CN1088090C - Hydrorefining catalyst for fraction oil and its preparing process - Google Patents

Abstract

The present invention discloses a hydrofining catalyst for distillate oil and a preparation method thereof. In the catalyst, metallic elements (particularly W and Ni) of group VIB and group VIII are used as hydrogenation active components, and a silicon and boron compounded auxiliary agent is simultaneously added. The catalyst is prepared from W-Ni / SiO2, B2O3 and Al2O3. The preparation method of the catalyst adopts a series of technical measures that silicon and boron of the compounded auxiliary agent are simultaneously immersed to a carrier, an organic complexing agent is added in a tungsten and nickel solution, an activating catalyst is calcined at low temperature, etc. Compared with the prior art, the hydrofining catalyst for distillate oil has the advantages of simple manufacture flow path of the catalyst, no environmental pollution, easy adjustment of pore structure, good mechanical strength, high activity of the catalyst, etc., and is suitable for the hydrofining process of the distillate oil.

Description

A kind of catalyst for hydrorefining distillate oil and preparation method thereof

The present invention relates to a kind of catalyst for hydrorefining distillate oil and preparation method thereof, particularly boiling range is the Hydrobon catalyst and the preparation process thereof of 180～550 ℃ of petroleum fractionss.

As everyone knows, hydrofining is one of important techniques in the petroleum refining industry, and hydrogenation catalyst then is one of the most important and The key factor in this process.Especially in recent years; along with crude oil poor qualityization tendency in the world wide is obvious day by day; while requirement on environmental protection increasingly stringent; quality to processed oil has proposed more and more stricter standard; particularly the restriction of the content of sulphur and aromatic hydrocarbons is strict gradually in the oil product; force enterprise and various research institution to continually develop, use various performances better, be more suitable for again in the high-activity hydrofining catalyst of inferior raw material hydrogenation process simultaneously.In the industrial application process, add the acidity that auxiliary agent improves carrier usually, active ingredient is in the dispersiveness of carrier surface, reductibility and curability, the adding of auxiliary agent is often played and is prolonged catalyzer work-ing life, the effect that improves selectivity and stability.The auxiliary agent of common usefulness has fluorine, chlorine, phosphorus, boron, titanium, zirconium, silicon, zinc, chromium and basic metal and alkaline earth metal oxide etc. in the Hydrobon catalyst.

Existing Hydrobon catalyst uses fluorine element as auxiliary agent mostly, because the compound of fluorine has toxicity, and contaminate environment, infringement workers'health; Easily cause the equipment in the loss corrosion downstream of fluorine in the industrial application process, spent catalyst is difficult to problems such as processing.So it is that composite assistant prepares Hydrobon catalyst that people more trend towards adopting silicon and boron, wherein the adding of silicon and boron can both strengthen the acidity of carrier and catalyzer significantly, particularly can strengthen Bronsted acid; The adding of report boron also has the γ of preventing-Al in the document ₂O ₃Form spinel, functions such as activity resistent component sintering with active ingredient.

For hydrodenitrification, add boron as the auxiliary agent best results, but adding boron with pickling process exists following difficulty; The boron-containing compound that adopts the earliest when adding boron is a boric acid, and boric acid solubleness in water is very low under the room temperature, can only dissolve the boric acid about 6g in the 100ml water, so when at room temperature using the boric acid aqueous solution impregnated catalyst, the loading of boron seldom on the catalyzer, do not have the effect that improves catalyst performance, B on the general requirement catalyzer ₂O ₃Content is at 2～10m%.If adopt kneading method in the extrusion molding process, to add the pore distribution disperse that boric acid can cause catalyzer, do not have the effect of effective improvement catalyst activity.

