CN100435954C

CN100435954C - Hydrotreating catalyst for gas oil, process for producing the same, and method of hydrotreating gas oil

Info

Publication number: CN100435954C
Application number: CNB2003801066788A
Authority: CN
Inventors: 藤川贵志; 加藤胜博; 中岛伸昌; 桥本稔
Original assignee: Cosmo Oil Co Ltd
Current assignee: Cosmo Oil Co Ltd
Priority date: 2002-12-18
Filing date: 2003-12-17
Publication date: 2008-11-26
Anticipated expiration: 2023-12-17
Also published as: CN1729056A

Abstract

A hydrotreating catalyst which can be produced with a simple means and with which gas oil can be superdeeply desulfurized and simultaneously made to have a reduced nitrogen content without necessitating severe operating conditions; and a method of desulfurizing gas oil with the catalyst. The catalyst comprises an inorganic oxide support and, deposited thereon, 10 to 40 wt.% Group 6 metal of the Periodic Table, 1 to 15 wt.% Group 8 metal of the Periodic Table, and 1.5 to 8 wt.% phosphorus each in terms of oxide amount based on the catalyst and 2 to 14 wt.% carbon in terms of element amount based on the catalyst. It has a specific surface area of 150 to 300 m<2>/g, a pore volume of 0.3 to 0.6 mL/g, and an average pore diameter of 65 to 140 AA. The catalyst, after sulfurization, shows a certain NO adsorption FT-IR spectrum.

Description

The method of light oil hydrotreating catalyst, its preparation method and light oil hydrotreatment

Technical field

The present invention relates to be used for the catalyst of hydrotreatment light oil, prepare the method for this catalyst and the method for the hydrotreatment light oil that uses this catalyst.More specifically, the present invention relates to compare with in hydrotreatment light oil, using the situation of the conventional catalyst of the type, having excellent activity can be reduced to lower level catalyst with sulphur composition and nitrogen component in the light oil, relates to the method for preparing this catalyst and uses this catalyst to carry out the method for hydrotreatment light oil.

Background technology

Recently, trend towards stricter quality regulation value to improve atmospheric environment for the light oil whole world.Particularly, wish to reduce the sulphur in the light oil, because sulphur can provide the durability of the after-treatment device of effective control to have a negative impact to diesel emissions to expectation, described after-treatment device for example oxidation catalyst, nitrogen oxide (NOx) reducing catalyst and be used for from diesel exhaust remove particle matter continuously-type filter of regenerating.

In these cases, a kind of ultra-deep desulfurization technology that is used for fully removing from light oil most of sulphur compositions of development just comes into one's own.The common feasible technology that is used for reducing light oil sulphur composition is to use the operating condition of the harshness that is used for hydrodesulfurization, for example, and reaction temperature and liquid hourly space velocity.

Yet, use the reaction temperature that raises to cause carbonaceous material to be deposited on the catalyst, thereby cause the rapid reduction of catalytic activity.On the other hand, though use lower liquid hourly space velocity to improve desulphurizing ability, cause the reduction of the ability of purifying, the size of therefore necessary increase equipment.

Therefore, realizing the light oil ultra-deep desulfurization and need not to use the best means of critical operation condition is that exploitation has good desulphurizing activated catalyst.

Recently, carried out many researchs at aspects such as the adjustment of the improvement of the dipping method of the kind of reactive metal, reactive metal, catalyst carrier, catalyst pores gap structure and activation methods, and the report of the existing new catalyst of being developed that is used for deep desulfuration.

For example, patent documentation 1 discloses a kind of method, and this method comprises floods aluminium oxide or silica supports with the solution that includes organic compounds and also comprise reactive metal, and this organic compound has the containing n-donor ligand as complexing agent; Carry out drying 200 ℃ or lower temperature subsequently.

Patent documentation 2 discloses a kind of method, this method comprises floods gamma-aluminium oxide carrier with dipping solution, this dipping solution be by to comprise periodic table the 8th family's metal (below, sometimes abbreviate " the 8th family's metal " as) the compound of compound, periodic table the 6th family's metal (below, abbreviate " the 6th family's metal " as) and the dipping solution of phosphoric acid in further add glycol or ether and obtain; Carry out drying 200 ℃ or lower temperature subsequently.

Patent documentation 3 discloses a kind of method, and this method comprises as in the method for the invention, and carrier is flooded with solution, and this solution comprises compound, the phosphorus composition of the 6th family's metal, the compound and the citric acid of the 8th family's metal; Undried and calcining subsequently.Patent documentation 4 discloses a kind of method, this method comprise with on it load have the carrier of compound of compound, phosphorus composition and the 8th family's metal of the 6th family's metal to flood with containing specified quantitative organic acid solution; Carry out drying 200 ℃ or lower temperature subsequently.

In addition, patent documentation 5 discloses a kind of method, this method comprises that the compound that will comprise the 6th family's metal, the compound of the 8th family's metal and the solution of phosphoric acid load on the oxide carrier, the gained carrier is carried out drying to obtain catalyst 200 ℃ or lower temperature, the organic acid soln that load is represented with the particular chemical formula on catalyst carries out drying 200 ℃ or lower temperature then.

On the other hand, also having proposed multiple suggestion aspect the Preparation of catalysts method, wherein carry out dipping twice with organic acid.

For example, patent documentation 6 discloses a kind of method, and this method comprises floods oxide carrier with solution, and this solution comprises the compound of the 6th family's metal, compound, organic acid and the phosphoric acid of the 8th family's metal; Carry out drying to obtain catalyst 200 ℃ or lower temperature subsequently; And further flood this catalyst with organic acid soln; Carry out drying 200 ℃ or lower temperature subsequently.

In addition, patent documentation 7 discloses a kind of catalyst preparation process, and this technology comprises floods inorganic oxide carrier with the compound of the 8th family's metal and the heteropoly acid of the 6th family's metal, carry out drying subsequently.

And patent documentation 8 discloses a kind of method for preparing catalyst, and this method comprises floods the solution of oxide carrier with the compound, mercaptan carboxylic acid and the phosphoric acid that comprise molybdenum, tungsten, the 8th family's metal.

This method mainly attempts to form the complex of mercaptan carboxylic acid and molybdenum, tungsten and the 8th family's metallic compound, with described complex high degree of dispersion on catalyst carrier.

Yet in said method, molybdenum and tungsten are highly dispersed on carrier, therefore, are difficult to form the laminate of molybdenum bisuphide (for example, the catalyst among the present invention that will describe in the back).This method does not cause forming the II type site that CoMoS phase, NiMoS equate by inference, and this site (that is, is positioned at the cobalt on the edge of the second layer of molybdenum bisuphide and overlying strata or the avtive spot of nickel as the avtive spot of desulfurization; I type site is to be positioned at the cobalt on the ground floor edge of molybdenum bisuphide or the avtive spot of nickel, and has the activity that is lower than II type site) be effective especially.

In addition,, therefore have such possibility because the mercaptan carboxylic acid contains sulphur: when acid be present in the 8th family's metal (Co or Ni) around or when forming complex, then acid does not provide desulphurizing activated site (CoMoS mutually or NiMoS equate), and provides inertia Co ₉S ₈Or Ni ₃S ₂Species.

And, there is following shortcoming in above-mentioned Preparation of catalysts method: the step that some method must be complicated and resulting some catalyst also are not suitable for the ultra-deep desulfurization of light oil, some has demonstrated poor efficiency in the ultra-deep desulfurization scope, and some has the short life-span.

In addition, patent documentation 9 discloses a kind of catalyst, this catalyst comprises the 8th family's slaine that is selected from cobalt and nickel and/or the complex compound on the oxide carrier and is selected from molybdenum and the heteropoly acid of the 6th family's metal of tungsten, wherein the 8th family's concentration of metal accounts for the about 2 weight %～20 weight % of carrier, the 6th family's concentration of metal accounts for the about 5 weight %～50 weight % of carrier, and catalyst is substantially free of free water.In addition, patent documentation 10 discloses a kind of catalyst, this catalyst is to make by the following method: with hydroxycarboxylic acid with amount with respect to 0.3～5 equivalent of the total mole number of the 6th family's metal and the 8th family's metal, join wherein that the 6th family's metal and the 8th family's metal are carried in the supported catalyst, carry out drying 200 ℃ or lower temperature subsequently.

Although reported multiple catalyst as mentioned above as development, but still lack the suggestion of such technology: the catalyst that can obtain having enough high desulfurization activities and long life with this technology, and this catalyst can make by straightforward procedure, also need not use harsh operating condition and can realize the ultra-deep desulfurization of light oil.

