CN1781605B - Method for manufacturing catalyst for hydrogenation of hydrocarbon oil and method for hydrogenation refining - Google Patents

Abstract

The invention provides a catalyst for the hydrogenation of hydrocarbon oil and a method for manufacturing the same. During the preparation of the catalyst for the hydrogenation of hydrocarbon oil, hydrous titanium oxide is brought into contact with the ions of the principal catalyst element and the ions of the promoter element, either together or separately, to effect ion exchange, then the pH is finally adjusted to a value in the range of 3-9 and the ion-exchanged product is molded, dried and calcined. The hydrogenation catalyst is composed of a porous 4 group metal oxide. Due to the adoption of the hydrogenation catalyst, the hydrogen consumption is obviously improved.

Description

The hydrogenization catalyst preparation method of hydrocarbon ils and the hydrofinishing process of hydrocarbon ils

The application be that January 15, application number in 2002 are 02814660.3 the applying date, denomination of invention divides an application for the application of " porous 4 group metal oxide and preparation method thereof ".

Technical field

Porous 4 group metal oxide that the present invention relates to use in the purposes such as catalyst carrier, catalyst, drier, adsorbent, filler and preparation method thereof and purposes especially relate to the porous 4 group metal oxide of high-specific surface area and Heat stability is good.

In addition, the present invention relates to high-specific surface area and Heat stability is good, accurately control size and the pore narrowly distributing of pore, porous 4 group metal oxide that the high-purity porous titanium oxide that uses as catalyst carrier or catalyst is formed and preparation method thereof.

In addition, the pore aperture that the present invention relates to high-specific surface area and Heat stability is good, has control is porous 4 group metal oxide of forming of the porous titanium oxide that might as well, use as catalyst carrier or catalyst of mechanical strength and preparation method thereof simultaneously.

And; The present invention relates to the petroleum distillate of this porous 4 group metal oxide, especially porous titanium oxide composition, the hydrogenation catalyst of coal liquefaction wet goods hydrocarbon ils; More particularly; Relate to and use titanium oxide (titanium dioxide with high-specific surface area; Also claim titanium oxide) make catalyst component (comprise primary catalyst component and co-catalyst component as catalyst carrier; These two kinds of compositions are called for short " catalyst component ") high concentration and the hydrogenation catalyst of high degree of dispersion in this titanium oxide equably, and use this hydrogenation catalyst to improve from the hydrocarbon ils of sulfur-bearing composition and nitrogen component, to remove nitrogen component with respect to the selectivity of removing the desulfuration composition, remove these sulphur compositions and nitrogen component, can obviously reduce the hydrocarbon oil hydrogenation Catalysts and its preparation method and the purposes of hydrogen consumption simultaneously with high removal efficiency.

Background technology

Preparation method to porous 4 group metal oxide; For example, with the porous titanium oxide example when roughly describing, known have method (vapor phase method) and a liquid phase method that uses oxygen burning titanium tetrachloride to prepare; In liquid phase method; The preparation of methods such as the alkali neutralization of employing titanium sulfate or titanyl sulfate hydrolysis, titanium tetrachloride or titanium sulfate, alkoxytitanium hydrolysis is carried out drying, roasting as the oxidizing aqueous titanium of precursors of titanium oxide to this oxidizing aqueous titanium, the preparation titanium oxide.

As adopting above-mentioned liquid phase method to prepare the exemplary process of titanium oxide, for example, following method is arranged: 1. as the method that adopts the titanyl sulfate hydrolysis; Titanyl sulfate is heated to more than 170 ℃, and hydrolysis under its pressure more than saturated vapor pressure prepares oxidizing aqueous titanium; At 400-900 ℃ roasting temperature, prepare spherical anatase-type titanium oxide (spy opens flat 05-163, No. 022 communique) then; 2. as the method that adopts the titanyl sulfate neutralization, the acicular crystal particle that makes titanyl sulfate is contacted dry, the roasting of the oxidizing aqueous titanium of the needle-like that makes with alkaline aqueous solution, (spy opens flat 05-139 to preparation needle-like titanium oxide; No. 747 communiques); And, will filter through the mixed sediment that gets of four alkoxytitaniums and water, after the washing 3. as the sol-gel process that alkoxytitanium is hydrolyzed; Add water and become slurries; The product that hydrothermal treatment consists is made carries out drying, the middle pore titanium oxide porous body (spy opens 2001-031, No. 422 communiques) of preparation pore volume 0.1-0.5ml/g, average pore aperture 3-30nm etc.

Yet these adopt the porous titanium oxide of method preparation in the past, general heat endurance extreme difference, because high temperature or long roasting cause specific area sharply to descend, existence can not be kept the problem of high-specific surface area.This is because in the process of high-temperature roasting in the preparation, the hydroxyl of oxidizing aqueous titanium causes dehydrating condensation after breaking away from; Or, cause crystalline particle obviously to be grown up, for example because so-called " sintering " takes place the titanium oxide that generates; Shown in the relation of the specific area of Fig. 1 and sintering temperature, along with sintering temperature raises, owing to sintering or dehydrating condensation cause by amorphous crystallization or crystalline transition to anatase, rutile etc.; Specific area sharply descends, and is difficult to keep high-specific surface area.

Therefore; Titanium dioxide carrier or titanium oxide catalyst are during as the hydroprocessing catalysts of hydrocarbon; Although the hydrotreatment activity of per unit specific area is very good, because poor heat stability, so at high temperature can not keep high-specific surface area; Therefore can not present sufficient performance as catalyst, not resemble and in industry, use catalyst carrier or the catalyst of aluminium oxide or silica system.

When using with catalyst as alkylation, in order to embody the acid matter of super acids, must carry out high-temperature process, but because poor heat stability, become low specific surface area, absolute magnitude that therefore should acid reduces, and can not guarantee the necessary performance as catalyst.

In addition, when using with catalyst as denitrogenation from exhaust smoke, although the denitrification activity of per unit specific area is very good, because the problem of heat endurance, usually just at 40-50m ²Use under the low specific surface area of/g, must use a large amount of catalyst, in addition,, have the problem of Applicable temperature narrow range also owing to the problem of this heat endurance.

In addition, although the abrasion intensity of titanium oxide is high, when reaction is used with catalyst as Fischer-Tropsch (FT),, therefore can't satisfy the titanium oxide that requires as catalyst on the obtained performance at present owing to only obtain low specific surface area.

In order to solve this type problem, several kinds of trials have been proposed also in the past.For example, in titanium oxide, add second composition of silica, aluminium oxide, phosphorus etc., preparation has the porous titanium oxide of high-specific surface area, Heat stability is good, can enumerate following motion.

Te Kaiping 07-275, No. 701 communiques proposed in acid solution dissolves silicon compound and titanium compound, add alkaline matter again carries out the method that co-precipitation, slaking prepare silica-titanium oxide.The ratio of titanium oxide and silica is the scope (ratio of titanium oxide is 13 weight % among the embodiment) of 1-50 weight % in this method, and the specific area of the silica-titanium oxide catalyst that made in 3 hours 500 ℃ of following roastings is high, is 558m ²/ g.

Te Kaiping 08-257-399 communique has proposed following method: with (1-x) TiO ₂XSiO ₂After the alkoxytitanium of mol ratio (x=0-0.5) and the hydrolytic sol of alkoxyl silicone carry out gelation, 350-1200 ℃ of following roasting, preparation titanium oxide base catalyst.In this titanium oxide base catalyst, the adding proportion of silica is lacked than titanium oxide, according to embodiment, and the mol ratio (TiO of titanium oxide and silica ₂: SiO ₂) be 0.95: 0.05, the specific area of the titanium oxide catalyst that made in 2 hours 500 ℃ of following roastings shows 160m ²The value of/g.

The spy opens 2,000-254, and No. 493 communique has proposed following method: the mixture of alkoxytitanium and alkoxyl silicone is reacted in alcoholic solvent, product is carried out roasting, the silica modified titanium oxide that the preparation catalyst carrier is used.The silica modified titanium oxide that this catalyst carrier is used, the Ti/Si atomic ratio is 5-50, during roasting, the BET surface area is 90m in the hot environment more than 800 ℃ ²More than/the g.According to embodiment, the Ti/Si atomic ratio is 10 o'clock, at the silica modified titanium oxide demonstration specific area 185m of 600 ℃ of following roastings ²The value of/g.

Te Kaiping 2,000-220, and No. 038 communique has proposed following method: alkoxytitanium is dissolved in the solvent; Interpolation water is hydrolyzed and reacts and polymerisation, generates polymer, 2. makes this polymer dissolution in organic solvent; Process spinning solution, 3. this spinning solution is carried out spinning, make precursor fiber; 4. before roasting and/or during roasting precursor fiber is carried out steam treatment, preparation contains the titanium dioxide fiber of catalyst component.In this method, operation 1. or operation 2. in the preferred silicon compound that adds, make silica content be about 5-30 weight %, and according to embodiment, silicon oxide-containing 12 weight % and V ₂O ₅19 weight %, the catalyst oxidation titanium fiber that 500 ℃ of following roastings made in 1 hour in air have specific area 173m ²The value of/g.

Open flat 5-184 according to the spy, No. 921 communiques disclose the preparation method of aluminium oxide-titanium oxide composite catalyzing agent carrier; Wherein, In the colloidal sol of the hydroxycarboxylate of titanium and/or titanyl compound, hydroxide and oxide and/or hydroxide that hydroxycarboxylic acid is added on aluminium, carry out mixing, roasting; The mol ratio that makes titanium oxide and aluminium oxide is below 2.0, and the mol ratio of hydroxycarboxylic acid and aforementioned titanium oxide is 0.2-2.0.According to embodiment, at 600 ℃ of roastings 2 hours, TiO ₂/ Al ₂O ₃Mol ratio be 1.53, hydroxycarboxylic acid/TiO ₂Specific area than being 1.0 carrier shows 200m ²The value of/g.

Te Kaiping 08-057; No. 322 communiques have proposed the preparation method of titanium dioxide carrier: the phosphoric acid that in the titanium oxide hydrate filter cake that the titanium salt hydrolysis makes, adds ormal weight; Mediate the back plasticizing, prescription moulding according to the rules, roasting make and contain 1-5 weight % phosphorus by the oxide conversion.Contain 5 weight %P among the embodiment of this method ₂O ₅, the titanium dioxide carrier that made in 2 hours 500 ℃ of roastings shows specific area 108m ²The value of/g.

Te Kaiping 07-232; No. 075 communique has proposed preparation and has removed the method for nitrogen oxide with catalyst; Wherein, with the compound of titanyl compound or hydrous oxide and phosphorus, making the combined amount of phosphorus is 0.1-6 weight % with respect to titanium oxide; The gained mixture is processed the roasting body 450-800 ℃ of roasting, make this roasting body load with vanadium.According to embodiment, the titanium oxide roasting body before load vanadium 550 ℃ of roastings 2 hours preparation, that with respect to the ratio of the phosphorus of titanium oxide be 2.5 weight % demonstrates specific area 125m ²The value of/g.

Yet; This technology that is employed in second composition that adds silica, aluminium oxide, phosphorus etc. in the titanium oxide even improved heat endurance, can prepare the porous titanium oxide that can keep high-specific surface area through high-temperature heat treatment; Can not control to close limit to the pore of porous titanium oxide and pore distribution; The most suitable catalyst for reaction pore aperture is few, therefore, has the other problem that can not obtain enough performances aspect the selectivity of reacting or activity and the catalyst life.

Here, catalyst carrier or catalyst that various chemical reactions use not only require high-specific surface area, Heat stability is good, and it is also quite important accurately to control the pore structure of pore aperture and pore distribution etc.It is considerable that the diffusion at the activity of such catalysts center easily of general relevant with chemical reaction reaction molecular, contact and reaction end back break away from easily; Therefore must control the scope in pore aperture, make it to become the pore aperture that is suitable for as the reactive material of object.That is, importantly, reactive material does not have diffusional resistance, and not to reacting invalid too little or too big useless pore.Therefore, it is desirable to control the catalyst in pore aperture according to the reaction purpose.For example, with regard to reacting effective catalyst pore aperture, when being purpose with the light oil hydrodesulfurization; Being 6-10nm, is 8-15nm when being purpose with the mink cell focus hydrodesulfurization, when being purpose with the HDM; Be 15-30nm, when being purpose, in the scope of 20-40nm with the hydrogenation diasphaltene.

From such viewpoint, also carried out the trial of the porous titanium oxide of pore structures such as preparation control pore aperture and pore distribution in the past, for example, enumerate following method.

Promptly; As making the pore pore-size distribution become the method for the control pore pore diameter range of narrow distribution; Special public clear 60-50; No. 721 communiques have proposed the preparation method of porous inorganic oxide; Comprise the operation of acquisition as the hydrosol of seed, make the alternately conversion between hydrosol soluble end and hydrosol areas of sedimentation of pH value (pH swing (swing) operation) of this hydrosol, thus make crystalline growth and obtain to form thick agglomerate the hydrosol operation and the hydrosol that forms this thick agglomerate carried out the operation that drying, roasting obtain metal oxide.But; Only adopt this method; For example, though can make titanium oxide have narrow pore pore-size distribution through control; Receive thermal process because the roasting of catalyst or the reaction heat in the reaction system etc. cause, be difficult to prepare specific area and do not reduce, do not cause the active titanium oxide catalyst that descends.

In addition, the spy opens flat 06-340, and No. 421 communiques have proposed to prepare the method for porous titanium oxide; Wherein, for example add ammoniacal liquor in the titanium tetrachloride, generate hydrous titanium oxide at water-disintegrable titanium compound; Add polybasic carboxylic acid again, make it chelatingization, make pH become neutrality with alkali again from faintly acid; The organic oxidation titanium compound is separated out, gained organic oxidation titanium compound is flocculated, calcining with inorganic acid; In the embodiment, calcining the total pore volume of porous titanium oxide that made in 24 hours down at 300 ℃ is 0.348ml/g, and the BET specific area is 112m ²/ g, pore, compare with commercially available porous titanium oxide mainly in the scope that with 120_ is the radius 32-120_ of main peak in the scope of pore radius 20-500_, are that the distribution of high surface and pore is not too wide.Yet, in this method,, be constrained to 300 ℃ low temperature to calcining heat in order to keep high surface, in addition, main pore is distributed in the wide region of pore radius 32-120_ very widely.

In addition; Te Kaiping 11-322; No. 338 communiques have proposed to prepare the method for porous titanium oxide: through in alkoxytitanium being dissolved in the solution that obtains with the miscible organic solvent of water, add from weak acid and weak base, weak acid and highly basic, and weak base and strong acid neutralize select the salt that makes more than a kind or 2 kinds, water, reach from the salt that contains the metal that belongs to rare earth element, select more than a kind or 2 kinds, prepare titanium-metal composite compound; Remove compoundization metal through acid treatment then; In addition, this moment, through making the hydrolysis inhibitor coexistence, the porous titanium oxide of fine structure was controlled in preparation well as required; Among the embodiment, the specific area of the porous titanium oxide that made in 2 hours 600 ℃ of roastings is 90m ²More than/the g, but pore is distributed in the scope of 100-600_, is wide distribution.

In addition, when using porous titanium oxide as catalyst, in order effectively to embody its characteristic as catalyst, titanium oxide must be a high-purity.

According to waiting (Togari, O., Ono, T., Nakamura, M., Sekiyu Gakkai shi (institute of Petroleum's will), 22, (6), 336 (1979)) report, catalyst carrier Al in the river, family ₂O ₃-TiO ₂And SiO ₂-TiO ₂Complex chemical compound, work as Al ₂O ₃And SiO ₂Content when increasing respectively, the acid strength of catalyst carrier shows the trend that increases, and in addition, opens flat 08-57 like the spy, No. 322 communique is said, when the content of phosphorus increases in the titanium oxide, strong acid site occurs.Therefore; In the hydrodesulfurization reaction of petroleum distillate, because the strong acid center on the catalyst generates coke; Cause the inactivation of catalyst easily; Therefore according to the inventor's research, keep the generation of the high desulfurization activity of distinctive per unit specific area, inhibition coke in order to make titanium oxide, the purity that is used as the titanium oxide of catalyst carrier is pressed oxide (TiO ₂) benchmark more than 97 weight %, be preferably more than the 98 weight %.

Yet; Contained sulphur composition or nitrogen component in the hydrocarbon ils from oil or coal; When this hydrocarbon ils acts as a fuel burning, generate oxysulfide or nitrogen oxide, be discharged in the atmosphere, not only become the reason of atmosphere pollution; And when the decomposition reaction of hydrocarbon ils or conversion reaction, become catalyst poison, become the reason that the reaction efficiency that causes these reactions reduces.In addition, the sulphur content in the transport fuel oil also is the catalyst poison of automobile or diesel locomotive exhaust after-treatment catalyst.

And, removed the hydrofinishing that sulphur composition or nitrogen component in the hydrocarbon ils are used in the past, the hydrogenation catalyst that relevant this hydrofinishing is used; For example also proposed to make aluminium oxide, zeolite-aluminium oxide, aluminium oxide-titanium oxide, phosphorus-silica-alumina etc. carrier loaded molybdenum (Mo), tungsten (W), cobalt (Co), nickel (Ni) etc. the metal with high active of hydrogenation catalysis many catalyst (for example; Te Kaiping 6-106, flat 9-155 is opened in No. 061, spy, and flat 9-164 is opened in No. 197, spy; 2000-79 is opened in No. 334, spy; 2000-93 is opened in No. 343, spy, and 2000-117 is opened in No. 804, spy, and 2000-135 is opened in No. 111, spy; No. 437, spy are opened 2001-62, each communique of No. 304 etc.).

