CN102161004B - 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 petroleum refining industry, and its effect is mainly to remove the impurity such as sulphur in 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 hydrofinishing; Perhaps can improve the character of hydrocarbon feed, for example the FCC raw material be carried out pretreatment, the improved hydrocarbon feed of character is re-used as the charging of FCC process, to improve the efficient of FCC process.The hydrogenation catalyst that uses in the hydrotreatment process 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.Carrier has the effect of holding with dispersed active metal, and its pore structure and surface nature directly affect metal in the power of dispersion, distribution and the metal of carrier surface-carrier interaction, therefore the activity of hydrogenation catalyst are had material impact.Preparing good catalyst carrier for hydrgenating, is the effective way that improves hydrogenation catalyst performance.Silica-alumina is because 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 prior art, having is much the report of the hydrogenation catalyst of carrier about silica-alumina carrier and preparation method thereof with adopting silica-alumina.For example:

Document (" aluminium oxide-silicon oxide is 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, comprise that nano level active Al (OH) x that adopts the aluminium powder hydrolysis and prepare is aluminum feedstock, take waterglass as the silicon raw material, and with Al ₂O ₃/ SiO ₂Be basic recipe at=2: 1, after introducing appropriate dispersant, fully mixes.Control by the pH value, to coat depositing technology, at surface, Al source parcel one deck Si raw material, thereby form the Al-Si complex at a certain temperature, go the work techniques 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 to obtain a kind of solution with a kind of silicon compound, wherein aluminium compound is aluminum alcoholate or aluminum carboxylate, and silicon compound is pure SiClx or silicone compounds; Make solution hydrolysis under acid condition and under 50-150 ℃, obtain gelinite after cooling, obtain paste after removing excessive volatile matter, carry out afterwards extrusion molding, 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 % by weight after its roasting, the aluminium oxide of 40-95 % by weight.It is characterized in that, the N value of described silica-alumina is 0.2-1, described N=P1/P2.P1 is that in the solid 27Al NMR spectrogram of described silica-alumina, chemical shift is the peak area at 60 ± 0.1-0.2ppm place, and P2 is that in the solid 27Al NMR spectrogram of described silica-alumina, chemical shift is the peak area at 5 ± 0.1-0.2ppm place.Described preparation method comprises the mixed liquor of a kind of boehmite of preparation and water, introduces afterwards a kind of solution of silicon-containing compound, and is aging and dry.

ZL200380105512 discloses a kind of preparation method of the cogelled catalyst of amorphous silica-alumina very uniformly, comprise: aqueous silicate solution is acutely mixed with the aqueous solution of acid aluminium salt, the pH that keeps simultaneously solution is lower than 3.0 and guarantee that described aluminium salt and silicate solutions fully mix tempestuously, are formed on the acidifying Ludox in aluminum salt solution; In the situation that the described solution of violent mixing adds alkaline precipitating agent that the pH of described solution is risen to greater than 3.0 gradually, produce cogelled slurries in described acidifying Ludox/aluminum salt solution; In the situation that the described cogelled slurries of violent mixing make whole cogelled slurries keep even pH to continue to add alkaline precipitating agent, 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 the 5-60 % by weight after its dehydration, the aluminium oxide of 40-95 % by weight, the preparation method of this silica-alumina comprises a kind of salic water mixed liquid of preparation, introduce afterwards a kind of solution, aging and dry of silicon-containing compound, 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 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, in particle diameter 1.5-2.5mm situation, the specific area 190-220m of per volume of catalyst ²/ ml.Catalyst prepares main points: in silicon-containing alumina bead 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 for heavy oil, contain at least a vib metal that is selected from molybdenum, tungsten, chromium and/or at least a VIII family metal that is selected from cobalt, nickel, iron on silica-alumina carriers, described silica-alumina carrier has ²⁹Si NMR spectrum, wherein-50ppm to-maximum main peak that 100ppm observes be positioned at-80ppm is to-100ppm, in carrier, the content of silica is 1-20%, and mixes with alumina source and sneak into carbon monoxide-olefin polymeric with the organo-silicon compound form that is selected from alkyl silane, alkoxy silane and straight chain or modified silicon oil.