[patent documentation 1]

JP-A-61-114737

[patent documentation 2]

No. 2900771 communique of Japan's special permission

[patent documentation 3]

No. 2832033 communique of Japan's special permission

[patent documentation 4]

JP-A-4-156948

[patent documentation 5]

JP-A-4-244238

[patent documentation 6]

JP-A-6-339635

[patent documentation 7]

JP-A-6-31176

[patent documentation 8]

JP-A-1-228552

[patent documentation 9]

JP-A-6-31176

[patent documentation 10]

No. 3244692 communique of Japan's special permission

Summary of the invention

An object of the present invention is to provide a kind of hydrotreating catalyst, this catalyst can make by straightforward procedure, and can realize the ultra-deep desulfurization of sulphur composition in the light oil and not need harsh operating condition, simultaneously can reduce nitrogen component, and a kind of method for preparing this catalyst is provided.

Another object of the present invention provides with this catalyst carries out the method that highly effective hydrogenation is handled to light oil distillate.

To achieve these goals, the invention provides the following catalyst that is used for hydrotreatment light oil, prepare the method for this catalyst and use this catalyst hydrogenation to handle the method for light oil.

(1) a kind of catalyst that is used for hydrotreatment light oil, this catalyst comprises at least a metal that is selected from periodic table the 6th family's metal of the 10 weight %～40 weight % on the inorganic oxide carrier, at least a metal that is selected from periodic table the 8th family's metal of 1 weight %～15 weight % and the phosphorus of 1.5 weight %～8 weight %, the amount of described each composition is the amount that accounts for catalyst behind the oxide that is converted into, and the carbon that comprises 2 weight %～14 weight %, described amount is the amount that carbon accounts for catalyst.

The specific area of wherein said catalyst is 150～300m ²/ g, pore volume is 0.3～0.6ml/g, and average pore size is 65～140

With

Wherein, after vulcanizing treatment and the absorption of NO subsequently, when catalyst is observed on diffuse reflection method Fourier transform infrared spectroscopy (FT-IR), the value of I8 family/(I8 family+I6 family) is in 0.7～1 the scope, wherein, the representative of I8 family is adsorbed on the NO spectrum (1840cm on periodic table the 8th family's metal ^-1) intensity, the representative of I6 family is adsorbed on the NO spectrum (1700cm on periodic table the 6th family's metal ^-1) intensity.

(2) according to the catalyst of above-mentioned (1), wherein said catalyst has such pore size distribution: the aperture is average pore size ± 15 The ratio in hole be 30%～75%.

(3) according to the catalyst of above-mentioned (1) or (2), wherein, after the presulfurization of described catalyst, the average of the laminate of the disulphide of periodic table the 6th family's metal by transmission electron microscope observation is 2.5～5.

(4) according to the catalyst of above-mentioned (1) or (2), wherein, after the presulfurization of described catalyst, direction length is 1～3.5nm in the centre plane of the disulphide layer of periodic table the 6th family's metal by transmission electron microscope observation.

(5) method of preparation as each described catalyst of above-mentioned (1)～(4), this method comprises with the metal that contains in periodic table the 6th family, metal in periodic table the 8th family, the solution of organic acid and phosphoric acid, at least a metal that is selected from periodic table the 6th family's metal of load 10 weight %～40 weight % on inorganic oxide carrier, at least a metal that is selected from periodic table the 8th family's metal of 1 weight %～15 weight % and the phosphorus of 1.5 weight %～8 weight %, the amount of described each composition is the amount that accounts for catalyst behind the oxide that is converted into, and the carbon of 2 weight %～14 weight %, described amount is the amount that carbon accounts for catalyst, and the specific area of described inorganic oxide carrier is 230～500m ²/ g, pore volume are that 0.5～1ml/g and average pore size are 60

～120 Under 200 ℃ or lower temperature, carry out drying subsequently.

(6) a kind of method of hydrotreatment light oil, this method are included under each the existence of catalyst of above-mentioned (1)～(4), are that 3～8MPa, temperature are that 300～420 ℃ and liquid hourly space velocity are 0.3～5hr at hydrogen partial pressure ^-1Condition under, light oil distillate is carried out catalytic reaction.

Description of drawings

Fig. 1 has shown the NO absorption FT-IR spectrogram of resulting catalyst A among the embodiment 1.

Fig. 2 has shown the transmission electron micrograph of resulting catalyst B among the embodiment 2.

The specific embodiment

As for achieving the above object and the further investigation the result, the present inventor finds when inorganic oxide carrier being used the compound that contains the 6th family's metal, the compound of the 8th family's metal, the solution of organic acid and phosphoric acid floods with thereon with these compositions of specified rate load and when 200 ℃ or lower temperature are carried out drying, (for example can accurately adjust high activity desulfurization site, CoMoS phase II type site, NiMoS phase II type site etc.) there are not to produce inertia species such as cobalt or nickel grade in an imperial examination 6 family's metals, the result, can make high performance desulphurization catalyst, owing to can effectively carry out desulphurization reaction and denitrification reaction, therefore this catalyst can promote the realization of ultra-deep desulfurization reaction, and need not use harsh reaction condition.

As pending in the present invention target oil, be suitable such as straight run light oil, catalytic cracking light oil, thermal cracking light oil, hydrotreatment light oil, desulfurization light oil, vacuum distillation light oil light oil distillates such as (VGO).

The example of the representational character of these feedstock oils comprises that boiling point is that 150～450 ℃ and sulfur content are for being less than or equal to 5 weight %.

Employed inorganic oxide carrier can be independent aluminium oxide in catalyst of the present invention.Yet, desulphurizing activated in order further to improve, preferred use comprise aluminium oxide as main component composite oxides.

As aluminium oxide, can use multiple aluminium oxide, for example Alpha-alumina, beta-alumina, gama-alumina, δ-aluminium oxide, hydrated alumina etc.Yet the aluminium oxide that porous and specific area are big is preferred.Particularly, gama-alumina is suitable.Purity is about 98 weight % or higher, and it is preferred being preferably about 99 weight % or higher aluminium oxide.

The example of the impurity in the aluminium oxide comprises SO ₄ ^2-, Cl ^-, Fe ₂O ₃, Na ₂O etc.The content of these impurity is low more, and then aluminium oxide is just preferred more.The total content of all impurity is 2 weight % or lower, is preferably 1 weight % or lower.The content of various impurity is preferably as follows: SO ₄ ^2-＜1.5 weight %, Cl ^-, Fe ₂O ₃, Na ₂O＜0.1 weight %.

The oxide components that is used for forming compound with aluminium oxide is preferably and is selected from least a in zeolite, boron oxide (boria), silica and the zirconia.The compound that forms with these compositions is favourable in the laminate that forms molybdenum bisuphide.

In these compositions, as passing through coulter counter method (the NaCl aqueous solution of 1 weight %; Aperture: 30 μ m; Ultrasonic processing 3 minutes) average grain diameter of the zeolite of being measured is about 2.5～6 μ m, is preferably about 3～5 μ m, more preferably about 3～4 μ m.In zeolite, based on all zeolite granulars, particle diameter is that 6 μ m or littler proportion of particles are about 70%～98%, is preferably about 75%～98%, more preferably about 80%～98%.

These character of zeolite are favourable for accurate adjustment aperture, thereby make the material that is difficult to desulfurization easily to spread in the hole.For example, when using zeolite in the preparation at composite oxide carrier with excessive average grain diameter or too high coarse granule content, in heating and calcination process, because the difference between hydrated alumina (alumina precursor) and the zeolite on water imbibition and crystallinity, hydrated alumina (alumina precursor) has demonstrated contraction in various degree with zeolite, therefore, be tending towards formation and have relatively large hole, the i.e. composite oxide carrier of mesopore or macropore.In addition, these macropores have not only reduced surface area, and under the situation with the catalyst treatment Residual oil, feasible metal ingredient as catalyst poison is easy to be diffused in the hole.As a result, these macropores cause the reduction of the catalytic activity in desulfurization, denitrogenation and cracking easily.

In the present invention, the preferred embodiment that is used for forming the zeolite of compound with aluminium oxide comprises octahedral X-type zeolite, octahedral Y-type zeolite, β zeolite, modenite, ZSM series zeolite (ZSM-4,5,8,11,12,20,21,23,34,35,38,46 etc.), MCM-41, MCM-22, MCM-48, SSZ-33, UTD-1, CIT-5, VPI-5, TS-1 and TS-2 etc.Particularly preferably be Y-type zeolite, stable Y-type zeolite and β zeolite.In addition, the proton type zeolite is preferred.