Generally, when being main purpose to remove sulphur composition (desulfurization) in the hydrocarbon ils, the catalyst of main working load molybdenum and cobalt, and with desulfurization not only but also when removing nitrogen component (denitrogenation) and be purpose, mainly the catalyst of molybdenum or tungsten and nickel is loaded with in use.This is because the nickel cause strong to the hydrogenation ability of aromatic compound.

Here, the nitrogen component in the hydrocarbon ils exists as aromatic compound basically, when adopting hydrofinishing to remove this nitrogen-containing aromatic compound, causes the hydrogenation of aromatic rings, and then cause the fracture of C-N key that nitrogen becomes ammonia and breaks away from, and carries out denitrification reaction.Therefore, denitrification reaction requires that aromatic series is had the high hydrogenation ability that adds.As a result, when using nickeliferous hydrogenation catalyst to carry out the hydrofinishing of hydrocarbon ils, the problem that exists the hydrogen consumption to increase.

Environmental Agency's centralized environment review conference is entitled as the report of " What thecountermeasures should be for reduction of antomobile exhaustgases in the future " for the 4th time according in November, 2000; To suitably the light oil sulfur composition as diesel car fuel be dropped to 50ppm from existing 500ppm by 2004, hope further low sulfur " in the future.In addition, the nitrogen component in the hydrocarbon ils such as light oil not only becomes the reason that color articles etc. causes quality to reduce, and when hydrofinishing owing to become the catalyst poisoning that causes hydrogenation catalyst, the material of inactivation, therefore hope to remove as much as possible.

Yet, using the hydrofinishing of above-mentioned hydrogenation catalyst in the past, desulfurization performance or nitrogen removal performance are not necessarily abundant, in order the sulphur composition in the light oil to be dropped to 50ppm or below the 50ppm, must to make hydrorefined treatment conditions very harsh.For example, must will lead to oil mass and drop to approximately 1/3, perhaps must catalytic amount be increased to about about 3 times.That is, reduce when leading to oil mass, must change the production schedule of oil plant significantly, when increasing catalytic amount, must set up 2 tower reactors.Perhaps, must reaction temperature be raise more than 20 ℃, the obvious sacrifice of existence this moment catalyst life etc. increases the weight of the problem of financial burden.In addition; Also be difficult to adopt removal efficiency to carry out hydrofinishing to nitrogen component with sulphur composition same degree; Want with high removal efficiency this nitrogen component to be carried out hydrofinishing, then the hydrogen consumption is inevitable excessive, the problem of the necessary newly-increased organizational system hydrogen production device of oil plant existence that Yu Qing is few etc.

As stated; As the reason that can not prepare the high activity desulphurization catalyst, just making aluminium oxide is the load hydrogenation catalyst of primary catalyst component molybdenum and co-catalyst component cobalt for example on the carrier of main body, and the load capacity of this molybdenum is pressed the oxide benchmark normally below the 25 weight %; If load capacity is high again; On carrier, generate the agglomerate of molybdenum, can't high degree of dispersion, thereby can not bring into play catalyst performance effectively; And, can not obtain desired activity owing to produce the harmful effect of pore obstruction or surface area, pore volume minimizing etc.

Summary of the invention

The inventor to Heat stability is good, have the result that the porous 4 group metal oxide of high-specific surface area and high degree of dispersion catalyst metals is studied with great concentration, find, at formula M O _(2-x)(OH) _2xAfter adding particle growth inhibitor in the hydrosol, hydrogel or these the dry thing of moisture 4 family metal oxides of (in the formula, M representes 4 family's metals, and x representes the number of x＞0.1) expression,, make 4 family metal oxides, have 80m through dry, roasting ²Specific area, above pore volume, the narrow degree of distribution of the pore more than 50% (pore sharpness degree) of 0.2ml/g that/g is above; Heat stability is good; And the catalyst metals high degree of dispersion, and, through suitable employing pH swinging operation; The porous 4 group metal oxide that can make narrow pore pore-size distribution, have sound response optionally to use as catalyst or catalyst carrier with control, thus the present invention accomplished.

In addition, the inventor also finds, through at formula M O _(2-x)(OH) _2x(in the formula; M representes 4 family's metals; X representes the number of x＞0.1) in the hydrosol, hydrogel or these the dry thing of oxidizing aqueous titanium of expression; Add the ion that contains the element of from silicon (Si), phosphorus (P), magnesium (Mg), calcium (Ca), barium (Ba), manganese (Mn), aluminium (Al) and zirconium (Zr), selecting that trace is provided compound more than a kind or 2 kinds as after the particle growth inhibitor; Carry out drying, roasting,, still can prepare and not only have 80m even under 500 ℃, 3 hours hot conditions, carry out roasting ²Above high-specific surface area, the Heat stability is good of/g, the purity that can control pore aperture and titanium oxide are the above high-purity porous titanium oxides of 97 weight %, thereby have accomplished the present invention.Promptly; The hydroxyl that the easy heat of the oxidizing aqueous titanium particle that the pore aperture is precisely controlled breaks away from is difficult to the multivalent ion ion-exchange of the above-mentioned element of heat disengaging; Because of also being appeared by the multivalent ion of the above-mentioned element of ion-exchange, the solid effect prevents that near hydroxyl breaks away from the effect of the polycondensation that is caused in addition; Therefore when the heat treatment of drying or roasting, can suppress and prevent the particle growth of the hydroxyl disengaging of oxidizing aqueous titanium particle effectively, thereby accomplish the present invention.

In addition; The inventor also finds, thus through synthetic pore distribute controlled make the pore narrowly distributing and the scope of regulation contain little pore, the pore asymmetrical oxidizing aqueous titanium that distributes, this oxidizing aqueous titanium is carried out drying, roasting; Obtain a kind of porous titanium oxide; It is controlled so as to and is pore aperture arbitrarily, and has the pore distribution shape that distributes along the reaction molecular amount, has more high-specific surface area than the porous titanium oxide of even control particle diameter; And mechanical strength, thereby accomplished the present invention.

And the inventor also finds, in the process of preparation this porous 4 group metal oxide, especially porous titanium oxide, through at formula M O _(2-x)(OH) _2x(in the formula, M representes 4 family's metals, and x representes the number of x＞0.1) or composition formula TiO _(2-x)(OH) _2xYH ₂O (in the formula, x is 0.1≤x＜2.0, and y is 0.3≤y≤40) or composition formula TiO _(2-x)(OH) _2xYH ₂In the hydrosol, hydrogel or these the dry thing of the oxidizing aqueous titanium that O (in the formula, x is 0.2≤x＜1.0, and y is 0.3≤y≤40) is represented; Add the compound that the ion that contains the element with high active of hydrogenation catalysis can be provided more than 2 kinds; Preferably add compound that the ion with the element that becomes primary catalyst component and co-catalyst component can be provided more than 2 kinds at least as the particle inhibitor of growing up, through dry, roasting, not only desulfurization performance is good; And nitrogen removal performance might as well; Hydrogen gas consumption is also not too big, can be used as to help in the industry realizing that the low sulfur " of hydrocarbon ils and the hydrocarbon oil hydrogenation catalyst of low nitrogenize use, thereby has accomplished the present invention.

Therefore, the object of the present invention is to provide Heat stability is good, specific area are big, catalyst metals is highly dispersed porous 4 group metal oxide and preparation method thereof.

In addition, another object of the present invention is to provide Heat stability is good, specific area is big and the porous 4 group metal oxide that uses as catalyst or catalyst carrier of catalyst metals high degree of dispersion, the narrow pore pore-size distribution with control, good reaction selectivity and preparation method thereof.

In addition, another object of the present invention is to provide high-specific surface area, Heat stability is good, accurately controls the size of pore and high-purity porous titanium oxide of pore narrowly distributing and preparation method thereof.Said " accurately controlling the size of pore " also means evenly and accurately controls the particle diameter of Titanium particles.

In addition, another object of the present invention also be to provide control to become any pore aperture and have the pore distribution shape that distributes along the reaction molecular amount, than the even porous titanium oxide of control particle diameter have high-specific surface area more and mechanical strength might as well porous titanium oxide.

And, the object of the present invention is to provide to have the few hydrocarbon oil hydrogenation Catalysts and its preparation method of good desulfurization performance and nitrogen removal performance and hydrogen consumption.

In addition, another object of the present invention also be to provide not only desulphurizing activated good but also denitrification activity might as well, the hydrogen consumption during hydrofinishing is not too big, help industry goes up the low sulfur " that realizes hydrocarbon ils and the hydrocarbon oil hydrogenation Catalysts and its preparation method of low nitrogenize.

In addition, another object of the present invention also is to provide and uses this desulphurizing activated and denitrification activity is all good and the not too big hydrocarbon oil hydrogenation catalyst of hydrogen consumption removes desulfuration composition and nitrogen component from the hydrocarbon ils of while sulfur-bearing composition and nitrogen component with high removal efficiency during hydrofinishing hydrofinishing process.

That is, the present invention relates to porous 4 group metal oxide, wherein, at formula M O _(2-x)(OH) _2xIn the hydrosol of 4 family's metal hydrous oxides that (M representes 4 family's metals in the formula, and x representes the number of x＞0.1) is represented, hydrogel or these the dry thing, behind the interpolation particle growth inhibitor, carry out drying, roasting, make 4 family metal oxides, have 80m ²Specific area, above pore volume, the narrow degree of distribution of the pore more than 50% of 0.2ml/g that/g is above.Here, above-mentioned formula M O _(2-x)(OH) _2x4 family's metal hydrous oxides of expression, preferred 4 family's metal M are that titanium (Ti) and 4 family's metal hydrous oxides are oxidizing aqueous titaniums, more preferably, are composition formula TiO _(2-x)(OH) _2xYH ₂The oxidizing aqueous titanium or the composition formula TiO of O (in the formula, x is 0.1≤x＜2.0, and y is 0.3≤y≤40) expression _(2-x)(OH) _2xYH ₂The oxidizing aqueous titanium of O (in the formula, x is 0.2≤x＜1.0, and y is 0.3≤y≤40) expression.

In addition, the present invention relates to the preparation method of porous 4 group metal oxide, wherein, in water solvent, react the formula M O that makes at 4 family's metallic compounds that make raw material and pH conditioning agent _(2-x)(OH) _2xIn the hydrosol, hydrogel or these the dry thing of 4 family's metal hydrous oxides of (in the formula, M representes 4 family's metals, and x representes the number of x＞0.1) expression, add after the particle growth inhibitor, carry out drying, roasting.Here, above-mentioned formula M O _(2-x)(OH) _2x4 family's metal hydrous oxides of expression, preferred 4 family's metal M are that titanium (Ti) and 4 family's metal hydrous oxides are oxidizing aqueous titaniums, more preferably composition formula TiO _(2-x)(OH) _2xYH ₂O (in the formula, x is 0.1≤x＜2.0, and y is 0.3≤y≤40) or composition formula TiO _(2-x)(OH) _2xYH ₂The hydrous oxide of O (in the formula, x is 0.2≤x＜1.0, and y is 0.3≤y≤40) expression.

In addition, the hydrocarbon oil hydrogenation catalyst that the porous 4 group metal oxide that the present invention relates to use compound that the ion that contains the element with high active of hydrogenation catalysis is provided to make as particle growth inhibitor constitutes.Here, preferred especially 4 family's metal M hydrocarbon oil hydrogenation catalyst that is titaniums (Ti).

In addition, the invention still further relates to and make this hydrogenation catalyst and hydrocarbon ils in the presence of hydrogen, at reaction temperature 280-400 ℃, reaction pressure 2-15MPa, LHSV0.3-10hr ^-1And the hydroprocessing condition of hydrogen/oil ratio 50-500N1/1 contact and remove sulphur composition and the hydrocarbon oil hydrogenation process for purification of nitrogen component in the hydrocarbon ils down.

And, adopting this scheme, the present invention typically is described below.

At first, first aspect of the present invention relates to porous 4 group metal oxide and preparation method thereof, through at formula M O _(2-x)(OH) _2xIn the hydrosol, hydrogel or these the dry thing of 4 family's metal hydrous oxides of (in the formula, M representes 4 family's metals, and x representes the number of x＞0.1) expression, add after the particle growth inhibitor, carry out drying, roasting, make said 4 family metal oxides, have 80m ²Specific area, above pore volume, the narrow degree of distribution of the pore more than 50% of 0.2ml/g that/g is above use as the catalyst or the catalyst carrier of Heat stability is good and catalyst metals high degree of dispersion.And relate to porous 4 group metal oxide that makes through suitable employing pH swinging operation and preparation method thereof; Said oxide has high-specific surface area and Heat stability is good, uses as catalyst metals high degree of dispersion, the catalyst with controlled narrow pore pore-size distribution, good reaction selectivity or catalyst carrier.

Second aspect of the present invention relates to porous titanium oxide and preparation method thereof, wherein, and through at general formula TiO _(2-x)(OH) _2x(in the formula; X representes the number of x＞0.1) in the hydrosol, hydrogel or these the dry thing of oxidizing aqueous titanium of expression; Add a kind or the two or more compound of the ion that contains the element of from silicon (Si), phosphorus (P), magnesium (Mg), calcium (Ca), barium (Ba), manganese (Mn), aluminium (Al) and zirconium (Zr), selecting that trace is provided as after the particle growth inhibitor, carry out drying, roasting, make titanium oxide; Roasting under 500 ℃, 3 hours hot conditions still has 80m ²The purity that specific area, above pore volume, the narrow degree of distribution of the pore 50% or more of 0.2ml/g that/g is above are high-specific surface area and Heat stability is good, not only control pore aperture but also titanium oxide be 97 weight % above highly purified, as the porous titanium oxide of catalyst or catalyst carrier use.

The third aspect of the invention relates to porous titanium oxide and preparation method thereof; Wherein, Thereby synthetic control pore distributes and makes the pore narrowly distributing and include little pore and pore is distributed as asymmetrical oxidizing aqueous titanium in the scope of regulation, should carry out drying, roasting by oxidizing aqueous titanium, makes titanium oxide; With calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A: the logarithm value of median diameter, the pore aperture logarithm value of B:2% pore volume, the pore aperture logarithm value of C:98% pore volume } the pore dissymmetryc coefficient N that draws is in the scope of 1.5≤N≤4; Be controlled to any pore aperture; And have the pore distribution shape that distributes along the reaction molecular amount, have more high-specific surface area than the porous titanium oxide of even control particle diameter, and mechanical strength is good; In the said method for preparing porous titanium oxide; Comprise the pH swinging operation when oxidizing aqueous titanium is synthetic, the low pH side scope of said pH swinging operation in the non-dissolving pH scope of oxidizing aqueous titanium { { carry out between 5.1≤pH≤7.1}, perhaps { near the pH scope the isoelectric point of 1＜pH≤4} and oxidizing aqueous titanium { is carried out between 8≤pH≤12} near the pH scope the isoelectric point by 5.1≤pH≤7.1} and high pH side scope; Perhaps in the said method for preparing porous titanium oxide; PH swinging operation when making oxidizing aqueous titanium synthetic, the low pH side scope in the pH scope of not dissolving of oxidizing aqueous titanium 1＜pH≤4} with surpass near the isoelectric point pH scope carry out in the scope of 5.1≤pH≤7.1}, and high pH side scope 8≤pH≤12} with { carry out in the scope of 5.1≤pH≤7.1} above near the pH scope the isoelectric point; { 5.1≤pH≤7.1} reserves the enough maturation time near isoelectric point pH scope, and particle is grown up fully simultaneously.

Fourth aspect of the present invention relates to the hydrocarbon oil hydrogenation Catalysts and its preparation method, wherein, and through at general formula TiO _(2-x)(OH) _2x(in the formula, x representes the number of x＞0.1) or composition formula TiO _(2-x)(OH) _2xYH ₂O (in the formula, x is 0.1≤x＜2.0, and y is 0.3≤y≤40) or composition formula TiO _(2-x)(OH) _2xYH ₂O is (in the formula; X is 0.2≤x＜1.0; Y is 0.3≤y≤40) in the hydrosol, hydrogel or these the dry thing of represented oxidizing aqueous titanium, interpolation can provide the compound of selecting in the compound of the ion that contains the element with high active of hydrogenation catalysis more than at least 2 kinds, and the compound more than 2 kinds that primary catalyst component and co-catalyst component preferably can be provided is as the particle inhibitor of growing up; After with the ion of these elements the hydroxyl of oxidizing aqueous titanium being exchanged; Carry out drying, roasting again, make titania oxide supported catalyst, specific area 80m ²More than/the g, more than the pore volume 0.2ml/g, the narrow degree of distribution of pore is more than 50%, has good desulfurization performance and nitrogen removal performance, and the hydrogen consumption is few.Also relate to the hydrocarbon oil hydrogenation process for purification that uses this hydrogenation catalyst.

Here, general formula TiO _(2-x)(OH) _2x, or composition formula TiO _(2-x)(OH) _2xYH ₂The oxidizing aqueous titanium that O representes can be divided into TiO _(2-x)(OH) _2xRepresented and oxidizing aqueous titanium carry out the part and the yH of chemically combined constitution water ₂The represented part with the Free water coexistence of oxidizing aqueous titanium physical property of O; Among the present invention, the gauge of this constitution water be decided to be under 120 ℃, 3 hours the drying condition with the weight of the dried dry titanium oxide of oxidizing aqueous titanium weight change amount with titania weight after 500 ℃, 3 hours condition should the roasting of drying titanium oxide.And, yH ₂The gauge of the Free water that O representes is decided to be the weight of undried oxidizing aqueous titanium and the weight change amount of dry titania weight.

