CN100556994C - Phosphorated diesel oil hydrofining catalyst and preparation method thereof - Google Patents

Abstract

The present invention relates to a kind of diesel oil hydrofining catalyst, its carrier is that the composite oxides of titanium dioxide and silicon-dioxide are handled product through the modification of phosphorus or HY molecular sieve or this molecular sieve modified thing, active ingredient is two kinds of metallic combinations in cobalt, molybdenum, nickel and the tungsten, the pore volume of this catalyzer is 0.4～0.7ml/g, and specific surface area is 150～350m ²/ g.The present invention relates to this Preparation of catalysts method simultaneously, especially carrier is implemented phosphorus or molecular sieve modified method.Utilize catalyzer of the present invention that catalytic cracking diesel oil is implemented hydrofining and handle, can effectively realize deep desulfuration, the denitrogenation of diesel oil and take off aromatic hydrocarbons.

Description

Phosphorated diesel oil hydrofining catalyst and preparation method thereof

Technical field

The present invention relates to be used for the catalyzer of diesel oil hydrofining, particularly relate to titanium dioxide and silica composite oxide carrier are carried out diesel oil hydrofining catalyst that obtains after the modification and preparation method thereof.

Technical background

Along with the raising day by day of environmental protection requirement, also strict further to the restriction of motor vehicle emission, content of harmful controlling index such as sulphur, nitrogen, aromatic hydrocarbons also improve constantly in the clean diesel specification.Hydrogenation is realization diesel fuel desulfurization, denitrogenation, takes off the most effective means of aromatic hydrocarbons, and employed catalyst performance plays a part crucial to the state of the art of hydrogenation technique in the hydrogenation process.Ideal diesel oil hydrogenation catalyzer should have higher catalytic desulfurization, denitrogenation and arene saturating activity concurrently, and hydrogenation process can be carried out under conditions such as demulcent temperature of reaction, pressure, to reduce the running cost of hydrogenation process, obtains the fine clean diesel.

Domestic and international employed diesel oil hydrofining catalyst major part is to be carrier with the aluminum oxide at present, is active ingredient with cobalt, molybdenum, nickel, tungsten.In recent years for the desulfurization, the denitrogenation that improve hydrogenation catalyst and take off the aromatic hydrocarbons performance, carried out a few thing at aspects such as the employing of support modification, novel material and preparation methods.

CN1289636A discloses a kind of preparation method and purposes of Ti-contained aluminium hydroxide, is the surperficial homodisperse titanium oxide layer at aluminum oxide, and avoids stopping up the micropore of aluminum oxide.With the aluminum oxide of titanium modification is that the performance of the hydrogenation catalyst of carrier can be brought certain improvement, but the contradiction that metal loading and pore volume descend is difficult to solve, thereby the performance difficulty of catalyzer is improved largely.

CN1040610A discloses to contain the γ-Al of titanium oxide ₂O ₃Be the Hydrodevulcanizing catalyst for hydro-carbons of carrier, active ingredient is a cobalt molybdenum nickel.γ-Al ₂O ₃The content of middle titanium oxide is 5～30wt%, and this catalyzer is lower because of its specific surface, and the surface acidity of carrier does not significantly improve simultaneously, and denitrification effect is also not obvious.

It is Mo, the Co of carrier and Ni, Mo Hydrobon catalyst that USP4392985 and CN96109048.0 disclose with aluminum oxide and aktivton respectively, improve the deliquescent method of metal component by in steeping fluid, adding phosphoric acid, improve the metal loading of catalyzer and the activity of catalytic desulfurhydrogenation.Though this class has initially desulphurizing activated preferably with the catalyzer of the direct modification of phosphorus to catalytic cracking diesel oil, but alkene in the diesel oil and polycyclic aromatic hydrocarbons be easily at the strong acid center condensation green coke of catalyst surface, thereby make catalyzer be difficult to keep comparatively ideal activity stability.And the raising of taking off fragrant performance and diesel cetane-number of catalyzer is also not satisfactory.