As above-mentioned boron oxide, silica and zirconia, usually can be as the carrier components of such catalyst.

Above-mentioned zeolite, boron oxide, silica and zirconia can use separately or two kinds or be used in combination.

The amount of the described composition that is added is not done special restriction.Yet, for the aluminium oxide that is approximately higher than 80 weight %～99.5 weight %, the amount of the described composition in composite oxide carrier is generally about 0.5 weight %～be lower than 20 weight %, preferably the aluminium oxide for about 85 weight %～99.5 weight % is about 0.5 weight %～15 weight %, and more preferably the aluminium oxide for about 90 weight %～99.5 weight % is about 0.5 weight %～10 weight %.

The difficulty that the excessive or too small meeting of the amount of these compositions causes the aperture to be adjusted.In addition, its too small amount can cause fully giving bronsted Acid site and lewis acid site, and its excessive amount can cause the 6th family's metal, the especially trend that is difficult to high degree of dispersion of molybdenum.

Employed in the present invention inorganic oxide carrier made by calcining down at 580～700 ℃ in 1.5～3 hours.

As hereinafter described, catalyst of the present invention only is after loading on active component on the inorganic oxide carrier, 200 ℃ or more low temperature carry out drying and make.Therefore, by the calcining inorganic oxide carrier, can obtain the mechanical performance (for example, side crushing strength, closs packing density etc.) of the catalyst that will describe the back.When the temperature that is lower than 580 ℃ is calcined less than 1.5 hours, can't obtain enough mechanical strengths.Even surpass under 700 ℃ the high temperature, calcining surpasses about 3 hours time expand, not only calcine effect and reach capacity, and will take place densified, thereby damaged the performance of inorganic oxide carrier, for example specific area, pore volume and average pore size.

The specific area of inorganic oxide carrier, pore volume and average pore size should be following value, so that catalyst has high activity in the hydrodesulfurization of hydrocarbon ils.The specific area of carrier is 230～500m ²/ g is preferably 300～450m ²/ g.Its pore volume is 0.5～1ml/g, is preferably 0.6～1ml/g.Its average pore size is 60 ～120

Be preferably 65

～110

Its reason is as follows.

It is believed that all there be (the 6th family's metal and phosphoric acid coordination form heteropoly acid, and the 8th family's metal and organic acid coordination form metal-organic complex) in the 6th family's metal and the 8th family's metal in dipping solution with the form of complex compound separately.Therefore, when the specific area of carrier less than 230m ²During/g, because complex compound is huge, each metal is difficult to high degree of dispersion when dipping.As a result, even when the gained catalyst is carried out vulcanizing treatment, also be difficult to accurately adjust the formation of above-mentioned avtive spot (for example, CoMoS phase, NiMoS phase, or the like).

When the specific area of carrier is 500m ²Therefore/g or more hour, carrier does not have minimum like this aperture has obtained not having equally the catalyst of small-bore like this, so this situation is preferred.When the aperture of catalyst hour because the diffusion that sulphur compound diffuses in the catalyst pores is not enough, so the desulphurizing activated reduction of catalyst.

When the pore volume of carrier is 0.5ml/g or when bigger, when using common immersion process for preparing catalyst, the quantity of solvent that is immersed in the hole is so not few, so this situation is preferred.Because quantity of solvent hour, the compound exhibits of reactive metal goes out weak dissolubility, has caused damaging the decentralization of metal, thereby obtains having weak active catalyst.Although add a large amount of acid for example the technology of nitric acid be effectively for the solubility of enhanced activity metallic compound, when too a large amount of sour of adding, this technology can cause the reduction of carrier surface area, and this reduction is the main cause of desulphurizing activated reduction.

When the pore volume of carrier is 1ml/g or more hour, carrier does not have so little specific area, so reactive metal shows good decentralization, produces the catalyst with high desulfurization activity.When the aperture of carrier is 60

Or when bigger, load has the catalyst of reactive metal not have so little aperture on it, so this situation is preferred.Because the diffusion that sulphur compound diffuses in the catalyst pores is not enough, has the desulphurizing activated reduction of the catalyst of small-bore.

When the aperture of carrier is 120

Or more hour, the specific area of gained catalyst is so not little, so this situation is preferred.When the specific area of catalyst hour, it is not enough that the decentralization of reactive metal becomes, and the desulphurizing activated reduction of gained catalyst.

The preference that is included in the 6th family's metal in the catalyst of the present invention is comprised molybdenum and tungsten.Molybdenum is particularly preferred.

Be converted into oxide and account for the amount of catalyst, the content of the 6th family's metal is 10 weight %～40 weight %, is preferably 16 weight %～35 weight %.

10 weight % or bigger content are enough for the effect that generation is attributable to the 6th family's metal.When content is 40 weight % or more hour, the gathering of the 6th family's metallic compound does not take place in dipping (load) step of the 6th family's metal, cause the good decentralization of the 6th family's metal.In addition, do not reduce significantly, therefore can observe the catalytic activity of enhancing, so this situation is preferred because the content of the 6th family's metal exceeds the limit and the surface area of effective dispersion.

The preference of the 8th family's metal comprises cobalt and nickel.

Be converted into oxide and account for the amount of catalyst, the content of the 8th family's metal is 1 weight %～15 weight %, is preferably 3 weight %～8 weight %.

When the content of the 8th family's metal is 1 weight % or when bigger, can fully obtain avtive spot, so this situation is preferred owing to the 8th family's metal.When content is 15 weight % or more hour, the gathering of the 8th family's metallic compound does not take place in dipping (load) step of the 8th family's metal, cause the good decentralization of the 8th family's metal.In addition, not it is believed that and form such as Co ₉S ₈And Ni ₃S ₂Deng species such as precursor CoO, the NiO of species and further be incorporated into species such as cobalt spinel in the support crystal lattice, nickel spinelle, described such as Co ₉S ₈And Ni ₃S ₂Deng species is inert metal species such as cobalt and nickel grade in an imperial examination 8 family's metals.Therefore, can observe the catalytic activity of enhancing, thereby this situation is preferred.

According to the amount of oxide, to be preferably the value of [the 8th family's metal]/[the 8th family's metal+the 6th family's metal] be about 0.1～0.25 to the optimum weight ratio of the 8th family's metal that comprises with above-mentioned amount and the 6th family's metal respectively.

When this ratio is 0.1 or when bigger, the formation of CoMoS phase, NiMoS phase (it is believed that it is the avtive spot of desulfurization) etc. is suppressed, and cause the improvement of desulphurizing activated enhancing, so this situation is preferred.When this ratio is 0.25 or more hour, the inertia species (Co of above-mentioned cobalt or nickel ₉S ₈Or Ni ₃S ₂) formation be suppressed the catalytic activity that produce to strengthen, so this situation is preferred.

Be converted into oxide and account for the amount of catalyst, the content of phosphorus is 1.5 weight %～8 weight %, is preferably 2 weight %～6 weight %, more preferably 3 weight %～6 weight %.

When content is 1.5 weight % or when bigger, the 6th family's metal has formed heteropoly acid on catalyst surface by inference, and has formed the multilayer MoS of high degree of dispersion in the presulfurization step ₂Crystal has fully produced the aforementioned avtive spot that is used for desulfurization, so this situation is preferred.Particularly,, make catalyst can have laminate, the content of phosphorus must be adjusted to 1.5 weight % or bigger with 2.5～5 average such as molybdenum bisuphide grade in an imperial examination 6 family's metal dithionite things for after above-mentioned presulfurization.

On the other hand, when content is 8 weight % or more hour, in the presulfurization step, the 6th family's metal fully forms heteropoly acid on catalyst surface, and the phosphorus that does not form heteropoly acid is dispersed on the surface of aluminium oxide and covers the above-mentioned high-quality avtive spot that is used for desulfurization, therefore activity does not reduce, thereby this situation is preferred.

In the content of phosphorus composition, the optimum weight ratio of reactive metal molybdenum and phosphorus is as [P ₂O ₅]/[MoO ₃] value be preferably 0.07～0.3, more preferably 0.09～0.25.

As above-mentioned ratio, when the weight ratio of molybdenum and phosphorus is 0.07 or when bigger, the integrated of Co and Mo can be realized and after sulfuration, the laminate of molybdenum bisuphide can be formed, by these two reasons, can easily obtain being used for the avtive spot of desulfurization: CoMoS mutually with NiMoS mutually, especially easily the CoMoS that obtains demonstrating high desulfurization activity at the avtive spot that is used for desulfurization mutually and NiMoS II type site mutually so can make and has highly active catalyst, thereby this situation is preferred.