The adding mode that silicon boron composite assistant is different has different influences to the character of catalyzer, and common adding mode is: add silicon earlier, the back adds boron.At publication number is in the patent of invention of CN1052501A, directly select aluminum oxide-silica support for use, the pore structure character of catalyzer is restricted because of the carrier source like this, realize the loading of two kinds of auxiliary agents of silicon boron then with the method for boric acid ammonia soln dipping boron, and be in carrier extruded moulding process, to add low sodium silicon sol (less than 50ppm) in publication number is the patent of invention of CN1086534A, add two kinds of auxiliary agents with the mode that contains molybdenum and boron ammonia soln dip loading boron then, this method adds low sodium silicon sol in carrier extruded moulding process.The mode that this silicon, boron add respectively exists following technology to cover end: at first, be difficult to make silicon homodisperse on carrier surface; Secondly,, will inevitably bring difficulty in the extruded moulding process,, also can cause the variation that the carrier hole structure is difficult to expect, also can influence the intensity of catalyzer if control is improper to extruded moulding because the low sodium silicon sol of tart peptizing agent and alkalescence uses simultaneously; Silicon and boron successively add in addition, and they are different with alumina supporter effect power, make silicon and boron can not bring into play synergy, cause prepared catalyst activity to be affected.

The objective of the invention is to bring into play better the synergy of silicon, boron, provide that a kind of to have a preparation flow simple, catalyst strength is good, hydrogenation activity height, the catalyst for hydrorefining distillate oil of environmentally safe.

Adopt the method that adds silicon boron composite assistant simultaneously among the present invention, silicon boron mixing solutions can add in the aluminum oxide moulding process, also can the mode by dipping add after the carrier moulding.If in the process of carrier moulding, add, enter the effect that does not have in the skeleton surface modification because of the part composite assistant, simultaneously since auxiliary agent and aluminum oxide have a style of one's own, a series of pyrolysis that are unfavorable for surface modification take place in the process of drying and roasting, and make carrier surface still have quite active centre bit, easily produce spinels (M with active metal component generation strong interaction ^‖Al ₂O ₄) and aluminate (Al for example ₂(WO ₄) ₃) wait non-active compound; So preferably adopt the mode of dipping to add,, effectively carrier carried out surface modification because this mode more helps the uniform distribution of composite assistant at carrier surface.Just be that example is described in detail the present invention below with the impregnation method.

Want to add simultaneously silicon, two kinds of auxiliary agents of boron and bring into play its synergy, the key of problem is the preparation of silicon, boron mixing solutions.In the present invention, selecting cheap and easy to get and low sodium silicon sol and solid boric acid (perhaps ammonium borate) for use is raw material, in order to be made into the higher silicon boron mixed stability solution of concentration with these two kinds of raw materials, must solve following two technical problems: the one, increase boric acid solubleness in water and (carry out under the room temperature, the too high meeting of temperature causes the coagulation of silicon sol), the 2nd, avoid silicon sol and silicon boron mixing solutions coagulation.In order to solve first technical problem, having adopted with ammoniacal liquor is the technical measures of solvent, and ammoniacal liquor can carry out complex reaction with boric acid, interrupts the intermolecular hydrogen bond of boric acid, thereby improves the solubleness of boric acid in water under the room temperature.In order to solve second technical problem, the major measure that is adopted is the pH value of the way of contact, system of control silicon sol and boric acid ammonia soln and temperature etc., more particularly, the way of contact of control silicon sol and boric acid ammonia soln refers to silicon sol is dispersed in the boric acid ammonia soln quickly and evenly, with passing through to control the pH value of ammoniacal liquor add-on regulation system between 6～8, hierarchy of control temperature just is unlikely to make the solution coagulation between room temperature to 45 ℃.In order to obtain the silicon boron mixed stability solution of greater concn, adopted two kinds of stablizers to come stabilizing solution.Except ammoniacal liquor, also adopt polynary organic alcohol, such as N.F,USP MANNITOL, glycerol, polyvinyl alcohol and polyoxyethylene glycol etc., be the best wherein with N.F,USP MANNITOL, glycerol.Polynary organic alcohol and boric acid carry out complex reaction, strengthen the acidity and the solvability of boric acid, thereby improve the solubleness of boric acid in water under the room temperature.A certain amount of polynary organic alcohol can all form tectum on each micelle surface, prevented between the micelle or micelle and electrolyte ion between direct the contact, play effect stable and protection silicon boron mixing solutions, make it not occur flocculation and coagulation phenomenon.Adopt the bistable agent to come the silicon boron mixing solutions of stable high concentrations, wherein the consumption of stablizer and feed way are crucial technology, and its technical key point is the aqueous solution that is mixed with polynary organic alcohol earlier, adds required boric acid then at a certain temperature; And another kind of stablizer ammoniacal liquor adds earlier in the silicon sol, then the silicon sol that contains ammoniacal liquor is dispersed in the above-mentioned boric acid aqueous solution that contains polynary organic alcohol quickly and evenly.The pH value of the hierarchy of control is between 6～8 in the operating process, and mixed solution system is more stable, and the temperature of the hierarchy of control just is unlikely to make the solution coagulation between room temperature to 45 ℃.