Disclose a kind of among applicant's the CN02116851.2 of patent formerly with nano level composite oxides TiO ₂-SiO ₂Hydrogenation catalyst for carrier loaded active metal nickel and tungsten, and show that this catalyzer compares with the hydrogenation catalyst that with the aluminum oxide is carrier, have desulfurization degree height, hydroconversion condition demulcent advantage, and compare with the hydrogenation catalyst that with titanium dioxide is carrier, then have the characteristics of active and good stability.But this catalyzer is still having deficiency aspect deep desulfuration, the denitrogenation, in the face of current diesel oil consumption increases, and to the also strict further present situation of the restriction of motor vehicle emission, is necessary further to be improved.

In sum, at the existing aluminum oxide catalyzer that is carrier with aluminum oxide or titanium dioxide, silicon-dioxide or modification when carrying out diesel oil hydrogenation, be difficult to have concurrently simultaneously the character of good hydrogenating desulfurization, denitrogenation and Tuo Fang, no matter be that the one-component carrier or the catalyzer of plural components carrier all can't satisfy the requirement to the deep refining of diesel oil, therefore, continually develop the striving direction that new diesel oil hydrofining catalyst is an industry.

Summary of the invention

Technical problem to be solved by this invention is the characteristic at diesel oil, and a kind of diesel oil hydrofining catalyst is provided, and by the modification of carrier is handled, this catalyzer is had concurrently diesel fuel desulfurization, denitrogenation and the performance of taking off aromatic hydrocarbons.

The present invention also provides this Preparation of catalysts method, especially carrier is implemented phosphorus or molecular sieve modified method, and catalyzer is significantly improved the performance of diesel oil hydrofining.

The present invention also provides and has adopted above-mentioned catalyzer to implement the method that catalytic cracking diesel oil hydrofining is handled, and can effectively realize deep desulfuration, the denitrogenation of diesel oil and take off aromatic hydrocarbons.

Diesel oil hydrofining catalyst provided by the invention, its carrier is that the composite oxides of titanium dioxide and silicon-dioxide are handled product through the modification of phosphorus or HY molecular sieve or this molecular sieve modified thing, active ingredient is two kinds of metallic combinations in cobalt, molybdenum, nickel and the tungsten, the pore volume of this catalyzer is 0.4～0.7ml/g, and specific surface area is 150～350m ²/ g.

Be converted to oxide compound in the support of the catalyst of the present invention, the titanium dioxide molar content is 20～80%, and the silicon-dioxide molar content is 20～80%, and the introducing amount of phosphorus is 1～5m% (mass content), and the introducing amount of HY molecular sieve is 1～15m% (mass content).In the final catalyzer, the content of active ingredient is in its oxide amount: NiO 1～3%, WO ₃10～20%, CoO 3～5%, MoO ₃10～15%.

At the characteristic of diesel oil, support of the catalyst of the present invention is by titanium dioxide (TiO ₂) and silicon-dioxide (SiO ₂) composite oxides the formed product after phosphorus or HY are molecular sieve modified, after supporting active metal component, can significantly improve diesel fuel desulfurization, denitrogenation and take off aromatic hydrocarbons refinement treatment process catalytic performance.Especially to sulfur-bearing, the higher diesel oil goods of nitrogen content, can improve catalytic efficiency, effectively realize deep removal.

Wherein, the introducing of phosphorus can be adopted following method: prepare TiO in sol-gel method ₂-SiO ₂Be the agent of all or part of hydrolysis pH regulator with phosphoric acid in the composite oxides process; Or with solution containing phosphate dipping TiO ₂-SiO ₂Composite oxide carrier.

The introducing of HY molecular sieve can be adopted the growth in situ method, forms TiO ₂-SiO ₂Coat the composite structure carrier of HY.HY molecular sieve used in the present invention can also be a kind of through the molecular sieve modified thing of the pretreated HY of sour modification, the present invention claims that pretreated HY molecular sieve is CY, its acidity and pore passage structure have obtained adjusting and have improved, described sour properties-correcting agent is oxalic acid, citric acid, tartrate or hydrochloric acid, and optimization citric acid is a properties-correcting agent.