Weight ratio is 0.3 or is preferred more for a short time, this be because, because the surface area and the pore volume of catalyst do not reduce, thereby activity of such catalysts do not reduce, and since the acid amount increase and do not cause carbon deposition, so more difficult active deterioration takes place.

Based on catalyst, the content of carbon is 2 weight %～14 weight %, is preferably 2 weight %～10 weight %, more preferably 2 weight %～4 weight %.

Carbon is to derive from organic acid, the carbon of optimization citric acid.When content is 2 weight % or when bigger, the 8th family's metal and organic acid fully form complex compound on catalyst surface.In this case, by inference in the presulfurization step, before the sulfuration of the 8th family's metal, to the 6th family metal sulfuration of complex form in the presulfurization step, fully formed thus be used for desulfurization avtive spot (for example, CoMoS phase, NiMoS phase, or the like), thereby do not form inertia species Co such as cobalt and nickel grade in an imperial examination 8 family's metals ₉S ₈Or Ni ₃O ₂, and form materials such as the spinelle be incorporated in the support crystal lattice, nickel spinelle, so this situation is preferred.

When carbon content is 14 weight % or more hour, the 8th family's metal and organic acid fully form complex compound on catalyst surface.On the other hand, the 6th family's metal and organic acid do not form complex compound, and the excess carbon that derives from the organic acid do not remain in catalyst surface, so this situation is preferred.

When the 6th family's metal and organic acid have formed complex compound, the 6th family's metal is vulcanized simultaneously with the sulfuration of the 8th family's metal in activation (sulfuration).By inference in sulfuration, and the avtive spot that is formed for desulfurization not yet in effect (for example, CoMoS phase, NiMoS phase, or the like), this has caused the inertia species Co such as cobalt and nickel grade in an imperial examination 8 family's metals ₉S ₈Or Ni ₃S ₂Formation.

In addition, excessive carbon is to cause the active reason that reduces, and this is because excessive carbon has covered desulphurizing activated site as catalyst poison in sulfurating stage.

For enhanced activity in the hydrodesulfurization of light oil and desulfurization, catalyst of the present invention should have above-mentioned composition, and has following specific area, pore volume and average particle size values.

The specific area of catalyst (measuring by nitrogen adsorption method (BET method)) is about 150～300m ²/ g is preferably about 180～280m ²/ g.

When specific area is 150m ²/ g or when bigger, it is believed that separately that all (the 6th family's metal forms heteropoly acid with the phosphoric acid coordination for the 6th family's metal of existing with complex form and the 8th family's metal, and the 8th family's metal forms metal-organic complex with the organic acid coordination), even each metal complex is all very huge, also can on catalyst surface, be in sufficient high degree of dispersion state separately.As a result, by vulcanizing the formation that can be easy to accurately adjust above-mentioned avtive spot, made catalyst thus with high desulfurization activity.Therefore, this situation is preferred.

When specific area is 300m ²/ g or more hour, it is very not little that the aperture becomes, so this catalyst do not have so little aperture, and because sulphur compound fully diffuses in the catalyst pores, so desulphurizing activated in the hydrotreatment reduces.

The pore volume of the catalyst of measuring by the mercury osmosis is 0.3～0.6ml/g, is preferably 0.3～0.5ml/g.When pore volume is 0.3ml/g or when bigger, because sulphur compound fully diffusion in catalyst pores, so catalyst has desulphurizing activatedly fully in hydrotreatment, so this situation is preferred.When pore volume is 0.6ml/g or more hour, the decentralization that catalyst does not have too small specific area and reactive metal does not reduce.Therefore, the gained catalyst has high desulfurization activity, thereby this situation is preferred.

The average pore size of the catalyst that the pore size distribution that records by the mercury osmosis is measured is about 65

～140

Be preferably about 90

～130

More preferably 96

～130

When average pore size is 65 Or when bigger, reactant is easy to be diffused in the hole, so desulphurization reaction can effectively carry out, thereby this situation is preferred.When average pore size is 140

Or more hour, the diffusion of Xiang Kongzhong is gratifying and the internal surface area in hole does not reduce, so the effective ratio area of catalyst do not reduce, and the gained catalyst has the activity of enhancing.

In order to increase effective quantity in the hole that meets the requirement of above-mentioned hole, the pore-size distribution of catalyst promptly can be had based on average pore size about ± 15 The ratio in the hole of the diameter in the scope is adjusted into 30%～75%, is preferably 35%～70%, and more preferably 40%～60%.When this ratio is 75% or more hour, compound to be desulfurization is not limited to specific sulphur compound, and all sulphur compounds all can be desulfurized, so this situation is preferred.On the other hand, when this ratio is 30% or when bigger, does not increase in the hole that is helpless to the light oil desulfurization, the result desulphurizing activatedly significantly reduces.

And catalyst of the present invention is preferably after vulcanizing treatment, and the average of the laminate by transmission electron microscopy observation such as molybdenum bisuphide grade in an imperial examination 6 family's metal dithionite things is 2.5～5 catalyst.

That is, these layers that are formed on molybdenum bisuphide on the inorganic oxide carrier etc. not only are used to increase the contact area of catalyst, and have the avtive spot that is formed at wherein, for example CoMoS phase, NiMoS phase, or the like.Yet, wherein the average of this laminate be 2.5 or bigger catalyst do not have the low activity I type site that the CoMoS phase, NiMoS of vast scale like this equate, therefore have high activity, thereby this situation is preferred.On the other hand, average be 5 or lower catalyst in formed the high activity II type site that CoMoS phase, NiMoS equate, and the absolute number of avtive spot does not reduce.Therefore, these catalyst have demonstrated high activity, thereby this situation is preferred.

In this respect, as the transmission electron microscope photo that is used to analyze, can use those can carry out in visual observation, the every visual field crystal number to the crystal such as molybdenum bisuphide grade in an imperial examination 6 family's metal dithionite things is 200 or higher photo.

And the average length such as on the direction in the face of the disulphide layer of molybdenum bisuphide grade in an imperial examination 6 family's metals by transmission electron microscope observation is 1～3.5nm suitably, is preferably 2～3.5nm.

1nm or the bigger interior direction length of face are preferred, this is because owing to the molybdenum bisuphide equimolecular not only exists as individual molecule, cobalt and nickel can form square tapered pentacoordinate sulphur structure, therefore can form CoMoS phase, NiMos phase as avtive spot, or the like.3.5nm or direction length also is preferred in the littler face, this is because because crystal of molybdenum disulfide does not increase dimensionally, the absolute number on limit does not reduce, and it is hereby ensured the CoMoS phase of enough numbers, the avtive spot that NiMoS equates.

Catalyst of the present invention with above-mentioned performance preferably makes by the method for the present invention of explained later.

Promptly, preferably make catalyst by such method, this method comprises with the solution with the compound that contains the 6th family's metal, the compound that contains the 8th family's metal, organic acid and phosphoric acid, have on the inorganic oxide carrier of above-mentioned characteristic, with at least a aforesaid the 6th family's metal of above-mentioned amount load, at least a aforesaid the 8th family's metal, phosphorus and carbon, carry out drying then respectively.Particularly, for example, this method can be carried out drying and finish subsequently by inorganic oxide carrier is flooded with the solution that contains compound etc.

The employed examples for compounds that contains the 6th family's metal comprises molybdenum trioxide, phosphomolybdic acid, ammonium molybdate, molybdic acid etc. in above-mentioned dipping solution.Molybdenum trioxide and phosphomolybdic acid are preferred.

These compounds can be joined in the dipping solution with such amount, make the gained catalyst contain to be in the 6th family's metal of the amount in the above-mentioned scope.

The examples for compounds that contains the 8th family's metal comprises cobalt carbonate, nickelous carbonate, citric acid cobalt compound, citric acid nickel compound, cabaltous nitrate hexahydrate and Nickelous nitrate hexahydrate etc.Cobalt carbonate, nickelous carbonate, citric acid cobalt compound and citric acid nickel compound are preferred.Particularly preferably be with cobalt carbonate and compare, have the citric acid cobalt compound and the citric acid nickel compound of low decomposition rate with nickelous carbonate.

That is, when decomposition rate was high, cobalt or nickel grade in an imperial examination 8 family's metals had formed and other independent stratum of disulphide layer phase region such as molybdenum grade in an imperial examination 6 family's metals, the insufficient formation that has caused high activity CoMoS phase, NiMoS to equate.In contrast, when decomposition rate was low, described high activity can form fully in the marginal portion of molybdenum bisuphide etc. mutually.