The present invention has adopted the moulding of aluminum oxide precursor elder generation, the method technology of preparing of two sections dippings again, and the ammonia soln (containing polynary organic alcohol when concentration is high) of promptly using siliceous and boron compound is for the precursor of silicon and boron is flooded, dry, roasting; Carry out the dipping second time with the aqueous solution that contains group vib, group VIII metallic compound that adds an amount of organic complex again, dry and lower maturing temperature activating activities component.The concrete preparation process of catalyzer of the present invention is:

(1) with suitable aluminum oxide predecessor mixing of materials aftershaping, 100～130 ℃ dry 3～6 hours down, in 500～700 ℃ of air, roasting 1～10 hour makes carrier.

(2) carrier that above-mentioned (1) is obtained, adopt the mode load silicon boron composite assistant of dipping with the silicon boron mixing solutions for preparing in advance, preferably adopt the mode of saturated dipping, operation at room temperature, 100～130 ℃ dry 3～6 hours down, in 400～550 ℃ of air calcination for activation 3～6 hours, make the carrier that contains silicon boron composite assistant.

(3) carrier that contains silicon boron composite assistant that again (2) is obtained contains group vib, group VIII solution of metal compound with what prepare in advance, adopt the mode load hydrogenation activity component of dipping, preferably adopt the mode of saturated dipping, operation at room temperature, 100～130 ℃ dry 3～6 hours down, at calcination activation (setting) between 300～450 ℃ of the lower temperature, can make described catalyzer.

(4), after the kerosene that adopts hydrogen sulfide or contain dithiocarbonic anhydride carries out online prevulcanized, promptly can be used for the unifining process of various sulphur content oil with the catalyzer of above-mentioned (3) gained.

The precursor of described aluminum oxide is meant with aluminum alkyls or aluminum alkoxide hydrolysis method, Tai-Ace S 150-sodium metaaluminate method, the boehmite of preparation such as sodium metaaluminate-carbon dioxide process, pseudo-boehmite, promise diaspore, surge aluminium stone, amorphous hydroted alumina or gibbsite.Can require to select the raw material of different aluminum oxide precursor according to the pore structure of final catalyst prod, also can be by changing condition of molding, factors such as maturing temperature and time are carried out suitable adjusting: such as adopting the aperture of improving temperature and overtime chien shih carrier to increase and pore distribution concentration.The ordinary method of metal load type catalyst is adopted in the moulding of aluminum oxide precursor: as dripping ball forming, compression molding, extruded moulding.

Technical characterictic of the present invention is to have adopted silicon boron mixing solutions pickling process load silicon and boron composite assistant simultaneously, described siliceous boron mixing solutions, be to adopt low sodium silicon sol, boric acid or ammonium borate, ammoniacal liquor and/or polynary organic alcohol are as raw material, under room temperature to 45 ℃, make silicon boron mixing solutions, SiO in this solution between the control pH value 6～8 ₂0.1～2.2mol/l, B ₂O ₃0.1～2.0mol/l.Concrete operation scheme is: get ammonia soln, at room temperature, adding boric acid (or, ammonium borate) make the boric acid solution that contains ammoniacal liquor, under stirring condition, dropwise silicon sol is added in the above-mentioned solution, make silicon boron mixing solutions.In order to obtain the higher silicon boron mixing solutions of concentration, also can adopt following technical scheme: between room temperature to 45 ℃, produce the aqueous solution of polynary organic alcohol earlier, under agitation condition, add boric acid (boric acid is CL not); Get silicon sol, add ammonia soln, after mixing, this silicon sol that contains ammoniacal liquor is dropwise added in the above-mentioned boric acid solution under agitation condition, continue to stir for some time after adding silicon sol, make silicon boron mixing solutions.