The preparation method of diesel oil hydrofining catalyst of the present invention has comprised the modification processing of composite oxide carrier and the process that supports of active metal component.

The preparation of composite oxide carrier adopts sol-gel process to form colloidal sol, and obtains gel through aging, and dry roasting gets final product, specifically can be referring to the record of Chinese patent CN1316486A.

Introduce phosphorus when this carrier is implemented the phosphorus modification and can adopt two kinds of methods: prepare TiO in sol-gel method ₂-SiO ₂Be the agent of all or part of hydrolysis pH regulator with solution containing phosphate in the composite oxides process; Or with solution containing phosphate dipping TiO ₂-SiO ₂Composite oxide carrier is implemented modification.The introducing amount of phosphorus is 1～5% (mass content), the available solution containing phosphate for example: Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid or ammonium phosphate etc.

This carrier is implemented the introducing of HY molecular sieve when molecular sieve modified and is adopted the growth in situ method, promptly prepares TiO in sol-gel method ₂-SiO ₂In the composite oxide carrier process, add the HY molecular sieve, the TiO that hydrolysis is generated ₂-SiO ₂Particle surface growth at molecular sieve forms TiO ₂-SiO ₂Coat the composite structure carrier of HY.The introducing amount of molecular sieve is 1～15% (mass content).

So the preparation method of diesel oil hydrofining catalyst of the present invention can comprise:

Adopt sol-gel method to prepare colloidal sol the salt or the ester of titanium and silicon, and make its aging gel, dry roasting of obtaining;

To predetermined phosphorus content, dry roasting obtains the titania-silica composite oxide carrier of phosphorus modification to this product of roasting with solution containing phosphate dipping;

Adopt solution dipping method determined active metal component to be supported on this composite oxide carrier dry roasting.

Perhaps, change the introducing mode of phosphorus, the preparation process of composite oxide carrier is:

Adopt sol-gel method to prepare colloidal sol the salt or the ester of titanium and silicon, add as part or all of hydrolysis pH regulator agent (also claiming hydrolysis inhibitor) with solution containing phosphate in this process, dry roasting obtains the titania-silica composite oxide carrier of phosphorus modification.

Adopt when molecular sieve modified, the preparation process of composite oxide carrier is:

Adopt sol-gel method to prepare colloidal sol the salt or the ester of titanium and silicon, add HY molecular sieve or its modifier in this process, the oxide compound that makes the hydrolysis generation forms the composite structure carrier that titania-silica coats molecular sieve in the sieve particle surface growth.

Be to adjust the acidity and the pore passage structure of HY molecular sieve, said process also comprises and adopts the method for sour dealuminzation to carry out suitable modification pre-treatment to used HY molecular sieve, and concrete method of modifying is to be 0.5～2.0mol.L with concentration ^-1(0.5～2.0M) acid soak molecular sieve (volume ratio can be 1: 1～5: 1), reacted 1～5 hour down at 20～90 ℃, dry roasting gets the molecular sieve CY of modification, preferably, soak reacted molecular sieve through 120 ℃ of oven dry roasting 2～5 hours in 400～600 ℃ of following air atmosphere after 2 hours, obtain molecular sieve CY.

Preparation in accordance with the present invention, the drying of composite oxide carrier can adopt supercritical carbon dioxide fluid drying, heated drying or lyophilize etc., and concrete operations are ordinary method, also can be with reference to the record of CN1316486A.Dried product also need be under 400～800 ℃ of air atmosphere roasting 3～8 hours, preferred maturing temperature is 500～600 ℃, roasting time 3～5 hours.