ZL02133122 discloses a kind of hydrotreating catalyst and preparation method thereof, this catalyst is loaded on a kind of silicon-containing alumina carrier for preparing by specific process by molybdenum, nickel, phosphorus and prepares, and the silicon-containing alumina 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 distribute ratio that accounts for total acid content of the middle strong acid amount of the weak acid amount of 150～250 ℃ and 250～400 ℃ is high, and it is suitable that acid strength distributes, when being used for mink cell focus hydrotreatment process, have higher hydrodesulfurization and hydrodenitrogenationactivity activity.

ZL200510064753 discloses a kind of preparation method of the hydrogenation catalyst of containing phosphor take silica-alumina as carrier, the 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 silicon-containing alumina, and active component is WO ₃And NiO, adjuvant component is P ₂O ₅, by the content of each component 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 impact of catalyst hydrogenation desulfurization performance ", petroleum journal＜PETROLEUM PROCESSING 〉,, 25 the 3rd phases of volume, 307 pages in 2009) and 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 is flooded Al ₂O ₃Carrier floods rear 100 ℃ of oven dry, the hydrolysis after in air atmosphere with higher temperature roasting 3h, prepare silica-alumina supports.Adopt afterwards the saturated infusion process in hole, the silica-alumina supports dipping NiW solution with above-mentioned preparation obtains NiW/Al after drying and 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 it is simple to operate.

Boehmite of the prior art generally is prepared by the 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, then obtain the boehmite product by processes such as aging, washing, dryings, this method often is called as alkali precipitation (acid system), as the method for ammonia neutralization alchlor; (2) acid precipitation method is namely in the aluminium salt of strong acid or strong acid and aluminate.First be settled out monohydrate alumina with acid from aluminate solution, then obtain the boehmite product by processes such as aging, washing, dryings, often be called as acid precipitation (alkaline process), common method comprises the most at present: CO ₂In 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 the reaction of steeping in water for reconstitution unboiled water solution, then obtains the boehmite product through aging, filtration, drying.Preparation process at boehmite generally all is comprised 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 quantity and the speed of growth that crystal grain generates, the preparation technology of various boehmites has proposed process conditions separately, control grain size, the degree of crystallinity of product, to reach the purpose of physical propertys such as controlling product pore volume and specific area.For example:

ZL200410024185 discloses a kind of preparation method of boehmite, the 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 passes into carbon dioxide, the pH value of controlling solution by the throughput of controlling carbon dioxide is 10-13, add complete after, increase rapidly the throughput of carbon dioxide, make the pH value of solution be reduced to rapidly 9.5-10.5, obtain reacting slurry.

ZL200510068393 discloses a kind of preparation method of boehmite, the method comprises in the process of producing boehmite take acid or aluminate as precipitating reagent, adds 6-18 gram melamine (CA) for after the expanding agent dissolution filter and contain the acidifying aluminum salt solution plastic of alchlor 20-40 grams per liter in the sodium aluminate solution that contains alchlor 60-180 grams per liter; The plastic temperature is 50-90 ℃, and plastic 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 turns brilliant 4-10 hour 320-350 ℃ of lower roasting, pulverizes namely to get the boehmite finished product.

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

USP4019978 discloses a kind of method of producing aluminium oxide, and the method is by pressing Al ₂O ₃Meter concentration is at least in 2% aluminum sulfate solution introduces sodium aluminate solution, by controlling the concentration of sodium aluminate and aluminum sulfate solution, the control sodium aluminate joins speed and the mixing speed in aluminum sulfate solution, to guarantee that absolutely large section hydrated alumina precipitates generation under acid condition, control mixture temperature and be 12-35 ℃ or 45-70 ℃, control alkaline ageing time, the low-density aluminium oxide that forms to produce boehmite.Hydrated alumina after filtration, washing, then dry.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 with these carriers for the preparation of catalyst, when particularly preparing hydrogenation class catalyst, the performance of catalyst, as still on the low side in aromatic saturation performance, hydrodesulfurization activity.