Among the present invention, formula M O _(2-x)(OH) _2x(in the formula; M representes 4 family's metals; X representes the number of x＞0.1) meaning of " x＞0.1 " in the hydrosol, hydrogel or these the dry thing of represented 4 family's metal hydrous oxides; The lower limit that is the hydrosol that means 4 family's metal hydrous oxides, hydrogel or these the OH that dry thing had base surpasses 0.1 value, but the scope of 0.1≤x＜2.0 preferably, is more preferably the scope of 0.2≤x＜1.0.The hydrosol of this 4 family's metal hydrous oxides, hydrogel or these dry thing; Its OH group is heated when breaking away from; Because sintering or dehydrating condensation cause particle and grow up; Improve heat endurance, and become high-specific surface area through replaceable OH base and other functional group etc. are replaced this moment.Therefore, as 4 family's metal hydrous oxides, can adopt the material of the method preparation of in the past general Hydrolyze method, neutralization reaction method, sol-gal process etc.

And as this 4 family's metal hydrous oxides, preferred 4 family's metal M are titanium (Ti), and general formula TiO preferably _(2-x)(OH) _2x(in the formula, x representes the number of x＞0.1) or composition formula TiO _(2-x)(OH) _2xYH ₂O (in the formula, x is 0.1≤x＜2.0, and y is 0.3≤y≤40) or composition formula TiO _(2-x)(OH) _2xYH ₂The oxidizing aqueous titanium of O (in the formula, x is 0.2≤x＜1.0, and y is 0.3≤y≤40) expression.The value of x is 0.1 when following in the above-mentioned general formula; The crystalline growth of oxidizing aqueous titanium; There is the problem that is difficult to obtain high-specific surface area; Or reduce with hydroxyl that the catalyst component on oxidizing aqueous titanium surface carries out ion-exchange, there is the problem that is difficult to high concentration and makes the catalyst component high degree of dispersion equably.On the contrary, the value of x is 2.0 when above, and oxidizing aqueous titanium does not form crystallization; Sometimes can not obtain the hydrosol or the hydrogel of oxidizing aqueous titanium, though consider from the viewpoint of loading with catalyst component, preferably to carry out the hydroxyl of ion-exchange many with catalyst component; But the crystalline particle of oxidizing aqueous titanium is little sometimes; It is amorphous that X-ray diffraction shows, the pore structure of the catalyst that drying and roasting makes is inapplicable or as the hydrotreating catalyst poor performance, is unfavorable.In addition, the value of y was less than 0.3 o'clock in the above-mentioned general formula, and oxidizing aqueous titanium is roughly dry status; Under such state, add catalyst component, be difficult to high degree of dispersion equably, in addition; Even stir after adding the solution that contains catalyst component; The particle of oxidizing aqueous titanium also condenses, and is difficult to even dispersion, and therefore this situation also is difficult to high degree of dispersion equably.As a result, when making to high concentration catalyst component load with on titanium oxide, high degree of dispersion equably forms the agglomerate or the caking of catalyst component, causes catalyst activity low.Otherwise the value of y surpasses at 40 o'clock, is not that the Free water of constitution water of oxidizing aqueous titanium is too many, and therefore oxidizing aqueous titanium can not moulding, even or moulding, also be difficult to keep its shape.In addition, when being added in the solution that contains catalyst component, this solution is diluted, and most of catalyst components do not carry out ion-exchange, produces the problem that does not have effect.

Here; 4 family's metallic compounds as the raw material used of the hydrosol, hydrogel or these dry thing of preparation 4 family's metal hydrous oxides; 4 family's metal oxygen-containing hydrochlorates of 4 family's slaines of the chloride of titanium (Ti), zirconium (Zr) or hafnium (Hf), fluoride, bromide, iodide, nitrate, sulfate, carbonate, acetate, phosphate, borate, oxalates, hydrofluoride, silicate, iodate etc., or metatitanic acid specifically, zirconic acid, hafnium acid etc. etc. and 4 family's metal alkoxide classes.Among these 4 family metallic compounds; When titanium (Ti); As most preferred, for example can enumerate titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium trichloride, methoxyl group titanium, ethanolato-titanium, titanium propanolate, titanium isopropoxide, tetraisopropoxy titanium, four titanium butoxide, ortho-titanic acid, metatitanic acid, titanium tetrabromide, titanium tetrafluoride, titanium trifluoride, potassium titanate, sodium titanate, barium titanate etc.In addition, as most preferred, for example can enumerate zirconium chloride, zirconium oxychloride, zirconium sulfate, zirconium nitrate, acetic acid zirconium, acetyl acetone zirconium, propoxyl group zirconium, tert-butoxy zirconium etc. during zirconium (Zr).Perhaps during hafnium (Hf) as most preferred, for example can enumerate hafnium chloride, hafnium sulfate, oxychlorination hafnium etc.In addition, 4 family's metallic compounds of these raw materials except can only using it a kind individually, can also use the mixture more than 2 kinds.

In addition; As the synthetic middle pH conditioning agent that uses of above-mentioned 4 family's metal hydrous oxides; Can enumerate 4 family's slaines etc. of the chloride, fluoride, bromide, iodide, nitrate, sulfate, carbonate, acetate, phosphate, borate, oxalates, hydrofluoride, silicate, iodate etc. of this 4 family metal, and compound (salt) that adds as the particle growth inhibitor of following explanation or various acid or alkali.

Here; If enumerate the preferred concrete example of the synthetic middle pH conditioning agent that uses of oxidizing aqueous titanium; As the salt of titanium, for example can enumerate titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium trichloride, titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, titanium trifluoride etc., and the compound (salt) that adds as particle growth inhibitor; For example can enumerate ferrous sulfate, ferric sulfate, frerrous chloride, iron chloride, ferrous nitrate, ferric nitrate, nickel nitrate, nickelous sulfate, nickel chloride, cobalt nitrate, cobaltous sulfate, cobalt chloride, manganese nitrate, manganese sulfate, manganese chloride, yttrium nitrate, yttrium sulfate, yttrium chloride etc.; In addition, as acid, for example can enumerate nitric acid (HNO ₃), hydrochloric acid (HCl), sulfuric acid (H ₂SO ₄), carbonic acid (H ₂CO ₃), formic acid (HCOOH), acetic acid (CH ₃COOH) etc., in addition,, for example can enumerate ammonia (NH as alkali ₃), NaOH (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂CO ₃), potash (K ₂CO ₃), sodium acid carbonate (NaHCO ₃), saleratus (KHCO ₃) alkali that waits.These pH conditioning agents except can only using individually a kind, can also use the mixture more than 2 kinds.

In addition, the water solvent that uses during as synthetic 4 family metal hydrous oxides does not have particular restriction, except water, can also use the aqueous solution etc. of the water-miscible organic solvent of methyl alcohol, ethanol, propyl alcohol, oxolane, acetone 、 diox etc.

In addition, the hydrosol of above-mentioned 4 family's metal hydrous oxides, hydrogel or these dry thing can adopt 4 family's metallic compounds that make above-mentioned raw materials and the method that the pH conditioning agent reacts in water solvent synthetic.For example, synthetic oxidizing aqueous titanium can use the acid of above-mentioned pH conditioning agent or alkali in water solvent, the titanium compound of above-mentioned raw materials to be hydrolyzed during as 4 family metal hydrous oxides, perhaps adopts the method preparation of alkali neutralization.

In addition, in the hydrolysis or alkali neutralization reaction of the titanium compound of this raw material, the concentration of titanium is pressed titanium oxide (TiO in the water solvent ₂) converting is generally 0.1-15 weight %, is preferably 0.5-10 weight %, 0.5-6 weight % more preferably, reaction temperature is a normal temperature-300 ℃; Preferred normal temperature-180 ℃, more preferably normal temperature-100 ℃, and reaction pressure is normal pressure (OMPa)-9.0MPa; Preferred 0-3.0MPa, more preferably 0-0.9MPa, preferred again 0-0.5MPa; In addition, thus in order to control the application target that pore structure makes it to meet titanium oxide, suitably select the pH value.

Here; Among the present invention in order to make the porous 4 group metal oxide of pore structures such as control pore aperture and pore distribution; When the hydrosol that synthesizes above-mentioned 4 family's metal hydrous oxides, hydrogel or these dry thing; Use the 4 family's metallic compounds and the pH conditioning agent of this raw material, the pH swinging operation more than alternately carrying out repeatedly between the pH value that in water solvent, differs from one another.

Especially for the size of accurately controlling pore and for obtaining the porous 4 group metal oxide of pore narrowly distributing, preferably carry out above-mentioned pH swinging operation with dissolving between the pH scope in the deposition pH scope of 4 family's metal hydrous oxides.For example; When the hydrosol of synthetic oxidizing aqueous titanium or hydrogel, preferably at the electrochemistry potential energy figure of titanium oxide (M.Pourbaix, " electrochemical equilibrium atlas in the aqueous solution "; Pergamon Press; London (1966) alternately more than the swing repeatedly, swings 2-20 time between the deposition pH scope of the oxidizing aqueous titanium shown in P.218) and the dissolving pH scope usually; Value, the pH value of soluble end and the number of times of swinging of areas of sedimentation pH through regulating this moment can be controlled the pore structure of pore aperture and the pore distribution etc. of the oxidizing aqueous titanium particle that is synthesized more to heavens.For example, when between pH1 and pH7, swinging 2 times, the peak value in pore aperture was 8.2nm during pore distributed, and when between pH1 and pH7, swinging 4 times, the peak value in pore aperture was 16.1nm etc. during pore distributed, and can prepare the porous titanium oxide of accurate control pore structure.

In addition; 4 family's metal M are porous titanium oxides of titanium (Ti); When requiring the performance of good mechanical strength; Porous titanium oxide can be prepared as follows: 1. to above-mentioned pH swinging operation; In the electrochemistry potential energy figure of titanium oxide in the scope of the pH scope of not dissolving (1＜pH≤12) of oxidizing aqueous titanium, low pH side scope near the pH scope the isoelectric point of 1＜pH≤4} and oxidizing aqueous titanium between 5.1≤pH≤7.1}, or near the pH scope the isoelectric point { 5.1≤pH≤7.1} and high pH side scope { are carried out between 8≤pH≤12}; Perhaps; 2. { 1＜pH≤4} and near the pH scope that surpasses the isoelectric point { carry out above-mentioned pH swinging operation between the scope of 5.1≤pH≤7.1}, and { 8≤pH≤12} are with { carry out above-mentioned pH swinging operation between the scope of 5.1≤pH≤7.1}, { 5.1≤pH≤7.1} reserves the enough maturation time near the pH scope of while isoelectric point to the low pH side scope in not dissolving pH scope (1＜pH≤12) above near the pH scope the isoelectric point in high pH side scope; Particle is fully grown up to; This method is suitable for preparing the porous titanium oxide of pore dissymmetryc coefficient N in 1.5≤N≤4 scopes that calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A), A in the formula: the logarithm value in the pore aperture of the logarithm value of median diameter, B:2% pore volume, the logarithm value in the pore aperture of C:98% pore volume } draws.

Among the present invention, in the hydrosol, hydrogel or these the dry thing of 4 synthetic like this family's metal hydrous oxides, add after the particle growth inhibitor, carry out drying, roasting, the preparation porous 4 group metal oxide.

Here, at general formula TiO _(2-x)(OH) _2xAdd in the hydrosol of the oxidizing aqueous titanium that (in the formula, x representes the number of x＞0.1) is represented, hydrogel or these the dry thing after the particle growth inhibitor, carry out drying, roasting, even preparation roasting under 500 ℃, 3 hours hot conditions still has 80m ²The high-specific surface area of the above pore volume of above specific area, the 0.2ml/g of/g, the narrow degree of distribution of pore 50% or more and Heat stability is good, the purity of not only controlling pore aperture but also titanium oxide are the above highly purified porous titanium oxides as catalyst or catalyst carrier use of 97 weight %; Preferred particle growth inhibitor; For example can enumerate the compound that the ion that contains the element of from silicon (Si), phosphorus (P), magnesium (Mg), calcium (Ca), barium (Ba), manganese (Mn), aluminium (Al) and zirconium (Zr), selecting is provided; These compounds can also use the mixture more than 2 kinds except using it a kind individually.In addition, at 4 family's metal hydrous oxides, the compound that adds as particle growth inhibitor in the especially oxidizing aqueous titanium; Except the effect of high-specific surface area of oxidizing aqueous titanium is kept in embodiment, in the time of also should distributing, can not become its obstacle at the pore of control titanium oxide; In porous titanium oxide, exist as oxide; Should not form catalyst poison, consider that from the viewpoint of economy inexpensive grade also is important factor in addition.

The compound of the ion that contains this dvielement is provided, the particle of the hydrosol, hydrogel or these the dry thing of oxidizing aqueous titanium is played the effect of particle growth inhibitor, relevantly suppress the mechanism that particle grows up and estimate it is because of following effect.That is, though the particulate of oxidizing aqueous titanium is charged in the aqueous solution, its isoelectric point is when the anatase crystal type, and the pH value is about 6.1.And; Be lower than in the solution of isoelectric point in the pH value; The hydroxyl positively charged on oxidizing aqueous titanium particle surface, in the solution electronegative anion easily attached to the particle surface of this oxidizing aqueous titanium, and in pH value above in the solution of isoelectric point; The hydroxyl on oxidizing aqueous titanium particle surface is electronegative, and the cation of positively charged is easily attached to the particle surface of this oxidizing aqueous titanium in solution.And in this case, anion in the solution or cation be because electrostatic interaction and in the particle surface high degree of dispersion of oxidizing aqueous titanium, even measure fewerly with respect to surface hydroxyl, also effectively and securely combines.Therefore, during with oxidizing aqueous titanium roasting, the part of being carried out ion-exchange by anion or cation; Owing to combine securely with anion or cation; Therefore do not form the crystal lattice (Ti-O-Ti) of oxidizing aqueous titanium, can not cause the growth of crystallization, in addition;, estimate to be difficult to combine owing to receive the sterically hindered of anion or cationic moiety near the hydroxyl of anion or cation bound fraction with other the hydroxyl on oxidizing aqueous titanium particle surface.

From this viewpoint, suppress anion or cation that oxidizing aqueous titanium particle is grown up as stated, the more hydroxyl of ions bind of comparable 1 valency of the ion of multivalence, the particle growth to oxidizing aqueous titanium when drying, roasting presents better obstruction effect.And; Form anion or the cation of this multivalence, as the preferred compound that the particle growth inhibitor of oxidizing aqueous titanium uses, be the compound of above-mentioned silicon (Si), phosphorus (P), magnesium (Mg), calcium (Ca), barium (Ba), manganese (Mn), aluminium (Al) and zirconium (Zr).

Here, as the employed preferred compound of particle growth inhibitor of above-mentioned oxidizing aqueous titanium, can enumerate following compound particularly.That is,, can enumerate silicon tetrachloride, silica, silicic acid, silicate, silicic acid anhydride, silicic acid molybdenum, silicic acid ion etc. as the compound that silicon (Si) is.And, can enumerate ammonium salt, calcium salt, magnesium salts, barium salt, sylvite, sodium salt of phosphoric acid, phosphorous acid, metaphosphoric acid, pyrophosphoric acid, phosphorous oxide, phosphoric acid etc. as the compound that phosphorus (P) is.In addition; The compound that as magnesium (Mg) is; Can enumerate magnesium nitrate, magnesium sulfate, magnesium carbonate, antifungin, magnesium acetate, magnesia, magnesium hydroxide, magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, magnesium carbide, the organic acid that contains magnesium, magnesium, magnesium ion, magnesium molybdate, and the hydrate of above compound etc.

In addition; As the compound that calcium (Ca) is, can enumerate organic acid, calcium, calcium ion, calcium molybdate, and the hydrate of above compound etc. of calcium nitrate, calcium sulfate, calcium carbonate, line borate, calcium acetate, calcium oxide, calcium hydroxide, calcirm-fluoride, calcium chloride, calcium bromide, calcium iodide, calcium carbide, calcic.And; As the compound that barium (Ba) is, can enumerate organic acid, barium, barium ions, barium molybdate, and the hydrate of above compound etc. of barium nitrate, barium sulfate, brium carbonate, barium borate, barium acetate, barium monoxide, barium hydroxide, barium fluoride, barium chloride, barium bromide, barium iodide, barium carbide, baric.As the compound that manganese (Mn) is, can enumerate manganese nitrate, manganese sulfate, ammonium sulfate manganese, manganese carbonate, manganese borate, manganese acetate, manganese oxide, manganous hydroxide, manganous fluoride, manganese chloride, manganous bromide, manganese iodide, manganess carbide, the organic acid that contains manganese, manganese, permanganate, manganese molybdate, reach the hydrate of above compound etc.

In addition; As the compound that aluminium (Al) is, can enumerate aluminum acetate, aluminum ammonium sulfate, aluminium bromide, aluminium chloride, aluminum fluoride, aluminium hydroxide, aluctyl, aluminum nitrate, aluminum perchlorate, aluminum potassium sulfate, alumina silicate, aluminum sodium sulfate, aluminum sulfate, aluminum trifluoride, aluminium, reach the hydrate of above compound etc.In addition; As the compound that zirconium (Zr) is, can enumerate zirconium sulfate, sulfated zirconia, zirconium carbide, zirconium chloride, zirconium oxychloride, zircoium hydride, zirconium tetraiodide, zirconia, n-propoxyzirconium, zirconium nitrate, zirconium carbonate, zirconium hydroxide, zirconium sulfate, acetic acid zirconium, zirconium, reach the hydrate of above compound etc.