The example of above-mentioned citric acid cobalt compound comprises citric acid cobalt (II) (Co ₃(C ₆H ₅O ₇) ₂), hydrogen citrate cobalt (CoHC ₆H ₅O ₇) and citric acid cobalt oxysalt (Co ₃(C ₆H ₅O ₇) ₂CoO) etc.The example of citric acid nickel compound comprises citric acid nickel (Ni ₃(C ₆H ₅O ₇) ₂), hydrogen citrate nickel (NiHC ₆H ₅O ₇) and citric acid nickel (II) oxysalt (Ni ₃(C ₆H ₅O ₇) ₂NiO) etc.

The citrate compound of cobalt and nickel can prepare with following manner.Under the situation that is cobalt,, cobalt carbonate makes this compound in the aqueous citric acid solution by being dissolved in.The citrate compound that obtains by this method can use by the former state in the Preparation of Catalyst thing, anhydrates and need not therefrom remove.

The 8th family's metallic compound can be joined in the dipping solution with such amount, make the gained catalyst comprise to be in the 8th family's metal of the amount in the above-mentioned scope.

The organic acid example comprises citric acid monohydrate, citric anhydride, isocitric acid, maleic acid, tartaric acid, oxalic acid, butanedioic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, M-phthalic acid, salicylic acid, malonic acid etc.Citric acid monohydrate is preferred.Using substantially not, the compound of sulfur-bearing is very important as organic acid.

When with citric acid when the organic acid, citric acid can be independent citric acid form or with the form of above-mentioned citrate compound such as cobalt or nickel grade in an imperial examination 8 family's metals.

It is important that organic acid is added with such amount: make the carbon that still has above-mentioned content in the gained catalyst.With respect to the 8th family's metal, such organic acid addition is favourable: the mol ratio of organic acid/the 8th family's metal is 0.2～1.2, is preferably 0.6～1.

Mol ratio be 0.2 or bigger be preferred, this is because can fully obtain avtive spot owing to the 8th family's metal.When this ratio is 1.2 or more hour, dipping solution does not have so high viscosity, and the step that therefore is used for load can not expend a large amount of time, and reactive metal can infiltrate the inside of carrier material grain fully, thereby can realize the fine dispersion state of reactive metal, so this situation is preferred.

In addition,, make that the mol ratio of organic acid/[(the 6th family's metal)+(the 8th family's metal)] is 0.35 or littler, be preferably 0.28 or littler with respect to the total amount of the 6th family's metal and the 8th family's metal, more preferably 0.26 or littler organic acid addition be favourable.0.35 or littler mol ratio is preferred, this is because the excessive organic acid that forms complex compound with metal does not remain on the surface of catalyst.When organic acid remained on the surface of catalyst, acid can be flowed out with feedstock oil in vulcanisation step.

The example of phosphoric acid comprises various phosphoric acid, for example orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, four phosphoric acid and polyphosphoric acid etc.Orthophosphoric acid is particularly preferred.

As phosphoric acid, can use as with the phosphomolybdic acid of the compound of the 6th family's metal.In this case, when the phosphorus content in the gained catalyst is lower than above-mentioned following prescribing a time limit, should further add phosphoric acid.

When the compound of the compound of the 6th family's metal or the 8th family's metal can not fully dissolve in dipping solution, can use with this compound such as nitric acid, organic acid acid such as (for example, citric acid, maleic acid, tartaric acid etc.).The preferred organic acid that uses.When using organic acid, exist still to have the situation that derives from organic acid carbon in the gained catalyst.Therefore, adjusting carbon content in the catalyst, it is in the above-mentioned scope is important.

In the superincumbent dipping solution, the solvent that is used for dissolving mentioned component is a water.

When the amount of solvent for use too hour, impregnated carrier fully.When this amount was too big, the part reactive metal that is dissolved did not load on the catalyst, but on the residual edge or other parts attached to the used container of dipping solution, therefore can not obtain desired load capacity.Therefore, every 100g carrier, the amount of solvent is 50～90g, is preferably 60～85g.

By being dissolved in the above-mentioned solvent, above-mentioned various compositions make dipping solution.At this moment, temperature can be for being higher than 0 ℃～100 ℃ or lower.As long as temperature is in this scope, above-mentioned various compositions can be dissolved in the solvent satisfactorily.

The pH of above-mentioned dipping solution is preferably less than 5.When pH less than 5 the time, the amount of hydroxyl ion does not increase, and has strengthened the coordination ability between organic acid and the 8th family's metal, so has accelerated the formation of the complex compound of the 8th family's metal.As a result, can increase the number of the avtive spot that is used for desulfurization (CoMoS mutually or the NiMoS phase, or the like) greatly, therefore, this situation is preferred.

Inorganic oxide carrier is flooded with the dipping solution that so makes, and the above-mentioned various compositions that will be included in thus in the solution are deposited on the above-mentioned inorganic oxide carrier.

Dipping can carry out under various conditions.Yet normally, dipping temperature is preferably and is higher than 0 ℃ and be lower than 100 ℃, more preferably 10～50 ℃, most preferably is 15～30 ℃.Dip time is preferably 15 minutes～and 3 hours, more preferably 20 minutes～2 hours, most preferably be 30 minutes～1 hour.

When dipping temperature is too high, drying can take place in dipping process, cause the inhomogeneous of degree of scatter.Preferably during dipping stir the mixture.

After solution impregnation, under the temperature of room temperature～about 80 ℃, in nitrogen or air stream or under vacuum, with water content remove to a certain degree (to 50% or lower LOI (loss on ignition)).Then, in air or nitrogen stream or under vacuum, carry out drying, preferably 80～200 ℃ of dryings 10 minutes～24 hours, more preferably 100～150 ℃ of dryings 5～20 hours 200 ℃ or lower temperature.

When at 200 ℃ or when more carrying out drying under the low temperature, it is believed that the organic acid that forms complex compound with metal does not discharge from catalyst surface.As a result, in the sulfuration of gained catalyst, can accurately adjust the formation of above-mentioned avtive spot (for example, CoMoS phase, NiMoS phase, or the like) by inference at an easy rate, and not form Co as the inertia species of cobalt and nickel ₉S ₈, Ni ₃S ₂, and be 2.5～5 such as the average number of the laminate of molybdenum bisuphide grade in an imperial examination 6 family's metal dithionite things.That is, made catalyst, so this situation is preferred with high desulfurization activity.

Yet, when under vacuum, carrying out drying, preferably carry out dry making and satisfy the said temperature scope that when 760mmHg pressure, converts.Pressure limit when dry is 300～900mmHg, is preferably 700～850mmHg, and more preferably 730～800mmHg most preferably is atmospheric pressure.

Pressure when drying is 300mmHg or when higher, boiling point becomes 200 ℃ that convert when not being higher than 760mmHg pressure, thereby is not easy to discharge with organic acid that metal forms complex form.It is believed that the organic acid that forms complex form with metal does not discharge from catalyst surface, the result, in the sulfuration of gained catalyst, can (for example accurately adjust above-mentioned avtive spot at an easy rate, CoMoS phase, NiMoS phase, or the like) formation, and do not form Co as the inertia species of cobalt and nickel ₉S ₈, Ni ₃S ₂Deng.That is, made catalyst, so this situation is preferred with high desulfurization activity.

In the present invention, the shape of catalyst is restriction especially, can be in the different shape of the common use of the type catalyst any one, for example, and cylindrical, trilobal, quatrefoil (quadlobe).Usually, it is about 1～2mm that size of catalyst is preferably diameter, and length is about 2～5mm.

The mechanical strength of catalyst is preferably about 2lbs/mm (pound/millimeter) or higher with regard to side crushing strength (SCS).When the SCS of catalyst was lower than this value, the catalyst granules that is filled in the reactor was damaged to produce pressure differential in reactor, made and can not carry out continuous hydrotreatment operation.

The closs packing density (CBD) of catalyst is preferably 0.6～1.2g/ml.

The distribution of reactive metal is preferably even type in the catalyst, and wherein reactive metal evenly distributes in catalyst.

It is that 3～8MPa, temperature are that 300～420 ℃ and liquid hourly space velocity are 0.3～5hr that hydrotreating method of the present invention is included in hydrogen partial pressure ^-1Condition under, the light oil distillate that includes the sulphur composition is contacted with above-mentioned catalyst, so that light oil distillate is carried out desulfurization, reduce the sulphur compound be included in the light oil distillate thus, comprise the sulphur composition that is difficult to remove.