Summary of the invention

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

The present inventor finds under study for action, when adopting boehmite directly mixes with silicon-containing compound, the method for roasting prepares silica-alumina carrier to prepare hydrotreating catalyst, 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, be cause this type of boehmite and the silicon-containing compound composition for the preparation of 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 refers to that 2 θ in XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of diffraction maximum, 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 carrier to prepare hydrogenation catalyst, catalyst performance be improved significantly.for example, hydrogenation active metals content at catalyst, in 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, in described composition, the content of aluminium oxide is 70 % by weight, the content of silica is 30 % by 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, in described composition, the content of aluminium oxide is 70 % by weight, the content of silica is 30 % by 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 refers to that 2 θ in XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, the D value is obtained by following formula, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, 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 one or more in esters of silicon acis, silanol, silicon ether, silicone and silicone oil, can be also 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, zeolite molecular sieve.Preferred silica gel, silicic acid and the Ludox that adopts in 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 namely they can be usual content, in oxide, the content of preferred boehmite is the 65-99 % by weight, more preferably the 75-97 % by weight, be more preferably 80-95% weight, and the content of silicon-containing compound is the 1-35% % by weight, more preferably the 3-25% % by weight, be 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; Carry out hydrated alumina obtained above aging, 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 carry out under the grain growth conditioning agent exists, 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 carry out realizing purpose of the present invention under the grain growth conditioning agent exists, but under preferable case, described hydrolysis and ageing process or described precipitation reaction and ageing process are all carried out under the grain growth conditioning agent exists, and can make like this n of gained boehmite in preferred 1.2≤n≤2.2 scopes.

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

In 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 crystal grain at the material of the speed of growth of 120 crystal faces and 031 crystal face, be preferably alditol and carboxylate thereof, be specifically as follows one or more in D-sorbite, glucose, gluconic acid, gluconate, ribitol, ribonic acid, ribose hydrochlorate.Described gluconate and ribose hydrochlorate can be their soluble-salt separately, for example, can be one or more in sylvite, sodium salt and lithium salts.

In boehmite preparation process of the present invention, the mode that adds 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, can be for example one or more the aqueous solution in aluminum sulfate, aluminium chloride, aluminum nitrate.Because price is low, preferably sulfuric acid aluminium, liquor alumini chloridi.Aluminium salt can use separately also and can use after two kinds or more of mixing.Described aluminate solution is 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/L with aluminium oxide.

Described acid can be various Bronsted acids or be acid oxide in aqueous medium, for example, can be one or more in sulfuric acid, hydrochloric acid, nitric acid, carbonic acid, phosphoric acid, formic acid, acetic acid, citric acid, oxalic acid, preferred Bronsted acid be selected from one or more in nitric acid, sulfuric acid, hydrochloric acid.Described carbonic acid can original position produce by pass into 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/L.

Described aqueous slkali can be hydrolyzed for hydroxide or in aqueous medium the salt that makes the aqueous solution be alkalescence, and preferred hydroxide is selected from one or more in ammoniacal liquor, NaOH, 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, potash.Concentration to described aqueous slkali is not particularly limited, preferred 0H ^-Concentration be the 0.2-4 mol/L.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 potassium metaaluminate with sodium metaaluminate and/or potassium metaaluminate.

Described organic aluminum contained compound can be various can the reaction with steeping in water for reconstitution unboiled water solution, one or more in the aluminum alkoxide of generation aqua oxidation aluminum precipitation can be for example one or more in aluminium isopropoxide, isobutanol aluminum, aluminium isopropoxide, three tert-butoxy aluminium and isooctanol aluminium.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 reactant or acid.