Yet,, consider that the effect when in the aqueous solution, existing with the form of oxo-anions is obvious as the silicon compound or the phosphorus compound that add the particle growth inhibitor in the oxidizing aqueous titanium to from the stable viewpoint of oxide.Compound form in the aqueous solution estimates that silicon compound mainly is SiO ₃ ^2-, phosphorus compound is PO ₄ ^3-And, the compound of the magnesium that ionization tendency is big, calcium, barium, zirconium and manganese, the effect when in the aqueous solution, existing with cationic form is obvious.The compound form of these particle growth inhibitor in the aqueous solution estimates it is respectively Mg ²⁺, Ca ²⁺, Ba ²⁺, Zr ⁴⁺, Mn ²⁺In addition, since the compound of aluminium as hydroxide Al ₂O ₃XH ₂O is more stable, but also can get anion or cationic any one form, pretend into anion with AlO ₃ ^3-Exist, and as cation with Al ³⁺Form exist.

In addition; In oxidizing aqueous titanium, add the concentration of compound during that the ion that contains the element of from this silicon (Si), phosphorus (P), magnesium (Mg), calcium (Ca), barium (Ba), manganese (Mn), aluminium (Al) and zirconium (Zr), being selected can be provided as particle growth inhibitor; There is not particular restriction; But preparation high-specific surface area and Heat stability is good, when accurately controlling the highly purified porous titanium oxide of size and pore narrowly distributing of pore; Because the purity of prepared porous titanium oxide preferably is the above high-purities of 97 weight % at least; Therefore press the oxide benchmark, the interpolation concentration in titanium oxide must be preferably in the scope of 0.2-2 weight % in the scope of 0.1-3 weight %.When the concentration of adding the particle growth inhibitor in this oxidizing aqueous titanium to is less than 0.1 weight %; The effect that increases the titanium oxide specific area is insufficient; Otherwise, during greater than 3 weight %, not only can not obtain highly purified porous titanium oxide; And the also less raising of the specific area of titanium oxide itself, there is not effect.

Here; In the for example oxidizing aqueous titanium of 4 family's metal hydrous oxides, add the method for above-mentioned particle growth inhibitor; There is not particular restriction; Can when the hydrosol for preparing oxidizing aqueous titanium or hydrogel, add in its synthesis material (for example 4 family's metallic compounds, pH conditioning agent, water solvent etc.), can also add in the reaction dissolvent when synthesizing; Can when carrying out the pH swinging operation, add to again in the 4 family's metallic compounds or pH conditioning agent of the raw material that its pH swinging operation uses, can also add in the stage before synthetic back, the dehydration in addition.

In addition; When using in the ammonia titanium chloride with raw material to prepare oxidizing aqueous titanium; Because the residual impurity that chlorine or ammonia etc. are arranged in the hydrosol of oxidizing aqueous titanium or the hydrogel; Therefore must remove these impurity with the washings washing,, can use the washings of the particle growth inhibitor that contains regulation as the washings that use in the filtration after this oxidizing aqueous titanium is synthetic, the washing procedure; Utilize these washings to add particle growth inhibitor in the oxidizing aqueous titanium to, can also particle grow up inhibitor mixed to the washing after the oxidizing aqueous titanium of gel in.At this moment, the concentration of particle growth inhibitor in the washings is by the oxide benchmark of this element, the preferably scope of 1-100ppm.Adopt these methods, then can be reduced at the operation of adding particle growth inhibitor in the oxidizing aqueous titanium significantly.In addition, the particle growth inhibitor of oxidizing aqueous titanium also can add in the oxidizing aqueous titanium after the dried.

In addition; When adding multivalent anions as the particle growth inhibitor of oxidizing aqueous titanium; Can make the pH value of colloidal sol or the gel of oxidizing aqueous titanium be lower than the isoelectric point of oxidizing aqueous titanium; When adding polyvalent cation as the particle growth inhibitor of oxidizing aqueous titanium, the pH value of colloidal sol or gel that preferably makes oxidizing aqueous titanium is above the isoelectric point of oxidizing aqueous titanium.In addition; Particle growth inhibitor as oxidizing aqueous titanium; When multivalent anions is added with polyvalent cation; The colloidal sol through making oxidizing aqueous titanium or the pH value of gel become isoelectric point ± 1.0 of oxidizing aqueous titanium, can make effectively on the colloidal sol or gel of particle growth inhibitor attached to oxidizing aqueous titanium.

Below, among the present invention, through at general formula TiO _(2-x)(OH) _2x(in the formula, x representes the number of x＞0.1) or composition formula TiO _(2-x)(OH) _2xYH ₂O (in the formula, x is 0.1≤x＜2.0, and y is 0.3≤y≤40) or composition formula TiO _(2-x)(OH) _2xYH ₂In the hydrosol, hydrogel or these the dry thing of the oxidizing aqueous titanium of O (in the formula, x is 0.2≤x＜1.0, and y is 0.3≤y≤40) expression, add after the particle growth inhibitor, carry out drying, roasting, preparation specific area 80m ²/ g is above, pore volume 0.2ml/g is above and the titania oxide supported catalyst of the narrow degree of distribution of pore more than 50%; When it is used as the hydrogenation catalyst of hydrocarbon ils; The compound that interpolation provides the ion that contains the element with high active of hydrogenation catalysis is as above-mentioned particle growth inhibitor, and the ion of these elements of usefulness exchanges the hydroxyl of oxidizing aqueous titanium.

The compound that uses as particle growth inhibitor in this purpose; Requirement provides the compound of the ion that contains the element with high active of hydrogenation catalysis; The compound that provides as the ion of the molybdenum (Mo) of major catalyst element and/or tungsten (W) must be arranged; Provide the compound of promoter elements of element that contains as other to comprise the element that contains the 9th family, the 10th family, the 13rd family and the 15th family; The preferred element from iron (Fe), nickel (Ni), cobalt (Co), phosphorus (P), boron (B), platinum (Pt), palladium (Pd), rhodium (Rh) and ruthenium (Ru); The compound of the ion of the element of more preferably from cobalt (Co), nickel (Ni), phosphorus (P) and boron (B), selecting, these compounds can only use a kind individually, also can use more than 2 kinds.

As the ion that the compound of particle growth inhibitor provides, in the aqueous solution, become anion or cation by these, anion is for example with Mo ₄ ^2-, WO ₄ ^2-, PO ₄ ^3-, BO ₃ ^3-Exist Deng oxo-anions or the anionic form of metal carbonyl, and cation is with Ni ²⁺, Co ²⁺Form Deng metal cation exists.When this type of load has the multiple element of high active of hydrogenation catalysis, not only can use compound each element of repeated boad repeatedly that contains various elements, can also use the mixture more than 2 kinds of the compound that contains each element, the multiple element of load simultaneously.

Here, as the compound that specially suitable oxo-anions is provided, can enumerate ammonium molybdate { (NH ₄) ₆Mo ₇O ₂₄4H ₂O, (NH ₄) ₂MoO ₄, (NH ₄) Mo ₂O ₇, sodium molybdate (Na ₂MoO ₄2H ₂O), molybdic acid (H ₂MoO ₄, H ₂MoO ₃H ₂O), molybdenum pentachloride (MoCl ₅), silicomolybdic acid (H ₄SiMo ₁₂O ₄₀NH ₂O), wolframic acid (H ₂WO ₄), ammonium tungstate { 5 (NH ₄) ₂O12WO ₃H ₂O, 3 (NH ₄) ₂O12WO ₃NH ₂O}, sodium tungstate (Na ₂WO ₄2H ₂O), H ₃PO ₄, HPO ₃, H4P ₂O ₇, P ₂O ₅, NH ₄H ₂PO ₄, (NH ₄) ₂HPO ₄, (NH ₄) ₃PO ₄H ₂O also can enumerate and make H ₃[PO ₄W ₁₂O ₃₆] 5H ₂O or Mo, W form the heteropolyacid salt of polyacid etc.

In addition, as the suitable compound that the anionic slaine of metal carbonyl is provided, be (NEt for example ₄) { Mo (CO) ₅(OOCCH ₃), Mo (CO) ₆-NEt ₃-EtSH, Ru ₃(CO) ₁₂-NEt ₃-EtSH, (η-C ₅H ₄Me) ₂Mo ₂Co ₂S ₃(CO) ₄, W (CO) ₆, W (CO) ₆-NEt ₃The metal carbonyl anion of representatives such as-EtSH.And as the suitable compound that the slaine of metal cation is provided, for example be nickel nitrate { Ni (NO ₃) ₂6H ₂O}, nickelous sulfate (NiSO ₄6H ₂O), nickel chloride (NiCl ₂), nickel acetate { Ni (CH ₃CO ₂) ₂4H ₂O}, cobalt acetate { Co (CH ₃CO ₂) ₂4H ₂O}, cobalt nitrate { Co (NO ₃) ₂6H ₂O}, cobaltous sulfate (CoSO ₄7H ₂O), cobalt chloride (CoCl ₂6H ₂O) etc.

In addition; The above-mentioned compound amount of adding as particle growth inhibitor for the hydroxyl with oxidizing aqueous titanium carries out the ion conversion with element of high active of hydrogenation catalysis; For the selectivity that improves denitrification reaction and improve desulfurization and two kinds of performances of denitrogenation; The amount of loading with of major catalyst molybdenum (Mo) and/or tungsten (W) is preferably more than the 15 weight % by the oxide benchmark; 20-40 weight % more preferably, and the amount of loading with of total catalyst composition is preferably more than the 20 weight % by the oxide benchmark, more preferably 30-47 weight %.When the amount of loading with of this major catalyst molybdenum (Mo) and/or tungsten (W) is lower than 15 weight %, can not obtain desired hydrogenation activity to hydrocarbon ils.

In addition; Has the few hydrocarbon oil hydrogenation catalyst of good desulfurization performance and nitrogen removal performance and hydrogen consumption in order to make; The ion exchange capacity that preferably makes the major catalyst element is 0.06-0.46 atom/1 atom titanium; And the ion exchange capacity that makes promoter elements is 0.02-0.26 atom/1 atom titanium, and total ion exchange capacity of these major catalyst elements and promoter elements is 0.08-0.82 atom/1 atom titanium.

In addition, as this method of preparation, can suitably use following method with titania oxide supported catalyst of high active of hydrogenation catalysis.Make the ion that contains the major catalyst element with the ion that contains promoter elements or contact with oxidizing aqueous titanium respectively and carry out ion-exchange, make the pH value at last after the scope of pH3-9, carry out moulding, drying, roasting again; Perhaps add oxidizing aqueous titanium in the dipping solution of ion that contains the major catalyst element and the ion that contains promoter elements to, under the condition of pH1-7 or pH9-11, contact, carry out ion-exchange; Then; Carry out moulding, drying, roasting after the filtration again, can also make the ion of the major catalyst element that contains molybdenum (Mo) and/or tungsten (W) composition, contact with the ion that contains the promoter elements of from cobalt (Co), nickel (Ni), phosphorus (P) and boron (B), selecting more than a kind; Carry out ion-exchange; Then, after the filtration, carry out moulding, drying, roasting.

More than 4 prepared family's metal hydrous oxides (oxidizing aqueous titanium) refilter, dewater, after dry, the roasting, become porous 4 group metal oxide (porous titanium oxide), and this moment; 4 families' metal hydrous oxides are dewatered or are dried to by solids benchmark water content is 200-900 weight %; Behind the preferred 250-600 weight %, be processed into desired shape, again at temperature 40-350 ℃; Preferred 80-200 ℃ was descended dry 0.5-24 hour; Preferred 0.5-5 hour, then temperature 350-1200 ℃, preferred 400-700 ℃ following roasting 0.5-24 hour, preferred 0.5-10 hour.

The porous 4 group metal oxide of the present invention that makes like this, the narrow degree of distribution of pore is more than 50% usually.And 4 family's metal M are the porous titanium oxide of titanium (Ti), even roasting under 500 ℃, 3 hours condition, the narrow degree of distribution of pore still is more than 50%, and pore volume is more than the 0.2ml/g, also to reach more than the 0.3ml/g sometimes.

In addition; Load of the present invention has the catalyst of the element of high active of hydrogenation catalysis; Be porous titanium oxide with good desulfurization performance and nitrogen removal performance as the hydrogenation catalyst of hydrocarbon ils, through in the presence of hydrogen, reaction temperature 280-400 ℃, reaction pressure 2-15MPa, LHSV0.3-10hr ^-1And contact under the hydroprocessing condition of hydrogen/oil ratio 50-500N1/1, can remove sulphur composition and nitrogen component in the hydrocarbon ils expeditiously.

Description of drawings

Heat treatment temperature when Fig. 1 is the titanium oxide hydrosol heat treatment before the expression embodiment 19 prepared interpolation particle growth inhibitor and the curve map of specific area relation.

Fig. 2 is the curve map that schematically shows the method for asking pore dissymmetryc coefficient N.

Fig. 3 is to use the porous titanium oxide of embodiment 1,9 and comparative example 2-4 to study the curve map of additive effect of the particle growth inhibitor of oxidizing aqueous titanium.

Fig. 4 is desulfurization degree and the curve map of denitrification percent relation in the hydrofinishing of Ni/Mo-aluminium oxide catalyst of Co/Mo-aluminium oxide catalyst and comparative example 12 of the expression titanium oxide catalyst and the comparative example 11 that use embodiment 27-30 and 32.

Fig. 5 is the curve map that expression embodiment 38 prepared hydrotreating catalysts adopt the line analysis result of X-ray microanalyzer (EPMA).

Fig. 6 representes the X-ray diffractogram of embodiment 38 prepared hydrotreating catalysts.

Fig. 7 representes molybdenum oxide (MoO ₃) X-ray diffractogram.

Fig. 8 is that expression uses the aluminium oxide catalyst of titanium oxide catalyst and comparative example 11 and 12 of embodiment 33 and 34 to make liquid air speed study the result's who concerns between denitrification percent and the hydrogen consumption curve map in the test of the range of 1-3.0l/h.

The preferred plan that carries out an invention

Below, according to embodiment and comparative example the preferred embodiments of the invention are described particularly.

Among the present invention, the method below the various physical properties of porous titanium oxide and oxidizing aqueous titanium adopt is measured.

[pore volume (TPV) and pore distribute]

The pore volume of porous titanium oxide and pore distribute, and use Shimadzu Seisakusho Ltd.'s system Autopore9200 type as determining instrument, and (write up is in E.W.Washburn, Proc.Natl to adopt mercury penetration method; Acad.Sci., 7,115 (1921), H.L.Ritter; L.E.Drake, Ind.Eng.Chem.Anal., 17,782; 787 (1945), L.C.Drake, Ind.Eng.Chem., 41; 780 (1949) and H.P.Grace, J.Amer.Inst.Chem.Engrs., documents such as 2.307 (1965)) measure.The surface tension of mercury is 0.48N/m, and using contact angle is 140 °, makes absolute mercury pressure change to 0.08-414MPa and measures.

[the narrow degree of distribution of pore]

About the accumulation pore distribution curve that the mercury porosimeter is measured, at first accumulate the longitudinal axis of pore volume and represent and ask the pore aperture (median diameter) of (1/2) PV of total pore volume (PVT) on the transverse axis of pore diameter (_) in expression.Then, the pore volume (PVM) of asking under the median diameter logarithm value ± having in 5% the pore pore diameter range by this pore volume (PVM) and total pore volume (PVT), is obtained the narrow degree of distribution of pore of expression pore distribution acutance according to following formula.

The narrow degree of distribution of pore

={ pore volume (PVM)/total pore volume (PVT) } * 100

Here the narrow degree of distribution of pore of definition is to estimate the pore that is suitable for reacting the most factor with respect to the degree of total pore volume, and the narrow degree of distribution of pore is big more, then has narrow pore more and distributes, and distributes for preferred pore more.

[crystalline texture]

Adopt X-ray diffraction method to measure the crystalline texture of catalyst and carrier, determining instrument uses pHILIPS corporate system PW3710.

[specific area]

The specific area of porous titanium oxide uses Mountec corporate system Macsorb Model-1201 as determining instrument, adopts the line-of-sight course of BET (seeing S.Brunauer for details, P.H.Emmett, E.Teller., J.Am.Chem., Soc., 60,309 (1938)) to measure.

[pore volume (TPV)]

The pore volume of porous titanium oxide uses Shimadzu Seisakusho Ltd.'s system Autopore 9200 types (mercury porosimeter) as determining instrument, and (write up is in E.W.Washburn, Proc.Natl.Acad.Sci., 7 to adopt mercury penetration method; 115 (1921), H.L.Ritter, L.E.Dr-ake, Ind.Eng.Chem.Anal.; 17,782,787 (1945); L.C.Drake, Ind.Eng.Chem., 41; 780 (1949) and H.P.Grace.J.Amer.Inst.Chem.Engrs., 2,307 (1965) etc. document) measures.The surface tension of mercury is 0.48N/m, and using contact angle is 140 °, makes absolute mercury pressure change to 0.08-414MPa and measures.

[pore dissymmetryc coefficient N]

Pore dissymmetryc coefficient N=(A-C)/(B-A) uses the figure shown in the relation of accumulation pore volume (longitudinal axis) that mercury porosimeter shown in Figure 2 measures and pore diameter (transverse axis: logarithm is represented) to obtain.That is, the logarithm value in the pore aperture (median diameter) at 50% pore volume place is A, and the logarithm value in the pore aperture at 2% pore volume place is B.In addition, the logarithm value in the pore aperture of 98% pore volume is C, shown in above-mentioned relational expression, representes with the ratio of distance between AB and the distance between CA.