Described group vib, the group VIII solution of metal compound of containing, be to mix to stir and make by water-soluble group vib, group VIII metallic compound and water of containing, in solution, add simultaneously citric acid or oxalic acid or EDTA organic complexing agents such as (ethylenediamine tetraacetic acid (EDTA)s), wherein oxalic acid preferably.Suitable organic complexing agent helps the dispersiveness of active ingredient at carrier surface, changes its reduction and curability.

Described saturated pickling process is to form good required active component solution amount and the concentration of calculating according to the water-intake rate of carrier and catalyzer, adopts the mode of spray to carry out in rotary drum then, treats to rotate 20～40 minutes after solution spraying finishes again.Preferably do a bit, otherwise easily cause the gathering of active ingredient and disperse inhomogeneous.The drying roasting promptly gets the catalyzer of oxidation state then.

Described catalyst vulcanization method can be used H ₂S carries out prevulcanized, preferably adopts the kerosene prevulcanized under 150～320 ℃, 12～24 hours condition that contains dithiocarbonic anhydride.

The content (with the catalyzer is benchmark, quality %) of the catalyzer that makes according to the inventive method is: silicon oxide 1～10%, and boron oxide 1～10%, group vib metal oxide 15～35%, group VIII metal oxide 2～10%, all the other are aluminum oxide; Each component concentration in this catalyzer (with the catalyzer is benchmark, quality %) is preferably: silicon oxide 2～4%, and boron oxide 2～4%, group vib metal oxide 20～30%, group VIII metal oxide 4～8%, all the other are aluminum oxide.

Catalyst pores textural property according to the inventive method preparation can be according to aluminum oxide precursor raw material properties difference, and Preparation of Catalyst condition difference factors such as (such as aluminum oxide precursor condition of molding, maturing temperature, time) is adjusted.The specific surface area of catalyzer is 100～300m ²/ g, the aperture is 2～15nm.

The catalyzer of gained of the present invention should can be used for hydrogenating desulfurization, the denitrogenation of various distillates and take off the refining of aromatic hydrocarbons, and the polycyclic aromatic hydrocarbons in the stock oil is had higher hydrogenation performance, and the hydrofining that is particularly suitable for diesel oil and decompressed wax oil is handled.

In a word, because auxiliary agents of silicon boron adopts the mode that adds simultaneously to impregnated on the carrier, make it to be different from the mode that silicon and boron join carrier respectively, can bring into play the synergy effect of silicon and boron better, adding auxiliary agent in the aluminum oxide that the coexists precursor moulding process compares, this method more can the promotes oxidn alumina supporter surface modification, do not resemble in oxide compound precursor moulding process and add auxiliary agent, make auxiliary agent enter skeleton easily, particularly aluminum oxide and auxiliary agent are in same temperature, roasting simultaneously easily at high temperature makes the surfactivity center too active because of pyrolysis under the atmosphere; In the process for preparation of tungsten nickel solution, can promote the dispersiveness of active metal component owing to add the organic acid complexing agent on the surface, adopted the low-temperature bake technology in the last calcination activation stage of catalyzer.Owing to adopt above-mentioned technology, make that the technology of the present invention preparation technology flow process is simple, easy-formation, intensity be good, and activity of such catalysts, stability have increased significantly.After selecting the aluminum oxide precursor elder generation moulding of Different Pore Structures, auxiliary agent and active ingredient are in the process of two step dippings, property effect to the carrier hole structure is little, the main Surface Physical Chemistry character that influences carrier, so the catalyst pores structure by the present invention's preparation is easily adjusted, thereby the stock oil scope that adapts to processing treatment is wide, be particularly suitable for resembling diesel oil and decompressed wax oil hydrogenating desulfurization, denitrogenation, take off the aromatic hydrocarbons treating process, because the highly active hydrogenation catalyst of such process need.Because the raising of catalyst activity in use can also reduce temperature of reaction and pressure, thereby reduce energy consumption, has reduced the requirement to equipment, the insecurity of having avoided high top pressure operation to bring; In addition, also can improve air speed, to enhance productivity.

