention, be benchmark with described catalyst, and in carbon, the content of described organic additive is no more than 10 weight %, further preferably is no more than 6 weight %.Described organic additive is selected from one or more the organic compound that contains in oxygen or the organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in organic pure and mild organic acid; Preferred organic compounds containing nitrogen is selected from one or more in the organic amine.For example, oxygen-containing organic compound can be enumerated ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetate, maleic acid, oxalic acid, aminotriacetic acid, 1, in 2-CDTA, citric acid, tartaric acid, the malic acid one or more, organic compounds containing nitrogen can be enumerated ethylenediamine, EDTA and ammonium salt thereof.When catalyst of the present invention further contains organic compound, the introducing method of described organic compound can be an arbitrary method, such as enumerating described organic compound and other components (comprising metal component and adjuvant component etc.) is mixed with impregnated carrier behind the mixed solution, dry method then; And the method that organic compound is mixed with impregnated carrier behind the solution separately.In a kind of method in back, preferred at first introducing contains the solution of other components to flood described carrier, and drying, roasting or not roasting are afterwards again with this carrier of solution impregnation that contains organic compound and dry method.Described drying can adopt customary way to carry out, and there is no particular limitation, is preferably 100-300 ℃ such as baking temperature, is preferably 1-12 hour drying time, and further preferred baking temperature is 100-250 ℃, and be 2-8 hour drying time.The condition of described roasting also is conventional, and for example described sintering temperature is 350-550 ℃, is preferably 400-500 ℃, and roasting time is 1-10 hour, is preferably 2-8 hour.

According to the present invention, when preparation contains the described catalyst of organic compound, in carbon and with described catalyst is benchmark, preferably make in the final catalyst by the introducing amount of selecting described organic compound, the content of described organic additive is no more than 10 weight %, further preferably is no more than 6 weight %.

According to catalyst provided by the invention, can also contain the material that any material that does not influence the catalytic performance that the invention provides catalyst maybe can improve the catalytic performance of catalyst provided by the invention.As containing in the components such as phosphorus or fluorine one or both, be benchmark in element and with the catalyst, the content of above-mentioned auxiliary agent is no more than 10 weight %, is preferably 0.5-5 weight %.

During one or both components in also containing components such as being selected from phosphorus or fluorine in the described catalyst, the described introducing method that is selected from components such as phosphorus or silicon can be an arbitrary method, as can be with the compound of auxiliary agent as described in containing directly with as described in boehmite mix with the composition of silicon-containing compound, moulding and roasting; Can be the compound that to contain described auxiliary agent and contact with described carrier after the compound that contains the hydrogenation active metals component is mixed with mixed solution; Can also be to contact and roasting with described carrier behind the independent obtain solution of the compound that contains auxiliary agent.When auxiliary agent and hydrogenation active metals are introduced described carrier respectively, preferably at first auxiliary compound solution contacts with described carrier and roasting with containing, contact with the solution of the compound that contains the hydrogenation active metals component more afterwards, for example pass through the method for dipping, described sintering temperature is 250-600 ℃, be preferably 350-500 ℃, roasting time is 2-8 hour, is preferably 3-6 hour.

According to the conventional method in this area, described hydrotreating catalyst is before using, usually can be in the presence of hydrogen, under 140-370 ℃ temperature, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material, this presulfurization can be carried out outside device also can original position sulfuration in device, and the active metal component of its load is converted into the metal sulfide component.

In another embodiment, the invention still further relates to the application of described catalyst in hydrocarbon oil hydrogenation is handled.Described hydrotreatment is included under hydrogen existence and the hydrotreatment reaction condition, and hydrocarbon oil feed is contacted with aforementioned hydrogenation catalyst of the present invention.

In hydrotreating method provided by the invention, to described hydroconversion condition without any special qualification, can adopt common reaction condition, for example can enumerate reaction temperature 200-420 ℃, more preferably 220-400 ℃, pressure 2-18 MPa, 2-15 MPa more preferably, liquid hourly space velocity (LHSV) 0.3-10 hour ^-1, more preferably 0.3-5 hour ^-1, hydrogen to oil volume ratio 50-5000,50-4000 more preferably.

The device of described hydrotreatment reaction can be enough to make described feedstock oil to carry out under the hydrotreatment reaction condition with in the catalytic reaction dress of the described catalyst device any, for example, at described fixed bed reactors, carry out in moving-burden bed reactor or the fluidized bed reactor.

Adopt hydrotreating method provided by the invention can directly process all kinds of hydrocarbon oil crude materials, so that it is carried out hydro-upgrading or hydrocracking.Described hydrocarbon oil crude material can be various heavy mineral oils or artificial oil or their mixed fraction oil, such as being selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and the heavy deasphalted oil one or more.Be particularly suitable for the hydrofinishing of diesel oil or poor ignition quality fuel and the hydrotreatment of wax oil.