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

Wherein, can add the compound of crystal grain growth regulating effect in hydrolysis or precipitation reaction obtain slurries that the slurries of hydrated alumina or filter cake after filtering add the water preparation again, also can add aqueous slkali or acid solution suitably to regulate the pH value to 7-10, then carry out aging at suitable temperature.Then separate, 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, also comprise the washing and the dry step that often comprise in preparation boehmite process after aging, 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, a preferred embodiment comprises the following 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 reaction vessel, obtain the hydrated alumina slurries; Perhaps add the reaction that is hydrolyzed of grain growth conditioning agent and aluminum alkoxide in deionized water, obtain the hydrated alumina slurries;

(2) filter cake after 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; The hydrated alumina slurries that also above-mentioned steps (1) can be obtained are without filtering in the existence of grain growth conditioning agent or being under 7-10 at pH not, 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 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 contained P2, in oxide and take the boehmite total amount as benchmark, the content of described P2 was not more than 70 % by weight, further preferably was not more than 50 % by weight, more preferably was not more than 30 % by weight.

Described composition can adopt any prior art that described boehmite and described silicon-containing compound are mixed to get.Wherein, described mixing can be the simple accumulation that described boehmite and described silicon-containing compound are placed in a place, can be also to adopt any one prior art, for example, can directly boehmite be mixed by the mode that stirs with silicon-containing compound in mixer, grinder, 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 control the uniformity that described mixing should reach, to this present invention to being not particularly limited.

During the consumption of each component makes final composition in described mixed process, in oxide, the content of preferred boehmite is the 65-99 % by weight, 75-97 % by weight more preferably, be more preferably 80-95% weight, the content of silicon-containing compound is the 1-35% % by weight, and more preferably the 3-25% % by weight, be 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: 400～900 ℃ of temperature are carried out, 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 the article shaped of convenient operation 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) step (2) gained extrusion molding thing is dry and roasting.

Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (2) step of introducing appropriate water, peptizing agent (as in being selected from nitric acid, acetic acid and citric acid one or more), extrusion aid (as being one or more in sesbania powder, cellulose) in the described composition and mixing.Described drying is 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 the roasting temperature 1-12 of 400-900 ℃ 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) step (2) gained extrusion molding thing is dry and roasting.

Wherein, be to guarantee carrying out smoothly of extruded moulding, comprise in step (1) and introduce appropriate water, peptizing agent (as in being selected from nitric acid, acetic acid and citric acid one or more), extrusion aid (as being one or more in sesbania powder, cellulose).Described drying is 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 the roasting temperature 1-12 of 400-900 ℃ 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 ml/g, and specific surface is 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 ml/g, and specific surface is 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, in oxide and take described catalyst as benchmark, described catalyst preferably contains the VIII family metal component of 1-10 % by weight, the group vib metal component of 5-35 % by weight; Further preferred catalyst contains the VIII family metal component of 1.5-5 % by weight, the group vib metal component of 6-30 % by weight.

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

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 containing at least a group VIII, as the method by dipping; 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 the regulation and control to concentration, consumption or the carrier consumption of the solution of metallic components, can prepare the described catalyst of specifying content, it is intelligible that this is that those skilled in the art hold.

According to the present invention, after described impregnation steps is completed, optionally can carry out the steps such as drying, roasting or not roasting.The condition of described drying and roasting is all 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 one or more in the nitrate, acetate, carbonate, chloride, soluble complexes of these metals.

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

Can also contain organic additive in catalyst provided by the invention, take described catalyst as benchmark, and in carbon, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.Described organic additive is selected from one or more the organic compound that contains in oxygen or organic compounds containing nitrogen, and preferred oxygen-containing organic compound is selected from one or more in Organic Alcohol and organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine.For example, oxygen-containing organic compound can be enumerated ethylene glycol, glycerine, polyethylene glycol (molecular weight is 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1, one or more in 2-CDTA, citric acid, tartaric acid, malic acid, 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 method arbitrarily, such as enumerating, described organic compound and other components (comprising metal component and adjuvant component etc.) is mixed with impregnated carrier after mixed solution, dry method then; And the method that organic compound is mixed with separately impregnated carrier after solution.In a kind of rear method, 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, such as baking temperature is preferably 100-300 ℃, 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 is also 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 take described catalyst as benchmark, preferably make in final catalyst by the introducing amount of selecting described organic compound, the content of described organic additive is no more than 10 % by weight, further preferably is no more than 6 % by weight.