Fig. 1 is catalyzer K ₀And K ₁X-ray diffraction (XRD) spectrogram;

Fig. 2 is sulphided state catalyzer K ₂Temperature programmed reduction(TPR) (TPR) spectrogram.

Further describe advantage of the present invention and technical characterstic below by embodiment and Comparative Examples.

Embodiment 1

Embodiment 1 usefulness extruded moulding is the preparation process that example is introduced carrier.

With aluminium hydroxide dry powder and an amount of acetic acid, sesbania powder and water are kneaded into uniform plastic, and extrusion molding is the cloverleaf pattern bar of 1.2mm, and 120 ℃ of dryings 4 hours in the corresponding time of different roasting temperatures, can obtain bar shaped carrier A, B, C, D respectively.Concrete operations and experimental result see Table 1,2.

Wherein a is the dry glue powder that first fertilizer plant of Qilu Petrochemical company produces with sodium metaaluminate-carbon dioxide process; B is with Tai-Ace S 150-homemade dry glue powder of sodium metaaluminate method; SB is the dry glue powder from U.S.'s import.

Table 1

The carrier aluminium hydrate powder acetic acid sesbania powder water maturing temperature time

g g g ml ℃ hr

A a/2000 40 60 1700 500 3

B a/2000 40 60 1700 650 6

C b/500 10 17 400 520 4

D SB/200 5 8 160 550 3

Table 2

Pore volume specific surface area mean pore size tap density intensity

ml/g m ²/g nm g/ml N/mm

A 0.68 327 8.3 0.61 18

B 0.67 270 10.0 0.63 17

C 0.76 232 13.0 0.40 10

D 0.43 421 4.1 0.65 21

Embodiment 2

Embodiment 2 has introduced a kind of compound method of silicon boron mixing solutions.

Get distilled water 370ml, add the ammonia soln 20ml of 7.76mol/l, constant temperature adds 48.3g technical grade boric acid in 30 ℃, makes the boric acid solution that contains ammoniacal liquor; (the new light remover in Shenyang City factory produces, and pH value is 9.3, contains SiO to get the 76.0ml silicon sol ₂: 30.0m%, Na ⁺Less than 1000ppm), under stirring condition, dropwise silicon sol is added in the above-mentioned solution, make the silicon boron mixing solutions F of 500ml at last, place 30 days these solution appearance and do not have considerable change.It consists of:

SiO ₂?0.90mol/l；B ₂O ₃?0.78mol/l；NH ₃?0.31mol/l。

Embodiment 3

Embodiment 3 has introduced a kind of method of silicon B solution preparation of higher concentration.

Get distilled water 250ml, add 9.2g technical grade N.F,USP MANNITOL, at 40 ℃ of constant temperature, treat that N.F,USP MANNITOL dissolves fully after, under agitation condition, add technical grade boric acid 103g, boric acid can not dissolve fully.Get the 160ml silicon sol, the ammonia soln 40ml that adds 7.76mol/l, after mixing, under agitation condition, dropwise add in the above-mentioned boric acid solution this silicon sol that contains ammoniacal liquor, continue to stir dissolving fully in 60 minutes after adding silicon sol, make desired silicon boron mixing solutions G 500ml, place 30 days these solution appearance and do not have considerable change.It consists of: SiO ₂1.92mol/l; B ₂O ₃1.67mol/l; NH ₃0.47mol/l; N.F,USP MANNITOL 0.10mol/l.

Embodiment 4

Present embodiment has been introduced the compound method of tungsten nickel solution.

Measure water 235ml, add 5.5g oxalic acid successively, 335g nickelous nitrate (Ni (NO ₃) ₂6H ₂O, Liaoning Province city's chemical reagent one factory that increases income), (technical grade contains WO to the 390g ammonium metawolframate ₃85.2%), make 500ml tungsten nickel solution after the stirring and dissolving, it consists of WO ₃2.86mol/L, NiO 2.29mol/L, oxalic acid 0.09mol/L.