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

Agents useful for same in the example except that specifying, is chemically pure reagent.Each constituent content removes and specifies in the catalyst, all adopts x-ray fluorescence spectrometry.

The n value of all boehmites all adopts XRD method to measure in the example of the present invention.The XRD test is carried out on SIMENS D5005 type X-ray diffractometer, CuK α radiation, and 44 kilovolts, 40 milliamperes, sweep speed is 2 °/minute.According to the Scherrer formula: (D is a crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) be that grain size that the calculation of parameter at 23-33 ° of peak goes out (120) is D (120), is that the grain size that the calculation of parameter at 34-43 ° of peak goes out (031) is D (031) with 2 θ with 2 θ respectively, and by formula n=D (031)/D (120) calculates the n value.

The boehmite P2 of boehmite P1, n＜1.1 of employed 1.1≤n≤2.5 in the embodiment of the invention, preparation method and originate as follows:

P1-1 (comprising P1-1a and P1-1b), adopt following method preparation:

In one 2 liters retort and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum sulfate solution of 3.6 gram ribitol and the ammonia spirit that concentration is 8 weight % and carry out precipitation reaction, reaction temperature is 40 ℃, reaction time is 10 minutes, it is 7 that the flow of control ammonia spirit makes the pH of reaction system, after precipitation reaction finishes, adding proper ammonia in slurries, to make the pH value of slurries be 8.5, slurries filtered after under 55 ℃ aging 60 minutes, filter cake washs 2 times with the deionized water making beating, and drying does not obtain hydrated alumina P1-1a; Through 120 ℃ of dryings 24 hours, obtain hydrated alumina P1-1b.XRD characterizes and shows that P1-1a and P1-1b have structure of similar to thin diaspore.

Characterizing the n value that calculates P1-1a and P1-1b through XRD lists in the table 1.

P1-2, adopt following method preparation:

To contain 210 gram aluminium oxide/liter, the causticity coefficient is 1.62 high concentration NaAlO ₂Solution and deionized water are mixed with Al ₂O ₃Concentration is 5 liters of the solution of 40 grams per liters, adds the NaAlO that gluconic acid sodium salt 16.3 grams obtain containing gluconic acid sodium salt then ₂Solution is transferred in the one-tenth glue reactor of cumulative volume 8L then, and the reactor ratio of height to diameter is 8, bottom band CO ₂Gas distributor.The control solution temperature is 25 ± 5 ℃, feeds the CO of concentration 90 volume % from reactor bottom ₂Gas is carried out to the glue reaction, becomes the glue temperature to be controlled at 20-40 ℃, regulates CO ₂Gas flow is 15 ± 2 liters/minute, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, promptly stops ventilation, finishes into the glue reaction.With aging 4 hours of gained slurries heat temperature raising to 70 ℃, filter with vacuum filter then, to be filtered intact after, on filter cake, replenish and added 20 liters of deionized waters (70 ℃ of temperature) flush cake about 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, obtain hydrated alumina P1-2.XRD characterizes demonstration, and P1-2 has structure of similar to thin diaspore, characterizes the n value that calculates P1-2 through XRD and lists in the table 1.

P1-3, adopt following method preparation:

In one 2 liters retort and stream add 1000 ml concns be 48 gram aluminium oxide/liter aluminum trichloride solution and 300 milliliters contain 200 gram aluminium oxide/liter, the causticity coefficient is 1.58, D-sorbite content is 1.82 grams per liters sodium aluminate solution carries out precipitation reaction, reaction temperature is during 80 ℃, conditioned reaction logistics capacity make and the pH value is 4.0, reaction time 15 minutes; Adding concentration in the gained slurries is the weak aqua ammonia adjusting slurries pH to 10.0 of 5 weight %, and be warming up to 80 ℃, aging 3 hours, filter with vacuum filter then, behind to be filtered the finishing, on filter cake, replenished adding 20 liters of deionized waters (80 ℃ of temperature) flush cake about 30 minutes.The qualified filter cake of washing is joined 1.5 liters of deionized water for stirring become slurries, slurries carry out drying with being pumped into spray dryer, control spray dryer outlet temperature about 2 minutes of dry materials time, obtains hydrated alumina P1-3 100-110 ℃ of scope after the drying.Adopt XRD to characterize, P1-3 has structure of similar to thin diaspore.The n value that adopts XRD method to calculate P1-3 is listed in the table 1.

P2-1 (comprising P2-1a and P2-1b), adopt following method preparation:

Method according to P1-1 prepares boehmite, and different is, the aluminum sulfate solution that contains ribitol by concentration be 96 gram aluminium oxide/liter aluminum sulfate solution replace, also be not contain ribitol in the aluminum sulfate solution.Filtration product not drying obtains hydrated alumina P2-1a; Drying obtains hydrated alumina P2-1b.XRD characterizes demonstration, and P2-1a and P2-1b have structure of similar to thin diaspore, characterizes the n value and the degree of crystallinity that calculate P2-1a and P2-1b through XRD and lists in the table 1.