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

During one or both components in also containing components such as being selected from phosphorus or fluorine in described catalyst, the described introducing method that is selected from the components such as phosphorus or silicon can be method arbitrarily, 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 with described carrier after the independent obtain solution of the compound that contains auxiliary agent and roasting.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 under hydrogen exists, carry out presulfurization with sulphur, hydrogen sulfide or sulfur-bearing raw material at the temperature of 140-370 ℃, 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 processed.Described hydrotreatment is included under hydrogen existence and 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 restriction, 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 described catalyst device any, for example, at described fixed bed reactors, carry out in moving-burden bed reactor or 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 be selected from crude oil, distillate, solvent-refined oil, slack wax, sweat oil, Fischer-Tropsch synthesis oil, liquefied coal coil, frivolous coal tar and 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.

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

Agents useful for same in example except specifying, is chemically pure reagent.In catalyst, each constituent content except specifying, all adopts x-ray fluorescence spectrometry.

In example of the present invention, the n value of all boehmites all adopts XRD method to measure.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 crystallite dimension to D=K λ/(Bcos θ), λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of corrected diffraction maximum, 2 θ are the position of diffraction maximum) calculation of parameter at ° peak goes out (120) take 2 θ as 23-33 respectively grain size is D (031) as D (120), the calculation of parameter at ° peak goes out (031) take 2 θ as 34-43 grain size, and by formula n=D (031)/D (120) calculates the n value.

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

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

In the retort of 2 liters and stream add 600 ml concns be 96 gram aluminium oxide/liter, wherein contain the aluminum sulfate solution of 3.6 gram ribitol and ammonia spirit that concentration is 8 % by weight carries 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 to make the pH value of slurries in slurries is 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 through XRD the n value that calculates P1-1a and P1-1b lists in 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, then adds gluconic acid sodium salt 16.3 grams to obtain containing the NaAlO of gluconic acid sodium salt ₂Then solution be transferred in the plastic reactor of cumulative volume 8L, and the reactor ratio of height to diameter is 8, bottom band CO ₂Gas distributor.Controlling solution temperature is 25 ± 5 ℃, passes into the CO of concentration 90 volume % from reactor bottom ₂Gas carries out the plastic reaction, and the plastic temperature is controlled at 20-40 ℃, regulates CO ₂Gas flow is 15 ± 2 liter/mins of clocks, makes reaction end pH value reach 8.0-8.5 in 4-6 minute, namely stops ventilation, finishes the plastic reaction.With the gained slurries be heated to 70 ℃ aging 4 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (temperature 70 C) flush cake approximately 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 through XRD the n value that calculates P1-2 and lists in table 1.

P1-3, adopt following method preparation:

In the retort of 2 liters 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 % by weight, and be warming up to 80 ℃, aging 3 hours, then filter with vacuum filter, to be filtered complete after, replenish on filter cake and added 20 liters of deionized waters (80 ℃ of temperature) flush cake approximately 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 the spray dryer outlet temperature 100-110 ℃ of scope, approximately 2 minutes dry materials time, obtain hydrated alumina P1-3 after 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 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, be also not contain ribitol in 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 through XRD the n value and the degree of crystallinity that calculate P2-1a and P2-1b and lists in table 1.

P2-2 is the business 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 table 1.

P2-3, adopt following method preparation:

Method according to P1-3 prepares boehmite, and different is, does not contain D-sorbite in 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 through XRD the n value that calculates P2-3 and lists in table 1.

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

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

From the results shown in Table 1, 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, take the degree of crystallinity of the business SB powder of Condea company as 100%, adopt the degree of crystallinity of boehmite of method preparation provided by the invention in the 60-80% scope.