Embodiment 5

Present embodiment has been introduced Preparation of catalysts process and method.

(1) method of pressing among the embodiment 2 is prepared 200ml silicon boron mixing solutions H, it is consisted of: SiO ₂

0.48mol/L；B ₂O ₃?0.41mol/L。

(2) get three parts of carrier A among the embodiment 1 and place rotary drum, use respectively silicon boron mixing solutions H, F,

G sprays, and the time of spraying was respectively 20,40,20 minutes, has sprayed the back and has taken out 120 ℃ of bakings down

Did 3 hours, and, made the carrier J of siliceous boron then 480 ℃ of following roastings 3 hours ₁, J ₂, J ₃

The results are shown in table 3.

The siliceous boron carrier vector of table 3 A silicon B solution SiO ₂B ₂O ₃Specific surface area

g ml m％ m％ m ²/gJ ₁ 100 H/80 2.2 2.2 295J ₂ 500 F/400 4.1 4.0 289J ₃ 100 G/81 8.0 7.9 273

(3) get carrier A among the embodiment and the carrier J in the embodiment step (2) respectively ₂, J ₃Place rotary drum

In, prepare a series of tungsten nickel solutions by the method for embodiment 4, spray respectively then, the time of spraying is

30 minutes, sprayed the back taking-up and dried 3 hours down at 120 ℃, then 350 ℃ of following roastings 4 hours,

Make catalyzer K ₀, K ₁, K ₂, K ₃, K ₄, preparation condition is listed in table 4, and the catalyzer physico-chemical property is listed in

Table 5.

Table 4

Catalyst support volume tungsten nickel solution oxalic acid

g (ml) WO ₃ NiO， (mol/L)

K ₀ A/100 80 2.13 2.13 0.07

K ₁ J ₂/100 75 2.92 2.34 0.09

K ₂ J ₂/200 150 2.85 2.27 0.09

K ₃ J ₂/100 75 2.23 1.87 0.07

K ₄ J ₃/100 70 1.87 1.85 0.07

Table 5 catalyst S iO ₂B ₂O ₃WO ₃NiO mean pore size specific surface area tap density intensity

m％ nm m ²/g g/ml N/mmK ₀ -- -- 26.0 8.3 6.9 186 0.94 19K ₁ 2.5 2.5 30.3 8.0 7.7 160 1.03 20K ₂ 3.7 2.5 30.2 7.9 7.1 176 1.02 20K ₃ 2.6 1.4 26.9 7.1 8.3 177 0.96 15K ₄ 5.9 5.7 20.9 6.7 7.9 187 0.89 13

Embodiment 6

Present embodiment has compared the different carrier acidity of silicon boron content.

Carrier in the present embodiment is selected from the carrier A of embodiment 1 and the carrier J among the embodiment 5 ₁, J ₂, J ₃With gravimetric determination the adsorptive capacity of pyridine under differing temps, the results are shown in Table 6, after silicon boron adds carrier as can be seen, the acidity between 250～350 ℃ of temperature increased significantly.

Can see by table 6, because the adding of silicon boron, increased the acidity of carrier, though add the acidity that molecular sieve also can improve carrier, but the anti-nitrogen ability of molecular sieve in the process of practical application is easily poisoned, and can not be applicable to the direct processing treatment of inferior feedstock oil, and silicon boron has anti-preferably nitrogen ability, and cheap.Particularly the acidity under 350 ℃ increases significantly, and in petroleum refining industry, the Hydrobon catalyst major part is used under 250～400 ℃ of temperature.Because the synergy of composite assistant silicon boron strengthens the acidity of carrier, increase acidity and the unmatched drawback of hydrogenation performance that causes with regard to the composition that overcomes because of active metal component like this, improve the utilising efficiency of active ingredient.

Table 6 temperature/carrier A J ₁J ₂J ₃

Mmol pyridine/g160 ℃ 0.463 0.451 0.430 0.512250 ℃ 0.285 0.289 0.287 0.314350 ℃ 0.093 0.150 0.186 0.164450 ℃ 0.069 0.053 0.094 0.047

Embodiment 7

Present embodiment has compared X-ray diffraction method (XRD) the crystalline phase analytical results that contains and do not contain two kinds of catalyzer of auxiliary agent.