The product oil that the hydroprocessing technique of the product oil ratio that obtains by method of the present invention by routine techniques obtains has lower sulfur content and nitrogen content.

In order to carry out hydrotreating method of the present invention with commercial size, the catalyst layer of fixed bed, moving bed or fluidized bed type that can be by catalyst of the present invention is provided in reactor, feedstock oil is introduced this reactor, and hydrotreatment is carried out in reaction under these conditions.

Under prevailing situation, in reactor, place the fixed bde catalyst layer, fixed bed is introduced and passed to feedstock oil from top to bottom from the top of reactor.Discharge product oil from the bottom of reactor.

Method of the present invention can be the single step hydrotreating method, in the method, in being filled with the single reactor of catalyst of the present invention, handle feedstock oil, perhaps can be multistep continously hydrogen adding facture, use a plurality of reactors that are filled with catalyst in the method.

Before using (that is, before hydroprocessing technique of the present invention), catalyst of the present invention activates by sulfuration in reactor.Can use the petroleum distillate that contains sulphur compound, and to wherein adding such as vulcanizing agents such as dimethyl disulphide or carbon disulfide, or under 200～400 ℃ temperature, under preferred 250～350 ℃ temperature, under more than or equal to the hydrogen atmosphere of normal pressure, carry out vulcanizing treatment with hydrogen sulfide at hydrogen partial pressure.

By vulcanizing treatment, catalyst of the present invention has formed the laminate such as molybdenum bisuphide grade in an imperial examination 6 family's metal dithionite things, and the number of plies that on average laminates of this laminate is 2.5～5, and direction length is 1～3.5nm in the centre plane.And catalyst has formed the high activity site that CoMoS phase, NiMoS equate, these high activity sites are formed at the marginal portion of molybdenum bisuphide etc.

Usually, the avtive spot structure that is known as the desulphurization catalyst avtive spot at present is CoMoS phase, the NiMoS phase that people (N-.Y.Tops Φ e, H.Tops Φ e, J.Catal.84,386 (1983)) such as Tops Φ e proposes, or the like.People such as Tops Φ e find after vulcanizing treatment and the NO absorption as probe molecule, as using FFIR (FT-IR) to CoMo/Al ₂O ₃The result that catalyst surface is studied, catalyst desulphurizing activated high more, it is just big more and to derive from the absorption of Mo side just more little then to derive from the absorption of Co side.They infer that the appearance of this phenomenon is because in having the catalyst of high desulfurization activity, CoMoS has covered MoS mutually effectively ₂The site, edge.

When catalyst of the present invention after vulcanizing treatment and NO subsequently absorption, FT-IR observes with the diffuse reflection method, the value of I8 family/(I8 family+I6 family) is 0.7～1, wherein is adsorbed on the NO spectrum (1840cm on the 8th family's metal ^-1) intensity represent with I8 family, be adsorbed on the NO spectrum (1700cm on the 6th family's metal ^-1) intensity represent with I6 family.

0.7 or bigger value is preferred, this is because can fully form to it is believed that it is CoMoS phase, the NiMoS phase in desulphurizing activated site, or the like, that therefore can realize strengthening is desulphurizing activated.As mentioned above, this value is preferably 0.7～1.When this value is 1, on the marginal portion of molybdenum bisuphide etc., fully formed CoMoS phase, NiMoS phase as desulphurizing activated site, or the like, therefore can observe high desulfurization activity, and not demonstrate any intensity peak of I6 family metal.The above-mentioned characteristic of catalyst of the present invention is to realize the major reason of the desired purpose of the present invention.

Embodiment

More specifically describe the present invention below with reference to embodiment and Comparative Examples, but the present invention is not limited to the following example.

Embodiment 1

With SiO ₂/ Al ₂O ₃Mol ratio is 6 zeolite SHY powder (average grain diameter: 3.5 μ m; Particle diameter be 6 μ m or littler zeolite granular account for all particles 87%) mediate with hydrated alumina.With the extrusion modling of gained mixture and 600 ℃ of calcinings 2 hours, to obtain the zeolite-alumina composite carrier of cylinder article shaped form, the diameter of this cylinder article shaped is 1/16 inch (1 inch=25.4 millimeters) (weight ratio of Zeolite/alumina: 5/95; Pore volume: 0.79ml/g; Specific area: 311m ²/ g; Average pore size: 93

).

In the 22.3g ion exchange water, add 10.27g citric acid cobalt and 2.24g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 17.61g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.52.

Above-mentioned zeolite-the alumina composite carrier of 30.0g of in eggplant type flask, packing into.To wherein adding all above-mentioned dipping solutions of amount, and carrier is immersed 3 hours at about 25 ℃ with pipette in solution.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst A.

Embodiment 2

In the 24.9g ion exchange water, add 4.53g cobalt carbonate, 12.86g molybdenum trioxide, 5.34g citric acid monohydrate and 2.63g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stir and prepared the solution that is used to flood in 30 minutes subsequently.At this moment, the pH of dipping solution is 0.54.

Identical zeolite-the alumina composite carrier of 30.0g and embodiment 1 of in eggplant type flask, packing into.To wherein adding all above-mentioned dipping solutions of amount, carrier is immersed 3 hours at about 25 ℃ with pipette in solution.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst B.

Embodiment 3

In the 22.1g ion exchange water, add 10.42g citric acid cobalt (II) and 3.06g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 17.89g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.54.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst C.

Embodiment 4

In the 21.9g ion exchange water, add 10.59g citric acid cobalt (II) and 3.91g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 18.18g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.54.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst D.

Embodiment 5

In the 22.3g ion exchange water, add 8.21g citric acid cobalt (II), 2.06g citric acid nickel and and 2.24g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 17.61g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.54.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst E.

Embodiment 6

In the 22.7g ion exchange water, add 8.34g citric acid cobalt (II), 2.09g citric acid nickel and 3.06g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 17.89g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.54.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst F.

Embodiment 7

Hydrated alumina is mediated, and with the kneaded material extrusion modling, 600 ℃ of calcinings 2 hours, to obtain the gamma-aluminium oxide carrier of cylinder article shaped form, the diameter of this cylinder article shaped was 1/16 inch (pore volume: 0.85ml/g then; Specific area: 249m ²/ g; Average pore size: 100

).

In the 23.7g ion exchange water, add 10.27g citric acid cobalt (II) and 2.24g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 17.61g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.52.

The above-mentioned gamma-aluminium oxide carrier of 30.0g of in eggplant type flask, packing into.To wherein adding all above-mentioned dipping solutions of amount, carrier is immersed 3 hours at about 25 ℃ with pipette in solution.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst G.

Embodiment 8

In the 25.4g ion exchange water, add 4.54g cobalt carbonate, 17.61g phosphomolybdic acid, 3.97g malonic acid and 2.24g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stir the solution that was used to flood with preparation in 30 minutes subsequently.At this moment, the pH of dipping solution is 0.53.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst H.

Embodiment 9

In the 25.4g ion exchange water, add 4.54g cobalt carbonate, 17.61g phosphomolybdic acid, 5.11g DL-malic acid and 2.24g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 30 minutes subsequently.At this moment, the pH of dipping solution is 0.56.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst I.

Embodiment 10

In the 25.4g ion exchange water, add 4.54g cobalt carbonate, 17.61g phosphomolybdic acid, 4.27g citric acid, 0.45g butanedioic acid, 0.57g tartaric acid and 2.24g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 30 minutes subsequently.At this moment, the pH of dipping solution is 0.56.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst J.

Embodiment 11

In the 22.1g ion exchange water, add 10.42g citric acid cobalt (II) and 3.06g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 17.89g phosphomolybdic acid and 0.50g tungstic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.57.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst K.

Embodiment 12

With SiO ₂/ Al ₂O ₃Mol ratio is 6 zeolite SHY powder (average grain diameter: 3.5 μ m; Particle diameter be 6 μ m or littler zeolite granular account for all particles 87%) mediate with hydrated alumina.With the extrusion modling of gained mixture and 600 ℃ of calcinings 2 hours, obtain the zeolite-alumina composite carrier of cylinder article shaped form, the diameter of this cylinder article shaped is 1/16 inch (weight ratio of Zeolite/alumina: 7/93; Pore volume: 0.69ml/g; Specific area: 374m ²/ g; Average pore size: 67

).

In the 19.8g ion exchange water, add 7.92g citric acid cobalt (II) and 3.68g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 12.08g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.48.