Table 1

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

Embodiment 1

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

At room temperature the 1600 gram synthetic boehmite P1-1a (butt 22%) in laboratory are added 3000 ml water making beating, stir after 30 minutes, (Silica Gel 955, U.S. Davison Chemical company product contains SiO under agitation to add business 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 % by 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 double screw banded extruder kneading, be extruded into the butterfly bar of 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 composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

First 400 synthetic boehmite P1-1b (butt 70%) and the Ludox in gram laboratory (are 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 kneading on double screw banded extruder, 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, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 24 % by 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 double 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 composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

First (Beijing chemical reagents corporation contains SiO for the boehmite P1-2 (butt 69%) that 450 gram laboratories are synthetic and ethyl orthosilicate ₂28% weight is analyzed pure) 46 grams, 12.5 gram sesbania powder mix, then 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 afterwards kneading equal on double screw banded extruder, 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, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 4 % by 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 double 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 composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

First (Siral 40, contain SiO for the boehmite P1-3 (butt 71%) that 400 gram laboratories are synthetic 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, after kneading on double screw banded extruder is even, obtain composition Z H-4 of the present invention afterwards.ZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-4, and the total amount of silica and aluminium oxide is as benchmark in oxide and 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 double 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 composition and the preparation thereof of boehmite of the present invention and silicon-containing compound:

First 300 synthetic boehmite P1-3 (butt 71%), business boehmite (Shandong Aluminium Industrial Corp produces, butt 67% weight, n value 1.02) 212 grams, the Ludox in gram laboratory (are contained 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, after continuation kneading on double screw banded extruder is even, obtain composition Z H-5 of the present invention afterwards.ZH-5 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of ZH-5, and the total amount of silica and aluminium oxide is as benchmark in oxide and 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 double 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 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 1600 gram synthetic boehmite P2-1a (butt 21%) in laboratory are added 3000 ml water making beating, stir after 30 minutes, (Silica Gel 955, U.S. Davison Chemical company product contains SiO under agitation to add business 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 % by 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 double screw banded extruder kneading, be 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-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:

First the 400 gram synthetic boehmite P2-1b (butt 68%) in laboratory (are 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, continue afterwards kneading on double screw banded extruder, 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, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 24 % by 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 double 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:

First (Beijing chemical reagents corporation contains SiO with 450 gram business boehmite P2-2 (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, then this mixture is mixed with 9 milliliters of nitric acid, 390 ml waters, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-3.CZH-3 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-3, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 4 % by 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 double 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:

First (Siral 40, contain SiO for the boehmite P2-3 (butt 68%) that 400 gram laboratories are synthetic and amorphous aluminum silicide ₂40% weight, Germany 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, west, Shantou), 446 ml waters mix, continue afterwards kneading on double screw banded extruder, obtain reference composition CZH-4.CZH-4 is a kind of plastic, adopts x-ray fluorescence method to measure the composition of CZH-4, and the total amount of silica and aluminium oxide is as benchmark in oxide and in the described composition, and silica content is 30 % by 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 double 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:

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

(2) reference silica-alumina and preparation thereof:

Continue on double 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 carrier all 60% of alumina contents.

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

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.

The raw material sources that Kaolinite Preparation of Catalyst uses 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 grams, with 190 milliliters of aqueous solution dippings that contain ammonium molybdate 36 grams, nickel nitrate 29 grams, phosphatase 11 1.9 grams 2 hours, in 120 ℃ of dryings 4 hours, 470 ℃ of roastings 4 hours obtained catalyst C-1.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst C1, 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 grams, 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.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC1, measurement result is as shown in table 3.

Embodiment 7

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

Comparative Examples 7

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

Embodiment 8

Get silica-alumina SA-3 200 grams, with 170 milliliters of the aqueous solution dipping that contains 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.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst C-3, measurement result is as shown in table 3.

Comparative Examples 8

Get reference silica-alumina CSA-3 200 grams, with 182 milliliters of the aqueous solution dipping that contains 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.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC-3, measurement result is as shown in table 3.

Embodiment 9

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

Get fluorine bar F-1 200 grams, with 158 milliliters of aqueous solution dipping fluorine bars that contain 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.Take catalyst weight as benchmark, adopt the chemical composition in XRF light measurement catalyst C-4, measurement result is as shown in table 3.