P2-2 is the commercial boehmite SB powder that German Condea company aluminium alcoholates Hydrolyze method is produced, and the n value that adopts the XRD characterizing method to calculate the P2-2 powder is listed in the table 1.

P2-3, adopt following method preparation:

Method according to P1-3 prepares boehmite, and different is, does not contain D-sorbite in the sodium aluminate solution, and drying obtains hydrated alumina P2-3.Method according to embodiment 1 adopts XRD to characterize, and P2-3 has structure of similar to thin diaspore, characterizes the n value that calculates P2-3 through XRD and lists in the table 1.

Be unfavorable for XRD test sample preparation owing to the undried sample is wet partially, P1-1a and P2-1a sample all carry out the XRD test again through 120 ℃ of dryings after 12 hours, obtain the n value.

Repeatedly prepare according to the method described above, to obtain enough for the boehmite raw material that uses in the example.

From the result of table 1 as can be seen, boehmite P1-1a, P1-1b, P1-2 and P1-3 have the feature of 1.1≤n≤2.5; The n of boehmite P2-1a, P2-1b, P2-2 and P2-3＜1.1.In addition, be 100% with the degree of crystallinity of the commercial SB powder of Condea company, the degree of crystallinity of boehmite that adopts method preparation provided by the invention is in the 60-80% scope.

Table 1

Embodiment 1～4 explanation is suitable for preparing composition, silica-alumina carrier of the boehmite of catalyst and silicon-containing compound and preparation method thereof.

Embodiment 1

(1) be suitable for the composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

At room temperature the synthetic boehmite P1-1a (butt 22%) in 1600 gram laboratories is added the making beating of 3000 ml waters, stir after 30 minutes, (Silica Gel 955, U.S. Davison Chemical company product contains SiO under agitation to add commercial silica gel ₂99.8% weight) 62 grams continue to stir after 150 minutes, filtered, and filter cake 120 ℃ of dryings 10 hours, is obtained composition Z H-1 of the present invention (butt 77%).Adopt x-ray fluorescence method to record the composition of ZH-1, in oxide and with butt, silica content is 15 weight %, and alumina content is 85% weight.

(2) be suitable for silica-alumina carrier of the present invention and preparation thereof:

420 gram ZH-1 are mixed with sesbania powder 4 grams, afterwards with this mixture and 13.5 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 530 ml waters mix, and on the twin-screw banded extruder, mix the butterfly bar pinch, be extruded into 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-1 through 120 ℃ of dryings.The silica content of SA-1, specific area, pore volume and pore size distribution data are listed in table 2

Embodiment 2

(1) be suitable for the composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

Earlier synthetic boehmite P1-1b (butt 70%) and the Ludox in 400 gram laboratories (contained SiO ₂30% weight, the production of Beijing flying dragon horse company) after 295 grams, sesbania powder 11 grams mix, again with 8.2 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west) and 310 milliliters of mixing of water, afterwards this mixture is continued to mix on the twin-screw banded extruder and pinch, obtain composition Z H-2 of the present invention.ZH-2 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-2, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 24 weight %, and alumina content is 76% weight.

(2) be suitable for silica-alumina carrier of the present invention and preparation thereof:

Continue whole aforementioned ZH-2 are extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-2 through 120 ℃ of dryings.The silica content of SA-2, specific area, pore volume and pore size distribution data are listed in table 2.

Embodiment 3

(1) be suitable for the composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

(Beijing chemical reagents corporation contains SiO for earlier that 450 gram laboratories are synthetic boehmite P1-2 (butt 69%) and ethyl orthosilicate ₂28% weight is analyzed pure) 46 grams, 12.5 gram sesbania powder mix, again with this mixture and 8.2 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west), 400 ml waters mix, and continue to mix on the twin-screw banded extruder afterwards to pinch all, obtain composition Z H-3 of the present invention.ZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-3, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 4 weight %, and alumina content is 96% weight.

(2) be suitable for silica-alumina carrier of the present invention and preparation thereof:

Continue whole aforementioned ZH-3 are extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-3 through 120 ℃ of dryings.The silica content of SA-3, specific area, pore volume and pore size distribution data are listed in table 2.

Embodiment 4

(1) be suitable for the composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

(Siral 40, contain SiO for earlier that 400 gram laboratories are synthetic boehmite P1-3 (butt 71%) and amorphous aluminum silicide ₂40% weight, Germany Condea company product) 304 grams, sesbania powder 19 grams mix, again with this mixture and 12 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 413 ml waters mix, afterwards mix on the twin-screw banded extruder pinch evenly after, obtain composition Z H-4 of the present invention.ZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-4, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 30%, and alumina content is 70%.