[mechanical strength (SCS)]

Use log cabin formula intensitometer to measure mechanical strength (SCS).That is, use the following cylindric extrusion molding thing of the long 6mm of disk compression of diameter 10mm, adopt following formula, mechanical strength is obtained in increasing the weight of when destroying except that this article shaped with the length of cylindric extrusion molding thing.

SCS＝W/L

Increasing the weight of when W=destroys (kg)

The length (mm) of the cylindric extrusion molding thing of L=

Embodiment 1

(synthesis procedure of oxidizing aqueous titanium particle)

Use silicon tetrachloride (SiCl ₄) as the particle growth inhibitor of oxidizing aqueous titanium, be added with the aqueous solution of above-mentioned silicon tetrachloride [silicon concentration (SiO ₂Convert) 0.29g/l] in the container of 5500g, add the titanium tetrachloride aqueous solution 165g and the ammoniacal liquor 166g of concentration 14 weight % of concentration 500g/l, synthesize the hydrosol slurries of oxidizing aqueous titanium.The synthesis temperature of this moment is 60 ℃.

In the hydrosol slurries of the oxidizing aqueous titanium that makes, add the titanium tetrachloride aqueous solution 165g of concentration 500g/l, carry out the pH swinging operation; Promptly; Make pH get back to the soluble end of the oxidizing aqueous titanium of acidic side, add the ammoniacal liquor of 166g concentration 14 weight % then, make the pH of slurries become the areas of sedimentation of the oxidizing aqueous titanium of alkaline side; Continue 1 this pH swinging operation of repetition again, synthetic oxidizing aqueous titanium particle.In addition, the pH value of the final solution of the oxidizing aqueous titanium hydrosol slurries of this moment is 5.

(filter and cleaning process)

Filter the hydrosol slurries of synthetic oxidizing aqueous titanium, in order to wash chlorine and the ammonium ion in the gained gel off, the water that in slurries, mixes 7.5 liters repeats 2 filtration washing operations then as washings.Behind this filtration washing EO, carry out suction filtration at last, make the gel of oxidizing aqueous titanium.The water content of this gel (constitution water+Free water) is 300 weight % by the solids benchmark.

(extrusion molding operation)

Using the piston-type gel extrusion molding device of die size φ 1.8mm, is cylindric with using the synthetic oxidizing aqueous titanium of pH swinging operation gel shaped.

(drying and roasting operation)

Use drier; The cylindric article shaped of the oxidizing aqueous titanium hydrogel that the extrusion molding operation is made is carried out drying under 120 ℃, 3 hours condition; Use electric furnace under 500 ℃, 3 hours condition, the dry thing that makes to be carried out roasting, make porous titanium oxide.After the roasting, in drier, put cold.

Be shown in table 1 to the rerum natura of gained porous titanium oxide.

[table 1]

Embodiment 2

Except using the aqueous solution [phosphorus concentration (P of phosphoric acid ₂O ₅Convert) 0.25g/l] be beyond 80 ℃ as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

Embodiment 3

Except the aqueous solution [magnesium density (MgO conversions) 0.08g/l] that uses magnesium chloride hexahydrate as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium be 100 ℃, generate with the condition of embodiment 1 with the oxidizing aqueous titanium of measuring under carry out the final solution of 2 pH swinging operation and oxidizing aqueous titanium hydrosol slurries the pH value be 8, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

Embodiment 4

Except the calcium chloride water of the aqueous solution [calcium concentration (CaO conversions) 0.17g/l] that uses calcium chloride dihydrate as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium be 120 ℃, generate with the condition of embodiment 1 with the oxidizing aqueous titanium of measuring under carry out the final solution of 6 pH swinging operation and oxidizing aqueous titanium hydrosol slurries the pH value be 8, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

Embodiment 5

Except the aqueous solution [barium concentration (BaO conversion) 0.24g/l] that uses barium chloride dihydrate is that 140 ℃, the pH value of the final solution of oxidizing aqueous titanium hydrosol slurries are 8 as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

Embodiment 6

Except using the aqueous solution [zirconium concentration (ZrO of zirconium oxychloride eight hydrates ₂Convert) 0.33g/l] be beyond 160 ℃ as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium, other and embodiment 5 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

Embodiment 7

Except the aqueous solution [manganese concentration (MnO conversions) 0.22g/l] that uses the manganese chloride tetrahydrate as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium be 180 ℃, generate with the condition of embodiment 1 with the oxidizing aqueous titanium of measuring under to carry out 2 pH map functions and make the pH value of the final solution of oxidizing aqueous titanium hydrosol slurries be 8, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

Embodiment 8

Except using the aqueous solution [aluminum concentration (Al of aluminium chloride ₂O ₃Convert) 0.30g/l] be 40 ℃ and to make the pH value of the final solution of oxidizing aqueous titanium hydrosol slurries be beyond 7 as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 2 to the rerum natura of gained porous titanium oxide.

[table 2]

Among each embodiment of table 1 and table 2, the purity of titanium oxide of the present invention is more than the 97 weight %, and specific area is 80m ²More than/the g, pore volume (PVT) is more than the 0.3ml/g and the narrow degree of distribution of pore is more than 50%.

Embodiment 9

Except using silicon concentration (SiO ₂Conversion) beyond the particle growth inhibitor of the silicon tetrachloride aqueous solution as oxidizing aqueous titanium of 0.05g/l, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 3 to the rerum natura of gained porous titanium oxide.

Embodiment 10

Except using silicon concentration (SiO ₂Convert) and phosphorus concentration (P ₂O ₅Convert) silicon tetrachloride-phosphate aqueous solution of being respectively 0.09g/l as particle growth inhibitor, the synthesis temperature of oxidizing aqueous titanium be 80 ℃, generate with the condition of embodiment 1 with the oxidizing aqueous titanium of amount under carry out beyond 6 pH map functions, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 3 to the rerum natura of gained porous titanium oxide.

Embodiment 11

Use silicon tetrachloride, calcium chloride dihydrate and magnesium chloride hexahydrate particle growth inhibitor, use silicon concentration (SiO as oxidizing aqueous titanium ₂Conversion), calcium concentration (CaO conversion) and magnesium density (MgO conversion) are respectively the water solvent of silicon tetrachloride-calcium chloride-magnesium chloride brine of 0.15g/l, 0.15g/l and 0.04g/l as synthesis procedure.Synthesis temperature is 100 ℃ in addition; Under the condition that generates the oxidizing aqueous titanium of measuring together with embodiment 1, carry out the pH swinging operation 9 times; And the pH value that makes the final solution of oxidizing aqueous titanium hydrosol slurries is 7, and in addition, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 3 to the rerum natura of gained porous titanium oxide.

Embodiment 12

Except the particle growth inhibitor that does not use oxidizing aqueous titanium, other and embodiment 1 likewise prepare oxidizing aqueous titanium hydrosol slurries.The washings that use in the washing procedure as gained titanium oxide hydrogel slurries use silicon concentration (SiO ₂Convert), calcium concentration (CaO conversion) and magnesium density (MgO conversion) silicon tetrachloride-calcium chloride-magnesium chloride brine of being respectively 0.03g/l, 0.03g/l and 0.01g/l carries out washing operation.Except these were operated, other and embodiment 1 likewise made porous titanium oxide.

Be shown in table 3 to the rerum natura of gained porous titanium oxide.

Embodiment 13

Except the particle growth inhibitor that does not use oxidizing aqueous titanium, other and embodiment 1 likewise make the oxidizing aqueous titanium hydrogel of having accomplished washing.

Be equivalent to TiO ₂{ water content (constitution water+Free water) is to add by P among the 300 weight %} by the solids benchmark to the oxidizing aqueous titanium hydrogel of weight 50g ₂O ₅The ammonium dihydrogen phosphate (ADP) powder of conversion 0.92g is as the particle inhibitor of growing up, and carries out mixingly, makes it evenly to sneak in the oxidizing aqueous titanium.

Likewise make porous titanium oxide with embodiment 1 then.

Embodiment 14

To be equivalent to 50gTiO ₂The shaping and drying thing of oxidizing aqueous titanium, be immersed in phosphorus concentration (P as the particle growth inhibitor of oxidizing aqueous titanium ₂O ₅Conversion) among the phosphoric acid solution 200ml of 4.8g/l, then, likewise makes porous titanium oxide with embodiment 1 again.

Be shown in table 3 to the rerum natura of gained porous titanium oxide.

[table 3]

Embodiment the 10, the 11st, the effect when adding to the particle growth inhibitor of multiple oxidizing aqueous titanium in the synthetic; Embodiment 12 is the situation when adding to the particle growth inhibitor of oxidizing aqueous titanium in the gel detergent, and embodiment 13 and 14 expressions are respectively through adding particle growth inhibitor in the porous titanium oxide situation with the mixing of oxidizing aqueous titanium gel or to the dipping of dry thing.Under any situation, the purity that all shows titanium oxide of the present invention is more than the 97 weight %, and specific area is 80m ²More than/the g, pore volume (PVT) is more than the 0.3ml/g and the narrow degree of distribution of pore is more than 50%.

Comparative example 1

In the container that is added with 2 liters of boiling water, 0.3 liter of the titanium tetrachloride aqueous solution of adding 500g/l concentration, and make the liquid temperature remain on 95 ℃, 0.4 liter of the ammoniacal liquor of adding concentration 14 weight %, the hydrosol slurries of synthetic oxidizing aqueous titanium.Then, the same operation of titanium tetrachloride aqueous solution and ammoniacal liquor is added in repetition for twice under fluidized state, synthetic oxidizing aqueous titanium particle.And making the pH value of the final solution of oxidizing aqueous titanium hydrosol slurries this moment is 7.Likewise make porous titanium oxide with embodiment 1 then.

Be shown in table 4 to the rerum natura of gained porous titanium oxide.

Comparative example 1

Do not use the particle growth inhibitor of oxidizing aqueous titanium and do not carry out the pH swinging operation; Adopt the synthetic oxidizing aqueous titanium that is equivalent to 3 pH swinging operation amounts of embodiment 1 of 1 secondary response; The pH that makes oxidizing aqueous titanium hydrosol slurries is 7; In addition, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 4 to the rerum natura of gained porous titanium oxide.

Comparative example 2

Except the synthesis procedure at oxidizing aqueous titanium uses silicon concentration (SiO ₂Conversion) beyond the silicon tetrachloride aqueous solution of 0.009g/l, other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 4 to the rerum natura of gained porous titanium oxide.

Comparative example 3

Except in the synthesis procedure of oxidizing aqueous titanium, using silicon concentration (SiO ₂Conversion) beyond the silicon tetrachloride aqueous solution of 0.60g/l, other and the foregoing description 1 likewise make porous titanium oxide.

Be shown in table 4 to the rerum natura of gained porous titanium oxide.

Comparative example 4

Except the synthesis procedure at oxidizing aqueous titanium makes the pH value of the final solution of oxidizing aqueous titanium hydrosol slurries is 8, and other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 4 to the rerum natura of gained porous titanium oxide.

Comparative example 5

Except the synthesis procedure at oxidizing aqueous titanium uses the magnesium chloride brine of magnesium density (MgO conversion) 0.08g/l and makes the pH of the final solution of oxidizing aqueous titanium hydrosol slurries is 4, and other and embodiment 1 likewise make porous titanium oxide.

Be shown in table 4 to the rerum natura of gained porous titanium oxide.

[table 4]

Comparative example 1 is that the spy opens clear 56-120 in the table 4, carries out the porous titanium oxide of 3 pH swinging operation preparations under 1/5 scale of the embodiment 32 of No. 508 communiques, and comparative example 1 is the porous titanium oxide that does not add the particle growth inhibitor preparation of oxidizing aqueous titanium.The specific area of comparative example 1 and comparative example 1 is all than 80m ²/ g is little.Comparative example 2 is 0.1 weight % when following at particle growth inhibitor, and specific area compares 80m ²/ g is little, and the particle growth inhibitor of comparative example 3 and 4 is greater than 3 weight %, and the purity of titanium oxide also is lower than 97 weight %.In addition; In the comparative example 5; In synthetic, add the particle growth inhibitor of estimating as the oxidizing aqueous titanium of polyvalent cation existence (magnesium chloride hexahydrate); The pH that makes the final solution of oxidizing aqueous titanium hydrosol slurries is 4, and is lower than the isoelectric point of anatase crystallization, is illustrated in only in titanium oxide, to add trace magnesium under this condition.

According to the result of embodiment 1,9 and comparative example 2-4, the additive effect of the particle growth inhibitor of oxidizing aqueous titanium is described.

In the container that is added with 5500g water, add the sodium silicate aqueous solution 150g of concentration 100g/l, add the sulfuric acid solution of 20 weight % then, making pH is 4, the hydrosol slurries of synthetic oxidizing aqueous silicon.After this repeat 2 same interpolation operations, carry out the pH swinging operation 3 times, make the hydrosol slurries of oxidizing aqueous silicon.Likewise make porous silica with embodiment 31 then.To the high-purity mangesium oxide silicon measurement the specific area of gained purity 99.4 weight %, the result shows 650m ²The value of/g.The specific area 60m of the high-purity porous titanium oxide of the titanium oxide purity 99.2 weight % that this silica and comparative example 2 make ²The specific area of the high-purity porous titanium oxide mixing gained mixture of/g can be represented with the silica and the ratio of the mixed proportion of titanium oxide.

The porous titanium oxide of embodiment 1,9 and comparative example 2-4 contains in its preparation process the porous silica that silicon tetrachloride that the particle growth inhibitor as oxidizing aqueous titanium added produces.Therefore; Except the independent specific area increase effect of the particle growth inhibitor that increases the oxidizing aqueous titanium of effect from the specific area of interpolation silicon tetrachloride, can be expressed as poor (the increase part of specific area) of the specific area value of mixed high-purity mangesium oxide titanium identical and high-purity mangesium oxide silicon gained mixture with employing and embodiment 1,9 and comparative example 2-4.

Therefore; Effect for the particle growth inhibitor of confirming only to add among embodiment 1,9 and the comparative example 2-4 oxidizing aqueous titanium; Deduct the specific area that silica produced, obtain the increase part of specific area corresponding to the silica content in the porous titanium oxide of each embodiment 1,9 and comparative example 2-4.

The silica content that is shown in porous titanium oxide to the result is that the increase of x axle, specific area is partly among Fig. 3 of y axle.

Explain clearly that by this Fig. 3 silica content reaches before the 3 weight %, the increase of specific area part obviously, especially silica content reach the specific area before the 2 weight % the increase part significantly.The particle growth inhibitor of oxidizing aqueous titanium presents tangible effect in the increase of specific area.But the silica content shown in the comparative example 2 can not reach the desired specific area 80m of the present invention below 0.1 weight % ²More than/the g.When silica content surpassed 3 weight %, the increase effect of specific area descended gradually, even the particle growth inhibitor that adds oxidizing aqueous titanium above 3 weight % is described, this effect is also very little.

Embodiment 15

(synthesis procedure of oxidizing aqueous titanium particle)

In 11kg water, add the titanium tetrachloride aqueous solution 330g of concentration 500g/l, the pH value that makes synthetic solvent is 1.5, adds the ammoniacal liquor 340ml of concentration 14 weight % then, and making the pH value is 6.5, the hydrosol slurries of synthetic oxidizing aqueous titanium.The synthesis temperature of this moment is 60 ℃.

Then, in the hydrosol slurries of the oxidizing aqueous titanium of gained, add the titanium tetrachloride aqueous solution 330g of concentration 500g/l; Make the pH of these slurries get back to the pH1.5 of the sour side scope of oxidizing aqueous titanium; The ammoniacal liquor 355ml that adds concentration 14 weight % then, the pH value that makes slurries repeats this pH swinging operation near the pH6.3 the isoelectric point of oxidizing aqueous titanium; Carry out altogether 2 times with 4 times pH swinging operation, the particle of synthetic oxidizing aqueous titanium.

The synthetic oxidizing aqueous titanium that use makes likewise prepares porous titanium oxide with filtration, washing procedure, extrusion molding operation and the drying and roasting operation of the foregoing description 1.

Be shown in table 5 to the rerum natura of the porous titanium oxide that makes by synthetic oxidizing aqueous titanium.

[table 5]

Embodiment 16

In 11kg water, add the titanium tetrachloride aqueous solution 330g of concentration 500g/l, the pH value that makes synthetic solvent is 1.5, adds the ammoniacal liquor 355ml of concentration 14 weight % then, and making the pH value is 7.5, the hydrosol slurries of synthetic oxidizing aqueous titanium.The synthesis temperature of this moment is 75 ℃.

Then, in the hydrosol slurries of the oxidizing aqueous titanium that makes, add the titanium tetrachloride aqueous solution 330g of concentration 500g/l concentration; Make the pH value of these slurries get back to the pH1.5 of the sour side scope of oxidizing aqueous titanium, add the ammoniacal liquor 355ml of concentration 14 weight % then, make the isoelectric point of the pH value of slurries above oxidizing aqueous titanium; Reach pH7.5; Carry out this pH swinging operation repeatedly, carry out the pH swinging operation altogether 4 times, the particle of synthetic oxidizing aqueous titanium.

With prepared synthetic oxidizing aqueous titanium, likewise prepare porous titanium oxide with the foregoing description 15.Be shown in table 6 to the rerum natura of this porous titanium oxide.