Comparative Examples 9

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

Get fluorine bar CF-1 200 grams, with 140 milliliters of aqueous solution dipping fluorine bars that contain 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.Take catalyst weight as benchmark, adopt the chemical composition in XRF light method mensuration catalyst DC-4, measurement result is as shown in table 3.

Embodiment 10

Get silica-alumina SA-5 200 grams, with the 148 milliliters of impregnated carriers of the aqueous solution 2 hours that contain ammonium molybdate 20 grams, phosphatase 11 6 grams, 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 grams, 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.Take catalyst weight as benchmark, adopt the chemical composition in XRF light method mensuration catalyst C-5, measurement result is as shown in table 3.

Comparative Examples 10

Get reference silica-alumina CSA-5 200 grams, with the 161 milliliters of impregnated carriers of the aqueous solution 2 hours that contain ammonium molybdate 20 grams, phosphatase 11 6 grams, 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 grams, 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.Take catalyst weight as benchmark, adopt the chemical composition in x-ray fluorescence method mensuration catalyst DC-5, measurement result is as shown in table 3.

Table 3

Embodiment 11-15 explanation 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 the present embodiment explanation catalyst C-1 of the present invention, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) hydrodesulfurization reaction performance.

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

Before formal charging, be first that sulfurized oil carries out presulfurization to catalyst with the mixed solution that contains 5 % by weight carbon disulfide and cyclohexane, 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 afterwards feedstock oil 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.

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

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

In formula, x is 4,6-DMDBT desulfurization degree, and the activity of getting catalyst DC-1 is 100,4 of catalyst C-1 of the present invention, and 6-DMDBT is relative, and hydrodesulfurization activity can be represented by the formula: relative activity=A _C-1/ A _DC-1* 100%.A in 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 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 the 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 nitrogen determination method 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 in formula, LHSV is liquid hourly space velocity (LHSV).

Comparative Examples 12

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

According to the method evaluation comparative catalyst DC-2 of embodiment 12, reaction result sees Table 6, take the activity of DC-2 catalyst as 100.

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 the 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.

According to the method evaluation reference catalyst DC-3 of embodiment 13, reaction result is listed in table 8, take the activity of DC-3 catalyst as 100.

Table 8

Embodiment 14

The saturated performance of catalytic diesel oil aromatic hydrogenation of the 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.

According to the catalytic diesel oil arene saturating activity of the method evaluation reference catalyst DC-4 of embodiment 14, reaction result is listed in table 10, take the toluene hydrogenation activity of DC-4 as 100.

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.

According to the method evaluation reference catalyst DC-5 of embodiment 15, result is provided by table 12, take the hydrodenitrogenationactivity activity of DC-5 as 100.

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 refers to that 2 θ in XRD spectra are the peak of 34-43 °, described 120 peaks refer to that 2 θ in XRD spectra are the peak of 23-33 °, D=K λ/(Bcos θ), K is the Scherrer constant, λ is the diffraction wavelength of target shaped material, B is the half-peak breadth of diffraction maximum, 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, in the composition of described boehmite and silicon-containing compound, the content of boehmite is the 65-99 % by weight, and the content of silicon-containing compound is the 1-35 % by weight.

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

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

6. according to claim 1,3, the 4 or 5 described catalyst of any one, 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 is selected from one or more in esters of silicon acis, silanol, silicon ether, silicone, silicone oil.

8. according to claim 1,3, the 4 or 5 described catalyst of any one, it is characterized in that, described silicon-containing compound is selected from one or more in 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 hydrated SiO 2, Ludox, silicic acid, 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, in oxide and take the boehmite total amount as benchmark, the content of described P2 is not more than 70 % by weight.

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

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

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

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

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

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

17. catalyst according to claim 16 is characterized in that, take described catalyst as benchmark and with carbon, the content of described organic additive is no more than 6 % by 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 the described catalyst of claim 1-17 any one.