(2) be suitable for silica-alumina carrier of the present invention and preparation thereof:

Continue whole aforementioned ZH-4 are extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-4 through 120 ℃ of dryings.The silica content of SA-4, specific area, pore volume and pore size distribution data are listed in table 2.

Embodiment 5

(1) be suitable for the composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

Earlier that 300 gram laboratories are synthetic boehmite P1-3 (butt 71%), commercial boehmite (Shandong Aluminium Industrial Corp produces, butt 67% weight, n value 1.02) 212 grams, Ludox (contain SiO ₂30% weight, the production of Beijing flying dragon horse company) 131 grams, sesbania powder 13 grams mix, again with 11 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 210 ml waters mix, afterwards continue to mix on the twin-screw banded extruder pinch evenly after, obtain composition Z H-5 of the present invention.ZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-5, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 10% weight, and alumina content is 90% weight.

(2) be suitable for silica-alumina carrier of the present invention and preparation thereof:

Whole aforementioned ZH-5 are extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains silica-alumina SA-5 through 120 ℃ of dryings.The silica content of SA-5, specific area, pore volume and pore size distribution data are listed in table 2.The aluminium oxide that is provided by P1-3 accounts in the carrier all 60% of alumina contents.

Comparative Examples 1-5 explanation reference composition, silica-alumina and preparation method thereof.

Comparative Examples 1

(1) reference composition and preparation thereof

At room temperature the synthetic boehmite P2-1a (butt 21%) in 1600 gram laboratories is added the making beating of 3000 ml waters, stir after 30 minutes, (Silica Gel 955, U.S. Davison Chemical company product contains SiO under agitation to add commercial silica gel ₂99.8% weight) 60 grams continue to stir after 150 minutes, filtered, and filter cake 120 ℃ of dryings 10 hours, is obtained composition CZH-1 of the present invention (butt 78%).Adopt x-ray fluorescence method to record the composition of CZH-1, in oxide and with butt, silica content is 15 weight %, and alumina content is 85% weight.

(2) reference silica-alumina and preparation thereof

420 gram CZH-1 are mixed with sesbania powder 4.2 grams, afterwards with this mixture and 13.5 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 530 ml waters mix, on the twin-screw banded extruder, mix the butterfly bar of pinching, be extruded into 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-1 through 120 ℃ of dryings.The silica content of CSA-1, specific area, pore volume and pore size distribution data are listed in table 2.

Comparative Examples 2

(1) reference composition and preparation thereof:

Earlier the synthetic boehmite P2-1b (butt 68%) in 400 gram laboratories (is contained SiO with Ludox ₂30% weight, the production of Beijing flying dragon horse company) 287 grams, sesbania powder 11.3 grams mix, again with this mixture and 8.8 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, west, Shantou), 313 ml waters mix, on the twin-screw banded extruder, continue to mix afterwards to pinch, obtain reference silica-alumina CZH-2.CZH-2 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-2, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 24 weight %, and alumina content is 76% weight.

(2) reference silica-alumina and preparation thereof:

Whole aforementioned CZH-2 are continued to be extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-2 through 120 ℃ of dryings.The silica content of CSA-2, specific area, pore volume and pore size distribution data are listed in table 2.

Comparative Examples 3

(1) reference composition and preparation thereof:

Earlier (Beijing chemical reagents corporation contains SiO with the commercial boehmite P2-2 of 450 grams (the SB powder that German Condea company produces, butt 75%) and ethyl orthosilicate ₂28% weight is analyzed pure) 49.5 grams, 9 gram sesbania powder mix, and this mixture are mixed with 9 milliliters of nitric acid, 390 ml waters again, and continuation is mixed on the twin-screw banded extruder afterwards pinches, and obtains reference composition CZH-3.CZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-3, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 4 weight %, and alumina content is 96% weight.

(2) reference silica-alumina and preparation thereof:

Continue whole aforementioned CZH-3 are extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-3 through 120 ℃ of dryings.The silica content of CSA-3, specific area, pore volume and pore size distribution data are listed in table 2.

Comparative Examples 4

(1) reference composition and preparation thereof:

(Siral 40, contain SiO for earlier that 400 gram laboratories are synthetic boehmite P2-3 (butt 68%) and amorphous aluminum silicide ₂40% weight, German Condea company product) 291 grams, sesbania powder 18.7 grams mix, again with this mixture and 12 milliliters of nitric acid (concentration 65-68%, analyze pure, chemical plant, Gansu Province, Shantou west), 446 ml waters mix, and continue to mix on the twin-screw banded extruder afterwards to pinch, and obtain reference composition CZH-4.CZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-4, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 30 weight %, and alumina content is 70% weight.