Embodiment 17

The ammoniacal liquor 300ml that in 11kg water, adds concentration 14 weight %; Making pH is 9; The ammoniacal liquor 355ml of the titanium tetrachloride aqueous solution 330g of working concentration 500g/l and concentration 14 weight % then makes the pH swinging operation at the pH3.8 of sour side scope with surpass between the pH7.5 of isoelectric point of oxidizing aqueous titanium and add up to repetition 5 times, when pH6, keeps around here about 2 minutes; In addition, other and embodiment 15 likewise prepare porous titanium oxide.Be shown in table 6 to the rerum natura of this porous titanium oxide.

Embodiment 18

In 11kg water, add NaOH, making pH is 11.5, adds the titanium tetrachloride aqueous solution of concentration 500g/l then, and making pH is 5.8, amounts to 3 this pH swinging operation of repetition, and in addition, other and embodiment 15 likewise prepare porous titanium oxide.Be shown in table 6 to the rerum natura of this porous titanium oxide.

[table 6]

Comparative example 6

The ammoniacal liquor 355ml of the titanium tetrachloride aqueous solution 330g of working concentration 500g/l and concentration 14 weight %; Make the pH swinging operation between the pH4.5 of pH2.0 that hangs down the pH scope and high pH scope, amount to repetition 4 times; In addition, other and embodiment 15 likewise prepare porous titanium oxide.Be shown in table 7 to the rerum natura of this porous titanium oxide.

Comparative example 7

The ammoniacal liquor 355ml of the titanium tetrachloride aqueous solution 330g of working concentration 500g/l and concentration 14 weight %; Between the pH6.5 of pH4.5 that hangs down the pH scope and high pH scope, add up to and repeat the pH swinging operation 4 times; In addition, other and embodiment 15 likewise prepare porous titanium oxide.Be shown in table 7 to the rerum natura of this porous titanium oxide.

Comparative example 8

The ammoniacal liquor 355ml that in 11kg water, adds concentration 14 weight % earlier; The titanium tetrachloride aqueous solution 330g that adds concentration 500g/l again; The hydrosol slurries that prepare oxidizing aqueous titanium, the ammoniacal liquor 355ml of working concentration 14 weight % and the titanium tetrachloride aqueous solution 330g of concentration 500g/l then add up between the pH7.5 of the pH9.5 of alkaline side scope and low pH scope and carry out the pH swinging operation repeatedly 4 times; In addition, other and embodiment 15 likewise prepare porous titanium oxide.Be shown in table 7 to the rerum natura of this porous titanium oxide.

[table 7]

Embodiment 19

(synthesis procedure of oxidizing aqueous titanium particle)

In the 10kg pure water, add the titanium tetrachloride aqueous solution 1500g of concentration 210g/l, the pH value that makes synthetic solvent is 0.5, adds the ammoniacal liquor 2300g of concentration 14 weight % then, making the pH value is 7.0, the hydrosol slurries of synthetic oxidizing aqueous titanium.The synthesis temperature of this moment is 60 ℃.

Then; In the hydrosol slurries of the oxidizing aqueous titanium that makes, add the titanium tetrachloride aqueous solution 1500g of concentration 500g/l, make the pH value of these slurries get back to the pH0.5 (hydrosol dissolving pH scope) of the sour side scope of oxidizing aqueous titanium; The ammoniacal liquor 2800ml that adds concentration 14 weight % then; Make the pH value of slurries get back to 7.0 (hydrosol is separated out the pH scope), add up to and carry out this pH swinging operation repeatedly 5 times, the particle of synthetic oxidizing aqueous titanium.

(filter and cleaning process)

After above-mentioned hydrosol synthesis procedure finishes, filter,, repeat washing operation, up to adopting silver nitrate titration to confirm do not have chlorion (Cl in the filtrating with pure water washing gained filter cake ^-), make the titanium oxide hydrosol.

(preparation section of dry thing)

The as above titanium oxide hydrosol of gained is carried out suction filtration; Dehydration becomes about 50 weight % up to water content (constitution water+Free water), uses the mould of aperture φ 1.8mm to carry out moulding then; The gained article shaped 120 ℃ of dryings 3 hours, is made titanium oxide drying and moulding thing.

(particle growth inhibitor adds operation)

The above-mentioned titanium oxide drying and moulding thing that makes, be immersed in corresponding to the containing in the aqueous solution of ammonium paramolybdate of 16.3 weight % of titanium oxide by the oxide benchmark, at room temperature place 2 hours after, filter with the filter paper of 5C, make and carry a molybdenum thing.

(drying and roasting operation)

,, make the molybdenum thing that carries to carry the molybdenum titanium oxide catalyst after 3 hours 120 ℃ of dryings 500 ℃ of roastings 3 hours.

The rerum natura of carrying gained the molybdenum titanium oxide catalyst is shown in table 8.

Embodiment 20

The hydrosol after the washing among the embodiment 19; Be immersed in corresponding to the containing in the aqueous solution of ammonium paramolybdate of 16.3 weight % of titanium oxide by the oxide benchmark, at room temperature place 2 hours after, suction filtration; Dewater, become 400 weight % up to water content (constitution water+Free water).Use the mould of aperture φ 1.5mm to carry out moulding then, the gained article shaped, 500 ℃ of roastings 3 hours, is made and carries the molybdenum titanium oxide catalyst after 3 hours 120 ℃ of dryings.

Be shown in table 8 to the rerum natura of gained catalyst.

Embodiment 21

Except use simultaneously corresponding to titanium oxide by the ammonium paramolybdate of the cobalt nitrate of oxide benchmark 3.0 weight % and 10.0 weight % as the particle growth inhibitor, other and embodiment 20 likewise make and carry a cobalt-molybdenum titanium oxide catalyst.

Be shown in table 8 to the rerum natura of gained catalyst.

Embodiment 22

The hydrogel after filtering among the embodiment 19; Be immersed in the aqueous solution that contains as particle growth inhibitor by the ammonium paramolybdate of the phosphoric acid of oxide benchmark 2.0 weight % and 8.0 weight % and 2.0 weight % cobalt nitrates corresponding to titanium oxide; After at room temperature placing 2 hours; Suction filtration dewaters, and becomes 400 weight % up to amount of moisture (constitution water+Free water) by the solids benchmark.Then, use the mould of aperture φ 1.8mm to carry out moulding, the gained article shaped, 500 ℃ of roastings 3 hours, is made and carries phosphorus, molybdenum, cobalt oxidation titanium catalyst after 3 hours 120 ℃ of dryings.

Be shown in table 8 to the rerum natura of gained catalyst.

[table 8]

Embodiment 23

As particle growth inhibitor; Except corresponding to the using simultaneously the nickel nitrate of ammonium paramolybdate and 2.0 weight % of phosphoric acid and 8.0 weight % of 2.0 weight % by the oxide benchmark of titanium oxide, other and embodiment 22 likewise make and carry phosphorus, molybdenum, nickel titanium oxide catalyst.

Be shown in table 9 to the rerum natura of gained catalyst.

Embodiment 24

As particle growth inhibitor; Except corresponding to the using simultaneously the cobalt nitrate of ammonium paramolybdate and 2.0 weight % of nickel nitrate and 8.0 weight % of 2.0 weight % by the oxide benchmark of titanium oxide, other and embodiment 22 likewise make and carry nickel, molybdenum, cobalt oxidation titanium catalyst.

Be shown in table 9 to the rerum natura of gained catalyst.

Embodiment 25

As particle growth inhibitor; Except corresponding to the using simultaneously the nickel nitrate of ammonium metatungstate and 2.0 weight of phosphoric acid and 8.0 weight % of 2.0 weight % by the oxide benchmark of titanium oxide, other and embodiment 20 likewise make and carry phosphorus, tungsten, nickel titanium oxide catalyst.

Be shown in table 9 to the rerum natura of gained catalyst.

Embodiment 26

Adopt the method same with embodiment 19; With zirconium oxychloride as raw material; Zirconia hydrogel after filtering is immersed in containing in the aqueous solution of ammonium paramolybdate of 16.3 weight % by the oxide benchmark corresponding to titanium oxide; After at room temperature placing 2 hours, suction filtration, dehydration become 400 weight % up to amount of moisture (constitution water+Free water) by the solids benchmark.Then, use the mould of aperture φ 1.5mm to carry out moulding,,, make the gained article shaped to carry the molybdenum zirconia catalyst after 3 hours 120 ℃ of dryings 500 ℃ of roastings 3 hours.

Be shown in table 9 to the rerum natura of gained catalyst.

[table 9]

Comparative example 9

Carry out roasting to the titanium oxide shaping and drying thing before the interpolation particle growth inhibitor of embodiment 19 gained at 500 ℃, the preparation titanium dioxide carrier.

Be shown in table 10 to the rerum natura of gained titanium dioxide carrier.

Comparative example 10

The titanium oxide article shaped before the interpolation particle growth inhibitor of embodiment 2 gained 370 ℃ of dryings; After the amount of moisture of hydrous oxide is adjusted to low concentration; Interpolation corresponding to titanium oxide by the ammonium paramolybdate of oxide benchmark 16.3 weight % as the particle inhibitor of growing up; In addition, other and embodiment 19 likewise make and carry a molybdenum titanium oxide catalyst.

Be shown in table 10 to the rerum natura of gained catalyst.

[table 10]

Embodiment 27

(synthesis procedure of oxidizing aqueous titanium particle)

In the 10kg pure water, add the titanium tetrachloride aqueous solution 1500g of concentration 210g/l, the pH value that makes synthetic solvent is 0.5, adds the ammoniacal liquor 2300g of concentration 14 weight % then, and making the pH value is 7.0, the hydrosol slurries of synthetic oxidizing aqueous titanium.The synthesis temperature of this moment is 80 ℃.

Then, in the hydrosol slurries of the oxidizing aqueous titanium of gained, add the titanium tetrachloride aqueous solution 1500g of concentration 500g/l; Make the pH value of these slurries get back to the pR0.5 (hydrosol dissolving pH scope) of the sour side scope of oxidizing aqueous titanium; The ammoniacal liquor 2800ml that adds concentration 14 weight % again, the pH value that makes slurries is 7.0 (hydrosol is separated out the pH scope), adds up to carry out this pH swinging operation repeatedly 5 times; Filtered water gel then; With pure water washing gained filter cake, carry out this pure water washing repeatedly, up to adopting silver nitrate titration to confirm not have chlorion (Cl ^-), refilter, at normal temperatures the gained filter cake is dewatered, be about 300 weight % up to amount of moisture (constitution water+Free water) by the solids benchmark, make oxidizing aqueous titanium hydrogel.

(with the ion-exchange of the ion that contains catalyst component)

In the oxidizing aqueous titanium hydrogel that makes like this, add the ammonium paramolybdate [(NH that contains 30 weight % by the oxide benchmark ₄) ₆Mo ₇O ₂₄6H ₂O] and the phosphoric acid (H of 4 weight % ₃PO ₄) and the cobalt nitrate [Co (NO of 4 weight % ₃) ₂6H ₂O] the aqueous solution (ion that contains catalyst component), use kneader mixing 2 hours of limit at room temperature, the limit makes the mixing thing of ion-exchange.

(moulding of catalyst, drying, roasting)

Then, use the mould of aperture 2.4mm, mixing thing is processed into cylindric, 120 ℃ of dryings 3 hours,, make the hydrotreating catalyst that the titanium oxide of loading with catalyst component constitutes to this article shaped again 500 ℃ of roastings 3 hours.

Be shown in table 11 to the rerum natura of the hydrotreating catalyst of gained embodiment 46.

Embodiment 28

When preparing oxidizing aqueous titanium hydrogel, do not carry out the pH conversion and carry out the interpolation of titanium tetrachloride aqueous solution and ammonia spirit, in this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component, make molybdenum (MoO by the oxide benchmark ₃) be that 37 weight %, cobalt (CoO) they are 5 weight %, phosphorus (P ₂O ₅) be 5 weight %, in addition, other and the foregoing description 27 likewise make the hydrotreating catalyst of the titanium oxide formation of loading with catalyst component.

Be shown in table 11 to the rerum natura of the hydrotreating catalyst of gained embodiment 28.

Embodiment 29

When preparing oxidizing aqueous titanium hydrogel, carry out the interpolation operation (pH swinging operation) of 7 titanium tetrachloride aqueous solutions and ammonia spirit altogether.In this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component then, make molybdenum (MoO by the oxide benchmark ₃) be that 20 weight %, cobalt (CoO) they are 4 weight %, phosphorus (P ₂O ₅) be 7 weight %, in addition, other and the foregoing description 27 likewise prepare the hydrotreating catalyst of the titanium oxide formation of loading with catalyst component.

Be shown in table 11 to the rerum natura of the hydrotreating catalyst of gained embodiment 29.

Embodiment 30

When preparing oxidizing aqueous titanium hydrogel, carry out the interpolation operation (pH swinging operation) of 12 titanium tetrachloride aqueous solutions and ammonia spirit altogether, in this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component, make molybdenum (MoO by the oxide benchmark ₃) be that 23 weight %, cobalt (CoO) they are 4 weight %, phosphorus (P ₂O ₅) be 5 weight %, in addition, other and the foregoing description 27 likewise make the hydrotreating catalyst of the titanium oxide formation of loading with catalyst component.

Be shown in table 11 to the rerum natura of the hydrotreating catalyst of gained embodiment 30.

Embodiment 31

When preparing oxidizing aqueous titanium hydrogel, carry out the interpolation operation (pH swinging operation) of 4 titanium tetrachloride aqueous solutions and ammonia spirit altogether, in this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component, make tungsten (WO by the oxide benchmark ₃) be that 25 weight %, nickel (NiO) they are 5 weight %, in addition, other and the foregoing description 27 likewise make the hydrotreating catalyst of the titanium oxide formation of loading with catalyst component.

Be shown in table 11 to the rerum natura of the hydrotreating catalyst of gained embodiment 31.

Embodiment 32

When preparing oxidizing aqueous titanium hydrogel, carry out the interpolation operation (pH swinging operation) of 7 titanium tetrachloride aqueous solutions and ammonia spirit altogether, in this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component, make molybdenum (MoO by the oxide benchmark ₃) be that 30 weight %, cobalt (CoO) they are 4 weight %, boron (B ₂O ₃) be 3 weight %, in addition, other and the foregoing description 27 likewise make the hydrotreating catalyst of the titanium oxide formation of loading with catalyst component.

Be shown in table 11 to the rerum natura of the hydrotreating catalyst of gained embodiment 32.

[table 11]

Comparative example 11

Use industry to go up the BET specific area 241m that uses as light oil deep desulfuration purposes ²The aluminium oxide of/g is loaded with cobalt-molybdenum-catalyst (CoO 5.1 weight %/MoO ₃20.0 weight %/P ₂O ₅1.1 weight %).

Be shown in table 12 to the rerum natura of the hydrotreating catalyst of used comparative example 11.

Comparative example 12

Use the different BET specific area 241m of the catalyst component amount of loading with that goes up the above-mentioned comparative example 11 that uses with industry as light oil deep desulfuration purposes ²The aluminium oxide of/g is loaded with nickel-molybdenum (NiO 3.6 weight %/MoO ₃20.4 catalyst weight %).

Be shown in table 12 to the rerum natura of the hydrotreating catalyst of used comparative example 12.

Comparative example 13

The oxidizing aqueous titanium hydrogel that embodiment 27 is made carries out machine-shaping; Then the gained article shaped 120 ℃ of dryings 3 hours; 500 ℃ of roastings 3 hours, the preparation calcining matter made this calcining matter dipping and the embodiment 27 employed identical aqueous solution (ion that contains catalyst component) again; And, make the hydrotreating catalyst of titania oxide supported catalyst component 120 ℃ of dryings 3 hours and 500 ℃ of roastings of carrying out 3 hours.

Be shown in table 12 to the rerum natura of the hydrotreating catalyst of gained comparative example 13.

Comparative example 14

When preparing oxidizing aqueous titanium hydrogel, carry out the interpolation operation (pH swinging operation) of 20 titanium tetrachloride aqueous solutions and ammonia spirit altogether, in this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component, make molybdenum (MoO by the oxide benchmark ₃) be that 28 weight %, cobalt (CoO) they are 4 weight %, phosphorus (P ₂O ₅) be 4 weight %, in addition, other and embodiment 27 likewise make the hydrotreating catalyst of titania oxide supported catalyst component.

Be shown in table 12 to the rerum natura of the hydrotreating catalyst of gained comparative example 14.

Comparative example 15

When preparing oxidizing aqueous titanium hydrogel, carry out the interpolation operation (pH swinging operation) of 7 titanium tetrachloride aqueous solutions and ammonia spirit altogether, in this oxidizing aqueous titanium hydrogel, add the ion that contains catalyst component, make molybdenum (MoO by the oxide benchmark ₃) be that 14 weight %, cobalt (CoO) they are 4 weight %, phosphorus (P ₂O ₅) be 3 weight %, in addition, other and embodiment 27 likewise make the hydrotreating catalyst of titania oxide supported catalyst component.

Be shown in table 12 to the rerum natura of the hydrotreating catalyst of gained comparative example 15.

[table 12]

Test Example 1: the hydrofinishing test of light oil

Use the hydrotreating catalyst of the foregoing description 27 and comparative example 11; Carry out proportion (15/4 ℃) 0.850, sulphur composition 1.37 weight %, nitrogen component 101ppm and the distillation performance is: the hydrofinishing test that it is straight run light oil that 232 ℃ of initial boiling points, 50% distillate 295 ℃ and 90% Middle East that distillate 348 ℃, the performance of research hydrogenation catalyst.