Above-mentioned zeolite-the alumina composite carrier of 30.0g of in eggplant type flask, packing into.To wherein adding all above-mentioned dipping solutions of amount, carrier is immersed 3 hours at about 25 ℃ with pipette in solution.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst L.

Embodiment 13

In the 24.6g ion exchange water, add 5.34g cobalt carbonate and 4.29g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 15.26g molybdenum trioxide and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.56.

Then, carrier is dry in stream of nitrogen gas, then in Muffle furnace and under atmospheric pressure in air draught in about 16 hours of 120 ℃ of dryings, to obtain catalyst M.

Comparative Examples 1

3.31g cobalt carbonate, 11.41g phosphomolybdic acid and 1.17g orthophosphoric acid are dissolved in the 21.6g ion exchange water, make the solution that is used to flood thus.In eggplant type flask, pack into the gamma-aluminium oxide carrier (pore volume: 0.69ml/g of 30.0g; Specific area: 364m ²/ g; Average pore size: 64

).To wherein adding all above-mentioned dipping solutions of amount, carrier is immersed 1 hour at about 25 ℃ with pipette in solution.

Then, carrier is dry in stream of nitrogen gas, subsequently in Muffle furnace and under atmospheric pressure in air draught in about 4 hours of 120 ℃ of dryings, then 500 ℃ of calcinings 4 hours, to obtain catalyst a.

Comparative Examples 2

In the 20.2g ion exchange water, add 7.45g citric acid cobalt (II) and 1.17g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 11.41g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.

Then, carrier is dry in stream of nitrogen gas, subsequently in Muffle furnace and under atmospheric pressure in air draught in about 1 hour of 120 ℃ of dryings, then 500 ℃ of calcinings 4 hours, to obtain catalyst b.

Comparative Examples 3

In the 30.0g ion exchange water, add 2.61g cobalt carbonate, 6.41g molybdenum trioxide, 6.14g citric acid monohydrate and 2.77g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stir the solution that was used to flood with preparation in 30 minutes subsequently.At this moment, the pH of dipping solution is 0.82.

In eggplant type flask, pack into the gamma-aluminium oxide carrier (pore volume: 0.61ml/g of 30.0g; Specific area: 240m ²/ g; Average pore size: 72

Then, carrier is dry in stream of nitrogen gas, subsequently in Muffle furnace and under atmospheric pressure in air draught in about 4 hours of 120 ℃ of dryings, then 500 ℃ of calcinings 4 hours, to obtain catalyst c.

Comparative Examples 4

In the 19.3g ion exchange water, add 8.28g citric acid cobalt (II) and 5.76g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes then.Subsequently, to wherein adding 12.64g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.46.

Comparative Examples 5

In the 22.6g ion exchange water, add 3.31g cobalt carbonate and 1.17g phosphoric acid (85% the aqueous solution), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 11.41g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.54.

Comparative Examples 6

In the 20.5g ion exchange water, add 7.27g citric acid cobalt (II), be heated to 80 ℃ and stirred 10 minutes subsequently.Subsequently, to wherein adding 11.10g phosphomolybdic acid and dissolving, under uniform temp, stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 0.78.

Comparative Examples 7

In the 25.3g ion exchange water, add 4.34g cobalt carbonate and 12.29g phosphomolybdic acid, be heated to 80 ℃ and stir the solution that was used to flood with preparation in 15 minutes subsequently.At this moment, the pH of dipping solution is 1.95.

The elementary analysis value and the physical property of the catalyst that obtains in the foregoing description and Comparative Examples are as shown in table 1.

The method and the analytical instrument of physical property that is used to measure catalyst as shown in table 1 is as follows.

[measurement of specific area (SA)]

Specific area is measured by the BET method based on nitrogen adsorption.

As the nitrogen adsorption device, use the surface area test instrument of producing by Bell Japan Corporation (Belsorp 28).

[measurements of pore volume (PV), average pore size (MPD) etc.]

Pore volume, average pore size and pore size distribution are measured by the mercury osmosis.

(MICROMERITICSAUTO-PORE 9200 to use pore bridging; Produce by Shimadzu Seisakusho Ltd.) as the device that is used for the mercury infiltration.

With sample 400 ℃ of heating in vacuum 1 hour therefrom to remove volatile matter, measure then.

[measurement of curing molybdenum layer (TEM)]

The number of plies that laminates of molybdenum bisuphide is measured with following method with transmission electron microscope (TEM) (trade name " JEM-2010 ", JEOL Ltd. produces).

1) catalyst is filled in the circulation type reaction tube.The catalyst of being filled was at room temperature kept 5 minutes in stream of nitrogen gas, and use H ₂S (5 volume %) and H ₂Mixture displacement ambient gas.With the speed heating of catalyst with 5 ℃/minute.After catalyst temperature reaches 400 ℃, catalyst is kept being cooled to 200 ℃ then in identical atmosphere in 1 hour in this temperature.Subsequently, with the nitrogen replacement ambient gas and with the catalyst cool to room temperature to finish vulcanizing treatment.

2) catalyst after the vulcanizing treatment is ground in agate mortar.

3) catalyst through grinding is dispersed in the acetone on a small quantity.

4) with the gained hanging drop to microgrid, and at room temperature dry to obtain sample.

5) sample is placed on the detection position of TEM, and under the accelerating potential of 200kV, detects.Directly multiplication factor is 200,000 times, and has detected five area of visual field.

6) each photo is amplified, make that multiplication factor is 2,000,000 times of (size: 16.8cm * 16.8cm).Measure direction length in the face that laminates the number of plies and layer of molybdenum bisuphide with photo, wherein each area of visual field has 200 or more can visual identification such as the crystal of the disulphide of molybdenum bisuphide grade in an imperial examination 6 family's metals.

[measurement (NO-IR) of NO absorption FT-IR (FFIR)]

In order to study after the preliminary treatment gas absorption amount on the reactive metal (Co, Mo etc.) in catalyst, after the preliminary treatment NO is being adsorbed on the catalyst, and is going up catalyst is observed at diffuse reflection method FT-IR (FT-IR-8100M, Shimadzu Seisakusho Ltd. produces).At this moment, the heating, vacuum type diffuse reflection pond (KBr shadow shield) of using Spectratech Inc. to produce.

A) preliminary treatment of catalyst (vulcanizing treatment): after grinding, catalyst is placed in the diffuse reflection pond, and in the He air-flow, heats.After catalyst temperature reaches 400 ℃, catalyst was kept 30 minutes in this temperature.Then, use H ₂S (5%) and H ₂Mixture displacement ambient gas, and catalyst kept 2 hours in this temperature.Subsequently, with He gas displacement ambient gas, and at arc discharge (flashing) after 30 minutes, in same airflow with the catalyst cool to room temperature, to finish preliminary treatment.

B) FT-IR measures: catalyst after keeping 30 minutes under the room temperature in the NO gas flow, with He gas displacement ambient gas, and is carried out FT-IR in exhaust and measures after 30 minutes.

Measuring condition:

Wave-length coverage: 4600～400cm ^-1

Resolution ratio: 4cm ^-1

C) analysis of measurement result: the NO spectrum (1840cm on the 8th family's metal, adsorbing separately ^-1) intensity and the NO spectrum (1700cm that on the 6th family's metal, adsorbs ^-1) intensity study, and use the represented value of following formula come comparison such as on the edge of molybdenum bisuphide grade in an imperial examination 6 family's metal dithionite things, it is believed that it is the CoMoS phase in desulphurizing activated site, the number that NiMoS equates:

The avtive spot of ICoMoS etc.=I8 family/(I8 family+I6 family)

Wherein I8 family is illustrated in the NO spectral intensity of adsorbing on the 8th family's metal, and I6 family is illustrated in the NO spectral intensity of adsorbing on the 6th family's metal.

As typical example, the NO of catalyst A absorption FT-IR spectrum as shown in fig. 1.

And the transmission electron microscope photo (TEM) of catalyst B as shown in Figure 2.

[the hydrotreatment reaction of straight run light oil]

With the catalyst A～M in top embodiment and the Comparative Examples and a～g, the straight run light oil with character as follows is carried out hydrotreatment according to following method.

At first, catalyst is filled in the high pressure flow-through reactor to form the fixed bde catalyst layer, this fixed bde catalyst layer carries out preliminary treatment under the following conditions.

Then, introduce from the top of reactor, make and carry out the hydrotreatment reaction under the following conditions being heated to the feedstock oil of reaction temperature and the mixture of hydrogen-containing gas.Product oil is discharged from the bottom of reactor with the mixture of gas, and with gas/liquid separation products of separated oil.

Preliminary treatment: each catalyst is carried out liquid curing with feedstock oil.