(2) reference silica-alumina and preparation thereof:

Continue whole aforementioned CZH-4 are extruded into the butterfly bar of 1.3 millimeters of ф on the twin-screw banded extruder, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-4 through 120 ℃ of dryings.The silica content of CSA-4, specific area, pore volume and pore size distribution data are listed in table 2.

Comparative Examples 5

(1) reference composition and preparation thereof:

Earlier that 300 gram laboratories are synthetic boehmite P2-3 (butt 68%), commercial boehmite (Shandong Aluminium Industrial Corp produces, butt 67% weight, n value 1.02) 202 grams, Ludox (contain SiO ₂30% weight, Beijing flying dragon horse company produces) 126 grams, sesbania powder 13 grams mix, and this mixture are mixed with 11 milliliters of nitric acid, 265 ml waters again, and continuation is mixed on the twin-screw banded extruder afterwards pinches, and obtains reference composition CZH-5.CZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-5, is benchmark in oxide and with the total amount of silica and aluminium oxide in the described composition, and silica content is 10 weight %, and alumina content is 90% weight.

(2) reference silica-alumina and preparation thereof:

Continue on the twin-screw banded extruder to say that whole aforementioned CZH-5 are extruded into the butterfly bar of 1.3 millimeters of ф, wet bar after 4 hours, in 600 ℃ of roastings 3 hours, obtains reference silica-alumina CSA-5 through 120 ℃ of dryings.The silica content of CSA-5, specific area, pore volume and pore size distribution data are listed in table 2.The aluminium oxide that is provided by P2-3 accounts in the carrier all 60% of alumina contents.

PV in the table 2 (4-10)/PV is the pore volume of a 4-10 nanometer shared ratio in total pore volume for bore dia always.

As can be seen from Table 2, the invention provides that silica-alumina PV (4-10)/the PV total value is all greater than 75%, and the PV of Comparative Examples silica-alumina (4-10)/PV is all below 75%.Therefore, silica-alumina of the present invention has more concentrated pore size distribution.

Table 2

Embodiment 6-10 explanation the invention provides catalyst and preparation thereof.

Reference catalyst and preparation thereof are adopted in Comparative Examples 6-10 explanation.

Preparation catalyst employed raw material sources are as follows: ammonium molybdate, Anqing moon metallurgy of copper chemical industry Co., Ltd product, technical grade; Ammonium metatungstate, Zhuzhou diamond tungsten product Co., Ltd product, technical grade; Nickel nitrate, Beijing Yili Fine Chemicals Co., Ltd.'s product is analyzed pure; Basic nickel carbonate, Yixing Xu Chi chemical industry Co., Ltd product, chemical pure; Cobalt nitrate, Beijing Yili Fine Chemicals Co., Ltd. analyzes pure; Phosphoric acid, Beijing Chemical Plant's product, analyze pure, 85% concentration; Ammoniacal liquor, 25% concentration, Beijing Chemical Plant's product is analyzed pure; Citric Acid Mono, Beijing Chemical Plant's product is analyzed pure; Ammonium fluoride, chemical plant, Jinan product is analyzed pure.

Embodiment 6

Get silica-alumina SA-1 200 gram, flooded 2 hours with 190 milliliters of aqueous solution that contain ammonium molybdate 36 grams, nickel nitrate 29 grams, phosphatase 11 1.9 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtained catalyst C-1.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst C1, and measurement result is as shown in table 3.

Comparative Examples 6

Get reference silica-alumina CSA-1 200 grams, contain ammonium molybdate (Anqing moon metallurgy of copper chemical industry Co., Ltd product with 205 milliliters, technical grade) 36 grams, nickel nitrate (Beijing Yili Fine Chemicals Co., Ltd.'s product, analyze pure) 29 the gram, phosphoric acid (Beijing Chemical Plant's product, analyze pure, concentration 85%) aqueous solution dipping 2 hours of 11.9 grams, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtain catalyst DC-1.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst DC1, and measurement result is as shown in table 3.

Embodiment 7

Get silica-alumina SA-2200 gram, flooded 2 hours with 160 milliliters of dilute ammonia solutions (10% concentration) that contain ammonium molybdate 28 grams, cobalt nitrate 18 grams, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst C-2.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst C-2, and measurement result is as shown in table 3.

Comparative Examples 7

Get reference silica-alumina CSA-2 200 gram, flooded 2 hours with 164 milliliters of dilute ammonia solutions (10% concentration) that contain ammonium molybdate 28 grams, cobalt nitrate 18 grams, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst DC-2.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst DC-2, and measurement result is as shown in table 3.

Embodiment 8

Get silica-alumina SA-3 200 gram, with 170 milliliters of dippings of the aqueous solution that contain molybdenum oxide 57 grams, basic nickel carbonate 28 grams, phosphoric acid 23 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyst C-3.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst C-3, and measurement result is as shown in table 3.