Get catalyzer K among the embodiment 5 ₀And K ₁, suppose that at first the active ingredient individual layer is scattered in carrier surface, calculate atomic percent, respectively K in the catalyst surface active component ₀3.14 WO ₃/ nm ²3.11 NiO/nm ², K ₁4.42WO ₃/ nm ²3.62NiO/nm ², to catalyzer K ₀And K ₁Carry out the analysis of X-ray diffraction method crystalline phase, the results are shown in Figure 1.

As seen from Figure 1, the catalyzer K that does not contain auxiliary agents of silicon boron ₀The surface has the gathering of reactive metal to exist mutually, and contains the catalyzer K of sial composite assistant ₁The surface has only the diffraction peak of gama-alumina and amorphous alumina, and this explanation silicon boron additive has improved the dispersiveness of active ingredient at carrier surface.Simple alumina supporter has the gathering of active phase component to exist mutually, and does not exist in the crystalline phase of the active phase component of the alumina surface that contains composite assistant silicon boron, and the existence of auxiliary agents of silicon boron is described, active ingredient improves at the dispersing property of carrier surface.

Embodiment 8

Present embodiment has been introduced catalyzer temperature programmed reduction(TPR) (TPR) character after vulcanizing with the technology of the present invention preparation.

Get the catalyzer K among the embodiment 5 ₂In the 200ml small hydrogenation device, use the kerosene that contains dithiocarbonic anhydride, between 150～320 ℃ of temperature, this catalyzer was carried out prevulcanized 16 hours, make the sulphided state catalyzer, it is carried out temperature programmed reduction(TPR) (TPR) investigate, the actual measurement condition is: with the carrier gas of argon gas as hydrogen, 10 ℃/min of heat-up rate, use the thermal conductivity cell detection signal, get the TPR spectrogram, the results are shown in Figure 2.

The catalyzer that makes with the present invention has single reduction peak after sulfuration as can be seen from Figure 2, and reduction temperature is moderate, and between 300～500 ℃, it is concentrated to illustrate that this activity of such catalysts distributes mutually, has good hydrogenation performance under certain condition.And by moderate, the active phase homogeneous of sulphided state reduction temperature (only one of reduction peak) of the catalyzer of the present invention preparation.

Comparative Examples 1

This Comparative Examples has compared by the catalyzer of the present invention's preparation and the hydrofining effect of reference catalyst.

(1) be that method in the CN1052501A patent of invention makes catalyzer M according to publication number, main materialization

Matter is listed in table 7.

(2) catalyzer K among catalyzer M in the step (1) and the embodiment 5 ₂Carry out respectively using the Liaohe River after the prevulcanized

Subtracting third fractional oil is raw material (character is listed in table 8), at volume space velocity 1.0h ^-1, hydrogen to oil volume ratio

800 (v/v) compare evaluation under the reaction conditions of all temps and pressure, and experimental result is listed in

Table 9.

(3) by the experimental evaluation result, catalyzer of the present invention mainly shows as has higher aromatic hydrocarbons saturability

Energy.Be specially adapted to the hydrofining treating processes of diesel oil and decompressed wax oil.

The physico-chemical property catalyst S iO of table 7 reference catalyst M ₂B ₂O ₃WO ₃MoO ₃NiO mean pore size specific surface area spherical (diameter)