Pressure (hydrogen partial pressure): 4.9Mpa

Atmosphere: hydrogen and feedstock oil (liquid hourly space velocity: 1.5hr ^-1The ratio of hydrogen/oil: 200m ³(normal pressure, normal)/kl)

Temperature: introduce hydrogen and feedstock oil in about 22 ℃ temperature, heat up, kept 24 hours, be elevated to reaction temperature, promptly 350 ℃ with 20 ℃/hour speed subsequently at 300 ℃ with 20 ℃/hour speed.

The hydrotreatment reaction condition:

Reaction temperature: 350 ℃

Pressure (hydrogen partial pressure): 4.9Mpa

Liquid hourly space velocity: 1.5hr ^-1

The ratio of hydrogen/oil: 200m ³(normal pressure)/kl)

The raw material oil properties:

Oil kind: from the straight run light oil in the Middle East

Density (15/4 ℃): 0.8570

Distillation characteristic: initial boiling point is 212.5 ℃, and 50% is 303.5 ℃, and 90% is 354.0 ℃, and terminal point is 372.5 ℃

Sulfur content: 1.61 weight %

Nitrogen content: 140 ppm by weight

Dynamic viscosity: (@30 ℃): 5.857 cSt

Flow point :-2.5 ℃

Cloud point: 1.0 ℃

Cetane lndex: 54.5

Saybolt color :-6

By following methods analyst reaction result.

Reactor is 350 ℃ of operations.After six days, product oil is taken a sample and analyzed its character.Desulfurization degree, desulphurization reaction velocity constant and specific activity calculate by following.The results are shown in the table 2.[1] desulfurization degree (HDS) is (%):

To change into hydrogen sulfide and the sulphur components in proportions that removes is defined as desulfurization degree from feedstock oil by desulphurization reaction.According to following formula, calculate desulfurization degree by the assay value of the sulfur content in feedstock oil and the product oil:

Desulfurization degree (%)=[(Sf-Sp)/Sf] * 100

[2] desulphurization reaction velocity constant (Ks):

The velocity constant of the reaction velocity equation of 1.3 order reactions that will provide with respect to the minimizing of sulfur content in the product oil (Sp) is defined as desulphurization reaction velocity constant (Ks).And rate constant is high more, and catalytic activity is excellent more.

Desulphurization reaction velocity constant=[1/ (Sp) ^(1.3-1)-1/ (Sf) ^(1.3-1)] * (LHSV) * 1/ (1.3-1)

In the formula of above-mentioned desulfurization degree and desulphurization reaction velocity constant, Sf represents the sulfur content (weight %) in the feedstock oil, the sulfur content (weight %) in the Sp representative products oil, and LHSV represents liquid hourly space velocity (hr ^-1).

[3] specific activity:

Specific activity (%)=((each desulphurization reaction velocity constant)/(the desulphurization reaction velocity constant of comparative catalyst a)) * 100

Table 2

As indicated in the table 2, be to be understood that the method according to this invention can reach the ultra-deep desulfurization district at an easy rate with catalyst A～M.

And, can understand significantly among the result who provides from above, under roughly the same condition, for example under the hydrogen partial pressure and reaction temperature in the light oil hydrotreating method of routine, has very excellent activity in the desulphurization reaction of catalyst according to the invention light oil in the ultra-deep desulfurization district and the denitrification reaction.

Although the present invention is described in detail, to those skilled in the art, do not break away from the spirit and scope of the present invention and make various variations and change is conspicuous with reference to its specific embodiment.

The application is based on the Japanese patent application 2003-091844 of Japanese patent application 2002-366916 that submitted on December 18th, 2002 and submission on March 28th, 2003, and its content is hereby incorporated by reference.

The application relates to the commissioned research result's that Japanese government subsidizes patent application (from commissioned research in 2002 of new forms of energy and industrial technology development organizations (reduce petroleum refinement pollutant etc. technological development), it is applicable to the 30th of industrial dynamism regeneration special measure method).

Industrial applicibility

According to the present invention, demonstrated following effect.

(1) catalyst has high desulfurization and denitrification activity, the sulphur in therefore can decrease light oil Content and nitrogen content.

(2) can adopt with conventional hydrotreating method in almost identical reaction condition. Therefore, can Use conventional equipment and need not significantly to transform.

(3) can easily supply sulfur content with reduction and the light oil base material of nitrogen content.

Claims

1. catalyst that is used for hydrotreatment light oil, this catalyst comprises at least a metal that is selected from periodic table the 6th family's metal of the 10 weight %～40 weight % on the inorganic oxide carrier, at least a metal that is selected from periodic table the 8th family's metal of 1 weight %～15 weight % and the phosphorus of 1.5 weight %～8 weight %, the described at least a metal that is selected from periodic table the 6th family's metal, be selected from least a metal of periodic table the 8th family's metal and phosphorus amount separately and be the amount that accounts for catalyst behind the oxide that is converted into, and 2 weight %～14 weight % derive from organic acid carbon, described amount is the amount that carbon accounts for catalyst, and, with respect to per 1 mole of periodic table the 8th family's metal, add 0.2～1.2 mole of described organic acid, described periodic table the 6th family's metal is selected from molybdenum and tungsten, described periodic table the 8th family's metal is selected from cobalt and nickel

The specific area of wherein said catalyst is 150～300m ²/ g, pore volume is 0.3～0.6ml/g, and average pore size is 96

～130 With

Wherein, when after vulcanizing treatment and NO subsequently absorption, when described catalyst was observed on diffuse reflection method Fourier transform infrared spectroscopy, the value of I8 family/(I8 family+I6 family) was in 0.7～1 the scope, and wherein, I8 family represents at 1840cm ^-1The place is adsorbed on the intensity of the NO spectrum on periodic table the 8th family's metal, and I6 family represents at 1700cm ^-1The place is adsorbed on the intensity of the NO spectrum on periodic table the 6th family's metal.

2. catalyst as claimed in claim 1, wherein said catalyst has such pore size distribution: the aperture is average pore size ± 15

The ratio in hole be 30%～75%.

3. catalyst as claimed in claim 1 or 2, wherein, after the vulcanizing treatment of described catalyst, the average of the laminate of the disulphide of periodic table the 6th family's metal by transmission electron microscope observation is 2.5～5.

4. catalyst as claimed in claim 1 or 2, wherein, after the vulcanizing treatment of described catalyst, direction length is 1～3.5nm in the centre plane of the disulphide layer of periodic table the 6th family's metal by transmission electron microscope observation.

5. preparation is as the method for the catalyst of each described hydrotreatment light oil of claim 1～4, this method comprises with the metal that contains in periodic table the 6th family, metal in periodic table the 8th family, the solution of organic acid and phosphoric acid, at least a metal that is selected from periodic table the 6th family's metal of load 10 weight %～40 weight % on inorganic oxide carrier, at least a metal that is selected from periodic table the 8th family's metal of 1 weight %～15 weight % and the phosphorus of 1.5 weight %～8 weight %, the described at least a metal that is selected from periodic table the 6th family's metal, be selected from least a metal of periodic table the 8th family's metal and phosphorus amount separately and be the amount that accounts for catalyst behind the oxide that is converted into, and 2 weight %～14 weight % derive from described organic acid carbon, described amount is the amount that carbon accounts for catalyst, and the specific area of described inorganic oxide carrier is 230～500m ²/ g, pore volume are that 0.5～1ml/g and average pore size are 60

～120

, and, with respect to per 1 mole of periodic table the 8th family's metal, adding 0.2～1.2 mole of organic acid, described periodic table the 6th family's metal is selected from molybdenum and tungsten, and described periodic table the 8th family's metal is selected from cobalt and nickel; Under 200 ℃ or lower temperature, carry out drying subsequently, wherein, when after vulcanizing treatment and the absorption of NO subsequently, when described catalyst is observed on diffuse reflection method Fourier transform infrared spectroscopy, the value of I8 family/(I8 family+I6 family) is in 0.7～1 the scope, wherein, the representative of I8 family is at 1840cm ^-1The place is adsorbed on the intensity of the NO spectrum on periodic table the 8th family's metal, and I6 family represents at 1700cm ^-1The place is adsorbed on the intensity of the NO spectrum on periodic table the 6th family's metal.

6. the method for a hydrotreatment light oil, this method is included under the existence of each described catalyst of claim 1～4, is that 3～8MPa, temperature are that 300～420 ℃ and liquid hourly space velocity are 0.3～5hr at hydrogen partial pressure ^-1Condition under, light oil distillate is carried out catalytic reaction.