Comparative Examples 8

Get reference silica-alumina CSA-3 200 gram, with 182 milliliters of dippings of the aqueous solution that contain molybdenum oxide 57 grams, basic nickel carbonate 28 grams, phosphoric acid 23 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained catalyst DC-3.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst DC-3, and measurement result is as shown in table 3.

Embodiment 9

Get silica-alumina SA-4 200 gram, with the aqueous solution dipping of 172 milliliters of fluorinated ammoniums, 19 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain catalyst fluorine bar F-1.

Get fluorine bar F-1 200 gram, with 158 milliliters of dippings of the aqueous solution fluorine bar that contains ammonium metatungstate 109 grams, nickel nitrate 45 grams 2 hours, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst C-4.With the catalyst weight is benchmark, adopts the chemical composition among the XRF light measurement catalyst C-4, and measurement result is as shown in table 3.

Comparative Examples 9

Get reference silica-alumina CSA-4 200 gram, with the aqueous solution dipping of 156 milliliters of fluorinated ammoniums, 19 grams 2 hours, dried 2 hours in 120 ℃, 450 ℃ of roastings 3 hours obtain catalyst fluorine bar CF-1.

Get fluorine bar CF-1 200 gram, with 140 milliliters of dippings of the aqueous solution fluorine bar that contains ammonium metatungstate 109 grams, nickel nitrate 45 grams 2 hours, in 120 ℃ of dryings 4 hours, 430 ℃ of roastings 4 hours obtained catalyst DC-4.With the catalyst weight is benchmark, adopts the chemical composition among the XRF light method mensuration catalyst DC-4, and measurement result is as shown in table 3.

Embodiment 10

Get silica-alumina SA-5 200 gram, with 148 milliliters of impregnated carriers of the aqueous solution that contain ammonium molybdate 20 grams, phosphatase 11 6 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained containing molybdenum carrier 225 grams.

Contained the molybdenum carrier 2 hours with the 110 milliliters of dippings of the aqueous solution that contain ammonium metatungstate 45 gram, basic nickel carbonate 14 grams, Citric Acid Mono 32 grams, in 120 ℃ of dryings 4 hours, 200 ℃ of dryings 4 hours obtained catalyst C-5.With the catalyst weight is benchmark, adopts the chemical composition among the XRF light method mensuration catalyst C-5, and measurement result is as shown in table 3.

Comparative Examples 10

Get reference silica-alumina CSA-5 200 gram, with 161 milliliters of impregnated carriers of the aqueous solution that contain ammonium molybdate 20 grams, phosphatase 11 6 grams 2 hours, in 120 ℃ of dryings 4 hours, 450 ℃ of roastings 4 hours obtained containing molybdenum carrier 226 grams.

Contained the molybdenum carrier 2 hours with the 120 milliliters of dippings of the aqueous solution that contain ammonium metatungstate 45 gram, basic nickel carbonate 14 grams, Citric Acid Mono 32 grams, in 120 ℃ of dryings 4 hours, 200 ℃ of dryings 4 hours obtained catalyst DC-5.With the catalyst weight is benchmark, adopts the chemical composition among the x-ray fluorescence method mensuration catalyst DC-5, and measurement result is as shown in table 3.

Table 3

Embodiment 11-15 illustrates method provided by the invention and effect thereof.

Reference method and effect thereof are adopted in Comparative Examples 11-15 explanation.

Embodiment 11

4 of present embodiment explanation catalyst C-1 of the present invention, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) hydrodesulfurization reaction performance.

Be reflected on the little inverse spectral apparatus of continuous-flow and carry out, feedstock oil is for containing 4, the n-decane solution of 6-DMDBT 0.45 weight %, and the catalyst loading amount is 150 milligrams.

Before formal charging, be that sulfurized oil carries out presulfurization to catalyst with the mixed solution that contains 5 weight % carbon disulfide and cyclohexane earlier, conditions of vulcanization is: pressure 4.1 MPas, 360 ℃ of temperature, 4 hours time, sulfurized oil feed rate 0.4 ml/min, H ₂Flow velocity 400 ml/min; Cut feedstock oil afterwards and react, reaction condition is: pressure 4.1 MPas, and feedstock oil input 0.2 ml/min, volume of hydrogen oil ratio are 2000, temperature is 280 ℃, reacts the online gas chromatographic analysis of sampling after 3 hours.

Comparative Examples 11

4 of this Comparative Examples explanation reference catalyst DC-1,6-DMDBT hydrodesulfurization reaction performance, evaluation method is with example 7.

4, the 6-DMDBT hydrodesulfurization activity is calculated as follows;

$A=\ln \frac{100}{100-x}$

X is 4 in the formula, the 6-DMDBT desulfurization degree, and the activity of getting catalyst DC-1 is 100,4 of catalyst C-1 then of the present invention, 6-DMDBT is relative, and hydrodesulfurization activity can be represented by the formula: relative activity=A _C-1/ A _DC-1* 100%.A in the formula _C-1Be the activity of catalyst C-1 of the present invention, A _DC-1Activity for Comparative Examples catalyst DC-1.