High-pressure spray general formula reaction unit is used in the hydrotreatment of light oil, under the condition of reaction pressure 5.0MPa, 350 ℃ of reaction temperatures, liquid air speed 2.0l/h and hydrogen/raw material ratio 250N1/1, implements.In addition, to supplying with the catalyst of test, all uses and add dimethyl disulfide and the also presulfurization in advance of light oil of the concentration adjustment of sulphur composition to 2.5 weight %.

The reaction result of hydrofinishing test, desulphurization reaction is 1.2 order reactions, denitrification reaction is 1 order reaction, asks for rate constant, and the result of comparative example 1 as " 1.0 ", is represented with relative value, in addition, also obtains hydrogen consumption (N1/1).

Be shown in table 11 and table 12 to the result.

(relation of denitrification percent and hydrogen consumption)

Then, the titanium oxide (titanium oxide catalyst) and the denitrification percent of the aluminium oxide catalyst of comparative example 11 and 12 and the relation of hydrogen consumption of the supported catalyst composition of research the foregoing description 27-30 are shown in table 11-12 to the result.

As show shown in the 11-12; Embodiment 27-30 adopts catalyst of the present invention; Not only its denitrification activity is high, approximately near comparative example 11 load with 3 times of Co/Mo aluminium oxide catalyst, and the hydrogen consumption is identical; Denitrification activity not only than the hydrogenation activity of comparative example 12 higher to load with the Ni/Mo aluminium oxide catalyst high about 1.5 times, and the approximately low 10N1/1 of hydrogen consumption.

Conclude that as stated the titanium oxide catalyst of embodiment 27-30 can suppress the hydrogen consumption significantly.

(relation of desulfurization degree and denitrification percent)

In addition, the titanium oxide of loading with catalyst component (titanium oxide catalyst) of having studied the foregoing description 27-30 and 32 and the desulfurization degree of the Ni/Mo-aluminium oxide catalyst of the Co/Mo-aluminium oxide catalyst of comparative example 11 and comparative example 12 and the relation of denitrification percent.

The result is as shown in Figure 4, distinguishes that the titanium oxide catalyst of embodiment is good to the selectivity of denitrification reaction, and the hydrorefined hydrotreating catalyst that is suitable as desulfurization and two kinds of purposes of denitrogenation uses.

Embodiment 33

(synthesis procedure of oxidizing aqueous titanium particle)

In the 10kg pure water, add the titanium tetrachloride aqueous solution 1500g of concentration 210g/l, the pH value that makes synthetic solvent is 0.5, adds the ammoniacal liquor 2300g of concentration 14 weight % then, making the pH value is 7.0, the hydrosol slurries of synthetic oxidizing aqueous titanium.The synthesis temperature of this moment is 60 ℃.

Then, in the hydrosol slurries of the oxidizing aqueous titanium of gained, add the titanium tetrachloride aqueous solution 1500g of concentration 500g/l; Make the pH value of these slurries get back to the pH0.5 (hydrosol dissolving pH scope) of the sour side scope of oxidizing aqueous titanium; The ammoniacal liquor 2800ml that adds concentration 14 weight % then makes the pH value of slurries get back to 7.0 (hydrosol is separated out the pH scope), multiple 3 this pH swinging operation of gross weight; Filtered water gel then; With pure water washing gained filter cake, carry out this pure water washing repeatedly, up to adopting silver nitrate titration to confirm not have chlorion (Cl ^-), refilter, the gained filter cake is carried out normal temperature dewatering, be about 300 weight % up to amount of moisture (constitution water+Free water) by solids, make oxidizing aqueous titanium hydrogel.

(with the ion-exchange of catalyst component)

In the above-mentioned oxidizing aqueous titanium that makes, add the ammonium paramolybdate ((NH that is equivalent to 0.26 atom with respect to per 1 atom titanium ₄) ₆Mo ₇O ₂₄4H ₂O), the phosphoric acid (H that is equivalent to 0.05 atom ₃PO ₄) and be equivalent to the cobalt nitrate ((Co (NO of 0.06 atom ₃) ₂6H ₂O), use mixer mixing 2 hours at normal temperature.The pH of this moment is 6.5.

(moulding, drying, roasting)

Then; Use the mould of aperture 2.4mm, with catalyst component carry out oxidizing aqueous titanium after the ion-exchange be processed into cylindric, with the gained article shaped after drying under 120 ℃, 3 hours the condition; Roasting under 500 ℃, 3 hours condition makes the hydrotreating catalyst of embodiment 33.Be shown in table 13 to the rerum natura of this hydrotreating catalyst.

Embodiment 34

Embodiment 33 prepared oxidizing aqueous titaniums, drop into and fully be dissolved with the ammonium paramolybdate ((NH that is equivalent to 0.47 atom with respect to per 1 atom titanium ₄) ₆Mo ₇O ₂₄4H ₂O), the phosphoric acid (H that is equivalent to 0.06 atom ₃PO ₄) and be equivalent to the cobalt nitrate ((Co (NO of 0.10 atom ₃) ₂6H ₂O) in the solution of pH9, stirred 3 hours, make its dispersion, carry out ion-exchange.

Then, the oxidizing aqueous titanium of filter ions exchange after the dehydration, likewise makes the hydrotreating catalyst of embodiment 34 with embodiment 55.Be shown in table 13 to the rerum natura of gained catalyst.

Embodiment 35

In the process of synthetic oxidizing aqueous titanium; Except in the dissolving pH of titanium hydroxide scope (pH=0.5) with to separate out the number of times that alternately carries out the pH swinging operation between the pH scope (pH=7.0) be 7 times, the likewise synthetic oxidizing aqueous titanium of other and the foregoing description 33.The oxidizing aqueous titanium of gained is filtered in compression, makes the filter cake that amount of moisture (constitution water+Free water) is pressed the oxidizing aqueous titanium of the about 10 weight % of solids benchmark.

In this oxidizing aqueous titanium, add the ammonium paramolybdate ((NH that is equivalent to 0.16 atom with respect to per 1 atom titanium ₄) ₆Mo ₇O ₂₄4H ₂O), the phosphoric acid (H that is equivalent to 0.11 atom ₃PO ₄) and be equivalent to the cobalt nitrate ((Co (NO of 0.06 atom ₃) ₂6H ₂O), likewise make the hydrotreating catalyst of embodiment 35 with embodiment 33.

Be shown in table 13 to the rerum natura of gained catalyst.

Embodiment 36

With the likewise synthetic oxidizing aqueous titanium of embodiment 33, use filtration and dehydration after vacuum filter washs.The amount of moisture of the oxidizing aqueous titanium of gained (constitution water+Free water) is about 400 weight % by the solids benchmark.In this oxidizing aqueous titanium, add the ammonium paramolybdate ((NH that is equivalent to 0.16 atom with respect to per 1 atom titanium ₄) ₆Mo ₇O ₂₄4H ₂O), the phosphoric acid (H that is equivalent to 0.12 atom ₃PO ₄) and be equivalent to the nickel nitrate ((Ni (NO of 0.05 atom ₃) ₂6H ₂O), likewise make hydrotreating catalyst with embodiment 33.Be shown in table 13 to the rerum natura of this catalyst.

Embodiment 37

Except in oxidizing aqueous titanium, adding the ammonium tungstate (NH that per 1 atom titanium is equivalent to 0.12 atom ₄) ₂WO ₄And be equivalent to the nickel nitrate (Ni (NO of 0.08 atom ₃) ₂6H ₂O) in addition, other and embodiment 33 likewise prepare hydrotreating catalyst.Be shown in table 13 to the rerum natura of this catalyst.

Embodiment 38

Except in oxidizing aqueous titanium, adding the ammonium paramolybdate ((NH that per 1 atom titanium is equivalent to 0.38 atom ₄) ₆Mo ₇O ₂₄4H ₂O), the boric acid (H that is equivalent to 0.16 atom ₃BO ₃) and be equivalent to the cobalt nitrate ((Co (NO of 0.06 atom ₃) ₂6H ₂O) in addition, other and the foregoing description 33 likewise prepare hydrotreating catalyst.Be shown in table 13 to the rerum natura of this catalyst.

In addition, to the hydrotreating catalyst that this embodiment 38 makes, use the JXA-8900 of company of NEC type X-ray microanalyzer (EPMA) to carry out line analysis.The result is as shown in Figure 5, and the not only per 1 atom titanium of the amount of loading with of molybdenum is 0.38 atom nearly, and evenly loads with in pore.

In addition, use Phillips corporate system PW3710 type X-ray diffraction device, hydrotreating catalyst and molybdenum oxide (MoO that this embodiment 38 is made ₃) the mensuration X-ray diffractogram.As a result, the hydrotreating catalyst of embodiment 38 such as Fig. 6, molybdenum oxide (MoO ₃) as shown in Figure 7.If load with molybdenum as molybdenum oxide (MoO on the hydrotreating catalyst carrier of this embodiment 38 ₃) catalyst, then ought to present MoO ₃Diffraction pattern, but the catalyst of embodiment 38 shown in Figure 6 is not observed.This is because the molybdenum coordination only is that expression-be not forms layer and loads with form from the teeth outwards in the crystallization of titanium oxide.

Comparative example 16

In the process of synthetic oxidizing aqueous titanium, except 95 ℃ of synthesis temperatures, alternately to carry out the number of times of conversion be 9 times with separating out pH scope (pH=7.0) to make titanium hydroxide dissolving pH scope (pH=0.5), other and embodiment 33 likewise synthesize oxidizing aqueous titanium.Washing gained oxidizing aqueous titanium is after the filtration, 120 ℃ of dryings 10 hours.

The water content of the dried oxidizing aqueous titanium of gained (constitution water+Free water) is 0.5 weight % by the solids benchmark.

In addition, use the oxidizing aqueous titanium that makes like this, likewise prepare hydrotreating catalyst with embodiment 52.Be shown in table 14 to the rerum natura of this catalyst.

Comparative example 17

In the container of 30 liters of band mixers, add 10 premium on currency, add 1.5 liters of the titanium tetrachloride aqueous solutions of embodiment 55 preparations at normal temperatures while stirring, make pH drop to 0.5.In this solution, add 2.3 liters of 14 weight % ammonia spirits, make pH be raised to 7.0, stir about 5 minutes.The oxidizing aqueous titanium that washing is separated out thus filters, and makes oxidizing aqueous titanium.

This hydrosol is an amorphous state, and water content (constitution water+Free water) is about 1000 weight % by the solids benchmark.

In addition, plan this hydrosol and carry out moulding, the result because amount of moisture is too many, can not carry out moulding.

Comparative example 18

Except in oxidizing aqueous titanium, adding the ammonium tungstate (NH that per 1 atom titanium is equivalent to 0.05 atom ₄) ₂WO ₄With the nickel nitrate that is equivalent to 0.019 atom (Ni (NO ₃) ₂6H ₂O) in addition, other and the foregoing description 33 likewise prepare hydrotreating catalyst.Be shown in table 14 to the rerum natura of gained catalyst.

Comparative example 19

Except in oxidizing aqueous titanium, adding the ammonium paramolybdate ((NH that per 1 atom titanium is equivalent to 0.62 atom ₄) ₆Mo ₇O ₂₄4H ₂O) and be equivalent to the cobalt nitrate ((Co (NO of 0.27 atom ₃) ₂6H ₂O) in addition, other and the foregoing description 33 likewise prepare hydrotreating catalyst.Be shown in table 14 to the rerum natura of gained catalyst.

Test Example 2: the hydrofinishing of light oil

Use the hydrotreating catalyst of above-mentioned each embodiment 33-38 and comparative example 11,12 and 16,18; Carry out proportion (15/4 ℃) 0.850, sulphur composition 1.37 weight %, nitrogen component 101ppm and the distillation performance is: it is the hydrofinishing of straight run light oil that 232 ℃ of initial boiling points, 50% distillate 295 ℃, 90% Middle East that distillate 348 ℃, the performance of research hydrotreating catalyst.

The flow type reaction unit is used in the hydrofinishing of light oil, and at reaction pressure 5.0MPa, 350 ℃ of reaction temperatures, liquid air speed 2.0l/h and hydrogen/raw material ratio are to implement under the condition of 250N1/1.When carrying out this hydrofinishing test, use the interpolation dimethyl disulfide to make the sulphur constituent concentration be adjusted to the light oil of 2.5 weight %, implement presulfurization according to common method.

Hydrorefined reaction result, desulphurization reaction are 1.2 order reactions, and denitrification reaction is 1 order reaction, asks for reaction constant, as " 1 ", use relative value to represent with the result of comparative example 1, are shown in table 13 and table 14 to the result.

[table 13]

[table 14]

(relation of denitrification percent and hydrogen consumption)

Below; Use the hydrotreating catalyst (titanium oxide catalyst) of the foregoing description 52 and 53 and the industrial catalyst (aluminium oxide catalyst) of comparative example 22 and 23; Liquid air speed is made an experiment, the relation of research denitrification percent and hydrogen consumption in the range of 1-3l/h.

The result is as shown in Figure 8, and embodiment 33 and 34 titanium oxide catalyst can suppress the hydrogen consumption significantly.

(explanation of embodiment and comparative example)

Clearly illustrate that by result shown in the table 13 of above-mentioned Test Example 2 and the table 14 hydrotreating catalyst of embodiment 33-38 is compared with the industrial catalyst of comparative example 11, desulphurizing activated raising is about more than 2 times or 2 times, and denitrification activity improves more than 3 times in addition.The hydrotreating catalyst of this embodiment 33-38 is compared with the industrial catalyst of comparative example 12; Desulphurizing activated also improve about more than 1.8 times or 1.8 times; Denitrification activity improves approximately more than 1.5 times or 1.5 times in addition, and finds out that by Fig. 8 the hydrogen consumption lacks than comparative example 11 and 12.

In addition, with regard to the result of comparative example 16-19, the constitution water of oxidizing aqueous titanium and Free water be (comparative example 16) after a little while, and the ion-exchange between the catalyst component can not carry out fully, and be desulphurizing activated all roughly the same with comparative example 19, insufficient with denitrification activity.In addition; When the constitution water of oxidizing aqueous titanium and Free water are too many (comparative example 17); Preparation can not moulding during catalyst, when the tungsten amount of loading with of primary catalyst component is loaded with quantity not sufficient with the nickel of co-catalyst component (comparative example 18), does not desulphurizing activatedly improve; When the molybdenum amount of loading with of primary catalyst component is too many in addition (comparative example 19), do not improve desulphurizing activated and denitrification activity effectively.

The possibility of utilizing on the industry

According to the present invention, can easily prepare specific area not only big and also simultaneously heat endurance might as well porous 4 group metal oxide.In addition; Have the hydrosol of 4 family's metal hydrous oxides of controlled narrow pore pore-size distribution through use, can easily prepare have good reaction selectivity, specific area is big, good catalyst activity, simultaneously heat endurance might as well catalyst or the porous 4 group metal oxide that catalyst carrier is used of conduct 4 family's metals.

In addition, high-purity porous titanium oxide of the present invention, specific area height and Heat stability is good, and accurately control the size of pore, the pore narrowly distributing for example is well suited in the purposes of many requirement for height titanium oxide performances, using as catalyst or catalyst carrier.

In addition; According to the present invention; Can obtain being controlled under the pore aperture arbitrarily the pore distribution shape that distributes along the reaction molecular amount, have more high-specific surface area and the good porous titanium oxide of mechanical strength, can prepare this porous titanium oxide according to purpose, purposes as catalyst carrier or catalyst than being controlled to even spherical particle.

According to the present invention; Hydrogenation catalyst with the few hydrocarbon ils of good desulfurization performance and nitrogen removal performance and hydrogen consumption can be provided; Be particularly suitable for using as the refining hydrotreating catalyst that uses of the hydrocarbon oil hydrogenation of the ultra-deep desulfurization that requires light oil etc., advanced nitrogen; In addition, other low sulfur " and the hydrofinishing of low nitrogenize of hydrocarbon ils is handled, also helped industry and go up and use.

Claims (57)

1. the hydrogenization catalyst preparation method of hydrocarbon ils is characterized in that, preparation is during hydrogenation catalyst, make the ion that contains the major catalyst element with the ion that contains promoter elements or respectively with formula M O _(2-x)(OH) _2xIon-exchange is carried out in the 4 families metal hydrous oxides contact of expression, make the pH value become pH 3-9 at last after, carry out moulding, drying, roasting again, described hydrogenation catalyst is made up of porous 4 group metal oxide, described formula M O _(2-x)(OH) _2x4 family's metal hydrous oxides of expression are that 4 family's metallic compounds and the pH conditioning agent of raw material reacts in water solvent and obtain, and said porous 4 group metal oxide is through at formula M O _(2-X)(OH) _2XAdd in the hydrosol, hydrogel or these the dry thing of 4 family's metal hydrous oxides of expression and carry out 4 family metal oxides that drying, roasting make behind the particle growth inhibitor, specific area is 80m ²More than/the g; Pore volume is more than the 0.2ml/g; The narrow degree of distribution of pore is more than 50%, and in the formula, M representes 4 family's metals; X representes the number of x＞0.1; Contained element is the element with high active of hydrogenation catalysis in the particle growth inhibitor, uses the hydroxyl of ion pair 4 family's metal hydrous oxides of this element to exchange, and the element that has high active of hydrogenation catalysis in the said hydrogenation catalyst is the major catalyst element formed of molybdenum and/or tungsten and by the promoter elements of selecting in the 9th family, the 10th family, the 13rd family and the 15th family more than a kind.