m％ nm m ²/g mmM 4.4 3.5 19.8 7.8 5.0 8.0 150 1.5～2.5

Table 8 stock oil character

The stock oil title Liaohe River subtracts third fractional oil

Density (20 ℃), kg/m ³955.2

Sulphur, ppm 2100

Nitrogen, ppm 2476

Mass spectrum is formed, m%

Stable hydrocarbon 58.5

Aromatic hydrocarbons 38.8

Boiling range, ℃

Initial boiling point 373

10％ 425

50％ 445

90％ 477

Final boiling point 504

Molecular-weight average 382

Table 9 catalyzer K ₂With reference catalyst M evaluation result pressure, Mpa 8.0 12.0 15.0 temperature, ℃ 260 300 330 360 300 360 catalyzer M M K ₂M K ₂M K ₂K ₂M K ₂Sulphur, ppm 30.0 6.8 37.0 23.6 30.0 19.8 28.0-4.9 4.9 desulfurization degrees, % 98.6 99.7 98.2 98.9 98.6 99.1 98.7-99.8 99.8 nitrogen, ppm 206 42.8 44.5 22.0 37.0 46.9 39.0 2.7 8.4 8.5 denitrification percents, % 91.7 98.3 98.2 99.1 98.5 98.1 98.4 99.9 99.7 99.7 aromatic hydrocarbons, m% 34.6 32.4 23.2 30.6 24.9 31.8 26.8 14.7 16.2 10.7 takes off fragrant rate, and % 10.8 16.5 40.2 21.1 35.8 18.0 30.9 62.1 58.2 72.4

Annotate: the sulphur in the table 9, nitrogen, aromatic hydrocarbons are the content that generates in the oil; The content of aromatic hydrocarbons adopts mass spectrometric determination.

By this Comparative Examples, illustrate that this catalyzer has higher hydrofining effect, particularly has higher activity to aromatic hydrogenation.

Claims (9)

1. a catalyst for hydrorefining distillate oil is an active ingredient with group vib, group VIII metal, aluminum oxide is a carrier, it is characterized in that adopting two kinds of elements of silicon and boron to make compound auxiliary agent, with the catalyzer be benchmark its consist of: silicon oxide 1～10m%, boron oxide 1～10m%, group vib metal oxide 15～35m%, group VIII metal oxide 2～10m%, all the other are aluminum oxide, and the specific surface area of this catalyzer is 100～300m ²/ g, the aperture is 2～15nm.

2. according to the described catalyzer of claim 1, it is characterized in that with the catalyzer being that benchmark consists of: silicon oxide 2～4m%, boron oxide 2～4m%, group vib metal oxide 20～30m%, group VIII metal oxide 4～8m%, all the other are aluminum oxide.

3. by claim 1 or 2 described catalyzer, it is characterized in that said group vib metal oxide is a Tungsten oxide 99.999, the group VIII metal oxide is a nickel oxide.

4. the preparation method of a catalyst for hydrorefining distillate oil the steps include:

(1) with the aluminum oxide precursor, carrier is made in moulding, drying, roasting;

(2) carrier that (1) is obtained supports silicon and boron composite assistant with pickling process, operation at room temperature, and drying is 3～6 hours under 100～130 ℃, and calcination for activation is 3～6 hours in 400～550 ℃ of air atmospheres, makes the carrier of siliceous boron composite assistant;

(3) carrier of the siliceous boron composite assistant that (2) are obtained, with containing group vib and group VIII solution of metal compound dipping, operation at room temperature, 100～130 ℃ of dryings 3～6 hours, calcination for activation made catalyzer in 3～6 hours in 300～450 ℃ of air atmospheres;

It is characterized in that adopting in the step (2) silicon boron mixing solutions pickling process load silicon and boron composite assistant simultaneously, contain SiO in the silicon boron mixing solutions ₂0.1～2.2mol/l, B ₂O ₃0.1～2.0mol/l.

5. according to the described preparation method of claim 4, it is characterized in that the described catalyst activation maturing temperature of step (3) is between 300～350 ℃.

6. according to the described preparation method of claim 4, it is characterized in that described group vib of step (3) and group VIII metallic compound are tungsten compound and nickel compound.

7. according to the described preparation method of claim 4, it is characterized in that step (3) described containing also contain organic complexing agent citric acid, oxalic acid or EDTA (ethylenediamine tetraacetic acid (EDTA)) in group vib and the group VIII solution of metal compound.

8. according to the described preparation method of claim 6, it is characterized in that described tungsten compound and nickel compound are respectively ammonium metawolframate and nickelous nitrate.

9. according to the described catalyzer of claim 1, it is characterized in that this catalyzer can be used for the hydrofining and the hydrotreatment process of distillate after sulfuration.

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