4 of catalyst C-1 and DC-1, the 6-DMDBT hydrodesulfurization activity is listed in the table 4.

Table 4

	Catalyst	Relative hydrodesulfurization activity, %
			Embodiment 11	C-1	114
Comparative Examples 11	DC-1	100

Embodiment 12

The decompressed wax oil hydrotreatment performance of present embodiment explanation catalyst C-2 of the present invention.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-2 on 250 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 5, and reaction result sees Table 6.

The assay method of sulphur is SH/T 0253-92, and the assay method of nitrogen is SH/T 0657-1998.The hydrodesulfurization activity of catalyst calculates by 1.5 order reactions, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and related computing formula is as follows, and LHSV is a liquid hourly space velocity (LHSV) in the formula.

Comparative Examples 12

The decompressed wax oil hydrotreatment performance of this Comparative Examples explanation reference catalyst DC-2.

Method according to embodiment 12 is estimated comparative catalyst DC-2, and reaction result sees Table 6, is 100 with the DC-2 activity of such catalysts.

Table 5

Feedstock oil character	Decompressed wax oil
		Density (20 ℃), g/cm 3	0.9113
S，ppm	20000
		N，ppm	1100
Index of refraction (70 ℃)	1.4875
		Boiling range (D1160), ℃
Initial boiling point	258

50% point	452
		95% point	515
Reaction condition
		The hydrogen dividing potential drop, MPa	8.0
Catalyst volume, ml	100
		Temperature, ℃	375
Volume space velocity, h -1	1.4
		Hydrogen-oil ratio, v/v	800

Table 6

Embodiment 13

The straight-run diesel oil hydrofinishing performance of present embodiment explanation catalyst C-3 of the present invention.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-3 on 30 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 7, and reaction result sees Table 8.The hydrodesulfurization activity of catalyst calculates by 1.65 order reactions, and related computing formula is as follows, and hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is seen embodiment 12.

Table 7

Feedstock oil character	Straight-run diesel oil
		Density (20 ℃), g/cm 3	0.8456
S，ppm	8000
		N，ppm	144

Index of refraction (20 ℃)	1.4723
		Reaction condition
The hydrogen dividing potential drop, MPa	3.2
		Catalyst volume, ml	30
Temperature, ℃	350
		Volume space velocity, h -1	2.0
Hydrogen-oil ratio, v/v	300

Comparative Examples 13

The straight-run diesel oil hydrofinishing performance of this Comparative Examples explanation reference catalyst DC-3.

Method according to embodiment 13 is estimated reference catalyst DC-3, and reaction result is listed in table 8, is 100 with the DC-3 activity of such catalysts.

Table 8

Embodiment 14

The saturated performance of catalytic diesel oil aromatic hydrogenation of present embodiment explanation catalyst C-4 of the present invention.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-4 on 30 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 9, and reaction result sees Table 10.The arene saturating activity of catalyst calculates by first order reaction, and related computing formula is as follows.Arene content adopts the application of gas chromatorgraphy/mass method to measure.

Comparative Examples 14

The saturated performance of catalytic diesel oil aromatic hydrogenation of this Comparative Examples explanation reference catalyst DC-4.

Estimate the catalytic diesel oil arene saturating activity of reference catalyst DC-4 according to the method for embodiment 14, reaction result is listed in table 10, is 100 with the toluene hydrogenation activity of DC-4.

Table 9

Feedstock oil character	Catalytic diesel oil
		Density (20 ℃), g/cm 3	0.9026
S，ppm	4500
		N，ppm	833
Total aromatic hydrocarbons, %	64.5
		Reaction condition
The hydrogen dividing potential drop, MPa	6.0
		Catalyst volume, ml	30
Temperature, ℃	350
		Volume space velocity, h -1	1.5
Hydrogen-oil ratio, v/v	500

Table 10

	Catalyst	Relative arene saturating activity, %
			Embodiment 14	C-4	130
Comparative Examples 14	DC-4	100

Embodiment 15

This illustrates the hydrotreatment performance of the liquefied coal coil simulated oil of catalyst C-5 of the present invention to embodiment.

Catalyst breakage is become the 2-4 mm granules, evaluate catalysts C-5 on 250 milliliters of hydrogenation plants, raw materials used oil nature, reaction condition see Table 11, and reaction result sees Table 12.Hydrodenitrogenationactivity activity is calculated by 1 order reaction, and computing formula is seen embodiment 12.

Comparative Examples 15

The hydrotreatment performance of the liquefied coal coil simulated oil of this Comparative Examples explanation reference catalyst DC-5.

Estimate reference catalyst DC-5 according to the method for embodiment 15, the result is provided by table 12, is 100 with the hydrodenitrogenationactivity activity of DC-5.