2. the hydrogenization catalyst preparation method of claim 1 is characterized in that, said promoter elements is the element of from cobalt, nickel, phosphorus and boron, selecting more than a kind.

3. the hydrogenization catalyst preparation method of claim 1; It is characterized in that; The ion exchange capacity of major catalyst element is 0.06-0.46 atom/1 atom titanium; The ion exchange capacity of promoter elements is 0.02-0.26 atom/1 atom titanium, and total ion exchange capacity of these major catalyst elements and promoter elements is 0.08-0.82 atom/1 atom titanium.

4. the hydrogenization catalyst preparation method of claim 1 is characterized in that, 4 family's metal M are titaniums.

5. the described hydrogenization catalyst preparation method of claim 1 is characterized in that, 4 family's metal M are zirconiums.

6. the described hydrogenization catalyst preparation method of claim 1 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2XYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.1≤x＜2.0, y is 0.3≤y≤40.

7. the described hydrogenization catalyst preparation method of claim 1 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2xYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.2≤x＜1.0, y is 0.3≤y≤40.

8. each described hydrogenization catalyst preparation method of claim 1-7; It is characterized in that; 4 family's metal hydrous oxides obtain through following method: the 4 family's metallic compounds and the pH conditioning agent that use raw material; In synthetic, the pH swinging operation more than alternately carrying out repeatedly between the deposition pH scope of 4 family's metal hydrous oxides and the dissolving pH scope.

9. each described hydrogenization catalyst preparation method of claim 1-7; It is characterized in that; 4 family's metal M are titaniums; PH swinging operation more than titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material hockets repeatedly in synthetic obtains; Said pH swinging operation scope is that { { between 5.1≤pH≤7.1}, perhaps { 5.1≤pH≤7.1} and high pH side scope are { between 8≤pH≤12} near the pH scope the isoelectric point near the pH scope the isoelectric point of 1＜pH≤4} and oxidizing aqueous titanium for the interior low pH side scope of the pH scope of not dissolving of oxidizing aqueous titanium.

10. each described hydrogenization catalyst preparation method of claim 1-7; It is characterized in that; 4 family's metal M are titaniums; Titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material carries out the pH swinging operation and obtains in synthetic; Said pH swinging operation scope is the low pH side scope in the pH scope of the not dissolving { 1＜pH≤4} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1} at oxidizing aqueous titanium; And at high pH side scope { 8≤pH≤12} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1}, { 5.1≤pH≤7.1} reserves the enough maturation time near the pH scope isoelectric point, makes the particle growth simultaneously.

11. the described hydrogenization catalyst preparation method of claim 9; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

12. the described hydrogenization catalyst preparation method of claim 10; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

13. the described hydrogenization catalyst preparation method of each of claim 1-7 is characterized in that, particle growth inhibitor provides the compound of the ion that contains the element of from iron, nickel, cobalt, platinum, palladium, rhodium and ruthenium, selecting.

14. the hydrogenization catalyst preparation method of hydrocarbon ils is characterized in that, during the preparation hydrogenation catalyst, formula M O _(2-x)(OH) _2x4 family's metal hydrous oxides of expression add in the dipping solution that contains ion with major catalyst element and the ion with promoter elements; Under the condition of pH 1-7 or pH 9-11, contact; Carry out ion-exchange, then, filtration, moulding, drying, roasting; Described hydrogenation catalyst is made up of porous 4 group metal oxide, described formula M O _(2-x)(OH) _2x4 family's metal hydrous oxides of expression are that 4 family's metallic compounds and the pH conditioning agent of raw material reacts in water solvent and obtain, and said porous 4 group metal oxide is through at formula M O _(2-X)(OH) _2XAdd in the hydrosol, hydrogel or these the dry thing of 4 family's metal hydrous oxides of expression and carry out 4 family metal oxides that drying, roasting make behind the particle growth inhibitor, specific area is 80m ²More than/the g; Pore volume is more than the 0.2ml/g; The narrow degree of distribution of pore is more than 50%, and in the formula, M representes 4 family's metals; X representes the number of x＞0.1; Contained element is the element with high active of hydrogenation catalysis in the particle growth inhibitor, uses the hydroxyl of ion pair 4 family's metal hydrous oxides of this element to exchange, and the element that has high active of hydrogenation catalysis in the said hydrogenation catalyst is the major catalyst element formed of molybdenum and/or tungsten and by the promoter elements of selecting in the 9th family, the 10th family, the 13rd family and the 15th family more than a kind.

15. the hydrogenization catalyst preparation method of claim 14 is characterized in that, said promoter elements is the element of from cobalt, nickel, phosphorus and boron, selecting more than a kind.

16. the hydrogenization catalyst preparation method of claim 14; It is characterized in that; The ion exchange capacity of major catalyst element is 0.06-0.46 atom/1 atom titanium; The ion exchange capacity of promoter elements is 0.02-0.26 atom/1 atom titanium, and total ion exchange capacity of these major catalyst elements and promoter elements is 0.08-0.82 atom/1 atom titanium.

17. the hydrogenization catalyst preparation method of claim 14 is characterized in that, 4 family's metal M are titaniums.

18. the described hydrogenization catalyst preparation method of claim 14 is characterized in that, 4 family's metal M are zirconiums.

19. the described hydrogenization catalyst preparation method of claim 14 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2XYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.1≤x＜2.0, y is 0.3≤y≤40.

20. the described hydrogenization catalyst preparation method of claim 14 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2xYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.2≤x＜1.0, y is 0.3≤y≤40.

21. the described hydrogenization catalyst preparation method of each of claim 14-20; It is characterized in that; 4 family's metal hydrous oxides obtain through following method: the 4 family's metallic compounds and the pH conditioning agent that use raw material; In synthetic, the pH swinging operation more than alternately carrying out repeatedly between the deposition pH scope of 4 family's metal hydrous oxides and the dissolving pH scope.

22. the described hydrogenization catalyst preparation method of each of claim 14-20; It is characterized in that; 4 family's metal M are titaniums; PH swinging operation more than titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material hockets repeatedly in synthetic obtains; Said pH swinging operation scope is that { { between 5.1≤pH≤7.1}, perhaps { 5.1≤pH≤7.1} and high pH side scope are { between 8≤pH≤12} near the pH scope the isoelectric point near the pH scope the isoelectric point of 1＜pH≤4} and oxidizing aqueous titanium for the interior low pH side scope of the pH scope of not dissolving of oxidizing aqueous titanium.

23. the described hydrogenization catalyst preparation method of each of claim 14-20; It is characterized in that; 4 family's metal M are titaniums; Titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material carries out the pH swinging operation and obtains in synthetic; Said pH swinging operation scope is the low pH side scope in the pH scope of the not dissolving { 1＜pH≤4} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1} at oxidizing aqueous titanium; And at high pH side scope { 8≤pH≤12} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1}, { 5.1≤pH≤7.1} reserves the enough maturation time near the pH scope isoelectric point, makes the particle growth simultaneously.

24. the described hydrogenization catalyst preparation method of claim 22; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

25. the described hydrogenization catalyst preparation method of claim 23; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

26. the described hydrogenization catalyst preparation method of each of claim 14-20 is characterized in that, particle growth inhibitor provides the compound of the ion that contains the element of from iron, nickel, cobalt, platinum, palladium, rhodium and ruthenium, selecting.

27. the hydrogenization catalyst preparation method of hydrocarbon ils; It is characterized in that; When preparing described hydrogenation catalyst, the ion that contains the major catalyst element that molybdenum and/or tungsten constitutes is contacted with the ion that contains the promoter elements of from cobalt, nickel, phosphorus and boron, selecting more than a kind, carry out ion-exchange; Then; Filtration, moulding, drying, roasting, described hydrogenation catalyst is made up of porous 4 group metal oxide, and said porous 4 group metal oxide is through in water solvent, reacting the formula M O that obtains at 4 family's metallic compounds that make raw material and pH conditioning agent _(2-X)(OH) _2XAdd in the hydrosol, hydrogel or these the dry thing of 4 family's metal hydrous oxides of expression and carry out 4 family metal oxides that drying, roasting make behind the particle growth inhibitor, specific area is 80m ²More than/the g; Pore volume is more than the 0.2ml/g; The narrow degree of distribution of pore is more than 50%, and in the formula, M representes 4 family's metals; X representes the number of x＞0.1; Contained element is the element with high active of hydrogenation catalysis in the particle growth inhibitor, uses the hydroxyl of ion pair 4 family's metal hydrous oxides of this element to exchange, and the element that has high active of hydrogenation catalysis in the said hydrogenation catalyst is the major catalyst element formed of molybdenum and/or tungsten and by the promoter elements of selecting in the 9th family, the 10th family, the 13rd family and the 15th family more than a kind.

28. the hydrogenization catalyst preparation method of claim 27 is characterized in that, said promoter elements is the element of from cobalt, nickel, phosphorus and boron, selecting more than a kind.

29. the hydrogenization catalyst preparation method of claim 27; It is characterized in that; The ion exchange capacity of major catalyst element is 0.06-0.46 atom/1 atom titanium; The ion exchange capacity of promoter elements is 0.02-0.26 atom/1 atom titanium, and total ion exchange capacity of these major catalyst elements and promoter elements is 0.08-0.82 atom/1 atom titanium.

30. the hydrogenization catalyst preparation method of claim 27 is characterized in that, 4 family's metal M are titaniums.

31. the described hydrogenization catalyst preparation method of claim 27 is characterized in that, 4 family's metal M are zirconiums.

32. the described hydrogenization catalyst preparation method of claim 27 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2XYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.1≤x＜2.0, y is 0.3≤y≤40.

33. the described hydrogenization catalyst preparation method of claim 27 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2xYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.2≤x＜1.0, y is 0.3≤y≤40.

34. the described hydrogenization catalyst preparation method of each of claim 27-33; It is characterized in that; 4 family's metal hydrous oxides obtain through following method: the 4 family's metallic compounds and the pH conditioning agent that use raw material; In synthetic, the pH swinging operation more than alternately carrying out repeatedly between the deposition pH scope of 4 family's metal hydrous oxides and the dissolving pH scope.

35. the described hydrogenization catalyst preparation method of each of claim 27-33; It is characterized in that; 4 family's metal M are titaniums; PH swinging operation more than titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material hockets repeatedly in synthetic obtains; Said pH swinging operation scope is that { { between 5.1≤pH≤7.1}, perhaps { 5.1≤pH≤7.1} and high pH side scope are { between 8≤pH≤12} near the pH scope the isoelectric point near the pH scope the isoelectric point of 1＜pH≤4} and oxidizing aqueous titanium for the interior low pH side scope of the pH scope of not dissolving of oxidizing aqueous titanium.

36. the described hydrogenization catalyst preparation method of each of claim 27-33; It is characterized in that; 4 family's metal M are titaniums; Titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material carries out the pH swinging operation and obtains in synthetic; Said pH swinging operation scope is the low pH side scope in the pH scope of the not dissolving { 1＜pH≤4} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1} at oxidizing aqueous titanium; And at high pH side scope { 8≤pH≤12} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1}, { 5.1≤pH≤7.1} reserves the enough maturation time near the pH scope isoelectric point, makes the particle growth simultaneously.

37. the described hydrogenization catalyst preparation method of claim 36; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

38. the described hydrogenization catalyst preparation method of each of claim 27-33 is characterized in that, particle growth inhibitor provides the compound of the ion that contains the element of from iron, nickel, cobalt, platinum, palladium, rhodium and ruthenium, selecting.

39. the hydrofinishing process of hydrocarbon ils is characterized in that, makes hydrogenation catalyst and hydrocarbon ils in the presence of hydrogen, at reaction temperature 280-400 ℃, reaction pressure 2-15MPa, LHSV 0.3-10hr ^-1And the hydroprocessing condition of hydrogen/oil ratio 50-500Nl/l contact down; Remove sulphur composition and nitrogen component in the hydrocarbon ils; Described hydrogenation catalyst is made up of porous 4 group metal oxide, and said porous 4 group metal oxide is through in water solvent, reacting the formula M O that obtains at 4 family's metallic compounds that make raw material and pH conditioning agent _(2-X)(OH) _2XAdd in the hydrosol, hydrogel or these the dry thing of 4 family's metal hydrous oxides of expression and carry out 4 family metal oxides that drying, roasting make behind the particle growth inhibitor, specific area is 80m ²More than/the g; Pore volume is more than the 0.2ml/g, and the narrow degree of distribution of pore is more than 50%, in the formula; M representes 4 family's metals; X representes the number of x＞0.1, and contained element is the element with high active of hydrogenation catalysis in the particle growth inhibitor, uses the hydroxyl of ion pair 4 family's metal hydrous oxides of this element to exchange.

40. the hydrofinishing process of claim 39; It is characterized in that the element that has high active of hydrogenation catalysis in the said hydrogenation catalyst is the major catalyst element formed of molybdenum and/or tungsten and by the promoter elements of selecting in the 9th family, the 10th family, the 13rd family and the 15th family more than a kind

41. the hydrofinishing process of claim 39 is characterized in that, said promoter elements is the element of from cobalt, nickel, phosphorus and boron, selecting more than a kind.

42. the hydrofinishing process of claim 39; It is characterized in that; The ion exchange capacity of major catalyst element is 0.06-0.46 atom/1 atom titanium; The ion exchange capacity of promoter elements is 0.02-0.26 atom/1 atom titanium, and total ion exchange capacity of these major catalyst elements and promoter elements is 0.08-0.82 atom/1 atom titanium.

43. the hydrofinishing process of claim 39 is characterized in that, 4 family's metal M are titaniums.

44. the described hydrofinishing process of claim 39 is characterized in that, 4 family's metal M are zirconiums.

45. the described hydrofinishing process of claim 39 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2XYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.1≤x＜2.0, y is 0.3≤y≤40.

46. the described hydrofinishing process of claim 39 is characterized in that, 4 family's metal hydrous oxides are composition formula TiO _(2-X)(OH) _2xYH ₂The oxidizing aqueous titanium that O representes, in the formula, x is 0.2≤x＜1.0, y is 0.3≤y≤40.

47. the described hydrofinishing process of each of claim 39-46; It is characterized in that; 4 family's metal hydrous oxides obtain through following method: the 4 family's metallic compounds and the pH conditioning agent that use raw material; In synthetic, the pH swinging operation more than alternately carrying out repeatedly between the deposition pH scope of 4 family's metal hydrous oxides and the dissolving pH scope.

48. the described hydrofinishing process of each of claim 39-46; It is characterized in that; 4 family's metal M are titaniums; PH swinging operation more than titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material hockets repeatedly in synthetic obtains; Said pH swinging operation scope is that { { between 5.1≤pH≤7.1}, perhaps { 5.1≤pH≤7.1} and high pH side scope are { between 8≤pH≤12} near the pH scope the isoelectric point near the pH scope the isoelectric point of 1＜pH≤4} and oxidizing aqueous titanium for the interior low pH side scope of the pH scope of not dissolving of oxidizing aqueous titanium.

49. the described hydrofinishing process of each of claim 39-46; It is characterized in that; 4 family's metal M are titaniums; Titanium compound and the pH conditioning agent of oxidizing aqueous titanium through using raw material carries out the pH swinging operation and obtains in synthetic; Said pH swinging operation scope is the low pH side scope in the pH scope of the not dissolving { 1＜pH≤4} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1} at oxidizing aqueous titanium; And at high pH side scope { 8≤pH≤12} and surpass near the isoelectric point pH scope { between the scope of 5.1≤pH≤7.1}, { 5.1≤pH≤7.1} reserves the enough maturation time near the pH scope isoelectric point, makes the particle growth simultaneously.

50. the described hydrofinishing process of claim 48; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

51. the described hydrofinishing process of claim 49; It is characterized in that; By calculating formula { pore dissymmetryc coefficient N=(A-C)/(B-A); A is the logarithm value of median diameter in the formula, and B is the pore aperture logarithm value of 2% pore volume, and C is the pore aperture logarithm value of 98% pore volume } the pore dissymmetryc coefficient N of the porous titanium oxide that drawn is the scope of 1.5≤N≤4.

52. the described hydrofinishing process of each of claim 39-46 is characterized in that, particle growth inhibitor provides the compound of the ion that contains the element of from silicon, phosphorus, magnesium, calcium, barium, manganese, aluminium and zirconium, selecting.

53. the described hydrofinishing process of each of claim 39-46 is characterized in that, particle growth inhibitor provides the compound of the ion that contains the element of from sulphur, molybdenum, tungsten, vanadium and boron, selecting.

54. the described hydrofinishing process of each of claim 39-46 is characterized in that, particle growth inhibitor provides the compound of the ion that contains the element of from iron, nickel, cobalt, platinum, palladium, rhodium and ruthenium, selecting.

55. the described hydrofinishing process of each of claim 39-46; It is characterized in that; Particle growth inhibitor is with 4 family's metallic compounds of raw material; In the reaction dissolvent when synthetic 4 family metal hydrous oxides, before the synthetic back of 4 family's metal hydrous oxides, the dehydration, or any time before the 4 families metal hydrous oxides dehydration backs, roasting add.

56. the described hydrofinishing process of each of claim 39-46 is characterized in that, particle growth inhibitor adds in the filter and cleaning process of 4 family's metal hydrous oxides.

57. the described hydrofinishing process of each of claim 39-46 is characterized in that, as particle growth inhibitor; When adding anion; Under the pH of the isoelectric point that is lower than this 4 family metal hydrous oxide, add, when adding cation, under the pH more than the isoelectric point, add; When adding anion and cation simultaneously, under the pH of isoelectric point ± 1.0, add.

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