Table 11

Feedstock oil character	The liquefied coal coil simulated oil
		Density (20 ℃), g/cm 3	0.8814
S，ppm	2500
		N，ppm	5100
O，％	1.95
		Index of refraction (20 ℃)	1.4808
Reaction condition
		The hydrogen dividing potential drop, MPa	10
Catalyst volume, ml	30
		Temperature, ℃	380
Volume space velocity, h -1	2.5
		Hydrogen-oil ratio, v/v	500

Table 12

	Catalyst	Relative denitrification activity, %
			Embodiment 15	C-5	117
Comparative Examples 15	DC-5	100

By the result in table 4～table 12 as can be known, the hydrotreating catalyst that provides than prior art of hydrotreating catalyst provided by the invention has better hydrocarbons hydrogenation handling property.

Claims (18)

1. hydrotreating catalyst, contain carrier and at least a VIII of being selected from family and at least a metal component that is selected from group vib, described carrier contains silica-alumina, it is characterized in that, described silica-alumina is obtained through roasting by the composition of boehmite and silicon-containing compound, wherein, described boehmite is the boehmite P1 that comprises at least a 1.1≤n≤2.5; N=D (031)/D (120) wherein, the crystallite dimension of the crystal face of 031 peak representative in the XRD spectra of described D (031) expression boehmite crystal grain, the crystallite dimension of the crystal face of 120 peak representatives in the XRD spectra of D (120) expression boehmite crystal grain, described 031 peak is meant that 2 θ in the XRD spectra are 34-43 ° peak, described 120 peaks are meant that 2 θ in the XRD spectra are 23-33 ° peak, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target section bar material, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.

2. catalyst according to claim 1 is characterized in that, described P1 is the boehmite of 1.2≤n≤2.2.

3. catalyst according to claim 1 is characterized in that, in oxide, the content of boehmite is 65-99 weight % in the composition of described boehmite and silicon-containing compound, and the content of silicon-containing compound is 1-35% weight %.

4. catalyst according to claim 3 is characterized in that, in oxide, the content of boehmite is 75-97 weight % in the composition of described boehmite and silicon-containing compound, and the content of silicon-containing compound is 3-25% weight %.

5. catalyst according to claim 4 is characterized in that, in oxide, the content of boehmite is 80-95% weight % in the composition of described boehmite and silicon-containing compound, and the content of silicon-containing compound is 5-20% weight %.

6. according to claim 1,3,4 or 5 any described catalyst, it is characterized in that described silicon-containing compound is selected from one or more in organic silicon-containing compound.

7. catalyst according to claim 6, described silicon-containing compound are selected from one or more in esters of silicon acis, silanol, silicon ether, silicone, the silicone oil.

8. according to claim 1,3,4 or 5 any described catalyst, it is characterized in that described silicon-containing compound is selected from one or more in the inorganic silicon-containing compound.

9. catalyst according to claim 8 is characterized in that, described inorganic silicon-containing compound is selected from one or more in silica gel (hydrated SiO 2), Ludox, silicic acid, the waterglass.

10. catalyst according to claim 1, it is characterized in that, the boehmite P2 that contains 0.8＜n＜1.1 in the composition of described boehmite and silicon-containing compound is a benchmark in oxide and with the boehmite total amount, and the content of described P2 is not more than 70 weight %.

11. catalyst according to claim 10 is characterized in that, described P2 is the boehmite of 0.85≤n≤1.05, is benchmark in oxide and with the boehmite total amount, and the content of described P2 is not more than 50 weight %.

12. catalyst according to claim 11 is characterized in that, is benchmark in oxide and with the boehmite total amount, the content of described P2 is not more than 30 weight %.

13. catalyst according to claim 1 is characterized in that, is benchmark in oxide and with described catalyst, described catalyst contains the VIII family metal component of 1-10 weight %, the group vib metal component of 5-35 weight %.

14. catalyst according to claim 13 is characterized in that, is benchmark in oxide and with described catalyst, described catalyst contains the VIII family metal component of 1.5-5 weight %, the group vib metal component of 6-30 weight %.

15., it is characterized in that described catalyst also contains at least a auxiliary agent that is selected from phosphorus or the fluorine according to claim 1 or 13 described catalyst, be benchmark in element and with the catalyst, the content of described auxiliary agent is no more than 10 weight %.

16., it is characterized in that described catalyst also contains organic additive according to claim 1 or 13 described catalyst, be benchmark and in described catalyst with carbon, the content of described organic additive is no more than 10 weight %.

17. catalyst according to claim 16 is characterized in that, is benchmark and with carbon in described catalyst, the content of described organic additive is no more than 6 weight %.

18. a method for hydrotreating hydrocarbon oil is included under the hydrotreatment reaction condition, with hydrocarbon ils and catalyst haptoreaction, it is characterized in that, described catalyst is any described catalyst of claim 1-17.