Hydrobon catalyst of the present invention is an active ingredient with two kinds of metallic combinations in nickel (Ni), tungsten (W) or cobalt (Co), the molybdenum (Mo), and the active ingredient loading mode adopts the solution impregnation technology.Can be synchronous pickling process, complexes carrier be impregnated in the mixing solutions of active metal salt, for example, when being active ingredient, adopt the mixing solutions of the salts solution of Ni, W to flood composite oxide carrier synchronously with Ni-W; Also can adopt step impregnation method,, two kinds of active ingredients be supported on carrier respectively through twice dip operation.Preferably, when supporting one of active ingredient on carrier and be molybdenum, adopt step impregnation method, complexes carrier floods wherein a kind of salts solution of active ingredient (solution that for example contains molybdenum) earlier, floods the solution of another kind of reactive metal after drying, the roasting again, after drying and roasting, for example, when being active ingredient, composite oxide carrier being flooded earlier contain Mo solution with Co, Mo or Ni, Mo, flood again behind the drying and roasting and contain Co or Ni solution, after drying, roasting.In the step impregnation method, the impregnation sequence of two kinds of active ingredients does not have special requirement.The preferred metatungstic acid ammonia of the steeping fluid of described active ingredient, nickelous nitrate, Xiao Suangu, ammonium molybdate etc., the loading of active ingredient is in its oxide amount: NiO 1～3%, WO ₃10～20%, CoO 3～5%, MoO ₃10～15%.

Supporting in the process of active ingredient, preferred room temperature dipping, each dipping time 4～6 hours, after the complexes carrier dipping active ingredient preferably 110～120 ℃ of dryings 4～8 hours, 400～800 ℃ of roastings 3～4 hours.Identical with usual method, product after the roasting through overmolding, grind, sieve, become the final catalyst product, the present invention preferably collects 3～3.6mm after sieving granular product is a preformed catalyst, and this moment, its pore volume and specific surface area all met the needs of catalytic hydrogenation reaction.

According to another aspect of the present invention, provide the hydrofining treatment process to catalytic cracking diesel oil, that is, adopted above-mentioned catalyzer, realization is to diesel fuel desulfurization, denitrogenation and take off aromatic hydrocarbons.

In the catalyzer provided by the invention, metal active constituent needs could better performance catalytic activity with the form of sulfide, thereby catalyzer generally need carry out prevulcanized before use, and concrete vulcanization process can adopt technique known.Wherein, sulfidizing is preferably used CS ₂Cyclohexane solution handle described catalyzer, CS ₂Cyclohexane solution concentration be 2～6wt%, 260～360 ℃ of curing temperatures, sulfide stress 2～6MPa, curing time 2～10 hours, solution feed air speed 2～10h ^-1, hydrogen is 300～800 with the volume ratio (hydrogen to oil volume ratio) of sulfuration liquor charging.

So, catalytic cracking diesel oil hydrofinishing process provided by the invention comprise adopt above-mentioned catalyzer after sulfidizing with treat purified catalytic cracking diesel oil contact reacts, 280～380 ℃ of temperature of reaction, be preferably 320～360 ℃, reaction pressure 2～10MPa, be preferably 4～8MPa, liquid hourly space velocity 0.5～4h ^-1, 1～3h preferably ^-1, hydrogen to oil volume ratio 200～1200 is preferably 600～1000.

In the selection of reactor, can use fluidized-bed or moving-bed, but preferably use fixed bed.

Embodiment

Below further describe technical characterstic of the present invention by specific embodiment, with the beneficial effect that helps the reader to understand enforcement of the present invention better and produced, but do not constitute any qualification to the scope of the present invention.

Embodiment 1

Sol-gel method prepares TiO ₂-SiO ₂Composite oxide carrier CTS

Being dissolved in behind the ethanol tetraethoxy of 34.0g tetrabutyl titanate and 20.8g more respectively, uniform mixing gets solution A; With water, 41.2ml acetic acid and the 40ml dehydrated alcohol of 19ml mix solution B.Under intensive magnetic stirs, solution B dropwise splashed among the A react; Obtain colloidal sol behind the reaction certain hour, the aging under field conditions (factors) certain hour of colloidal sol just obtains gel; It is dry to adopt supercritical carbon dioxide fluid that this gel is implemented, and drying conditions is 40～60 ℃ of temperature, and pressure 8.0～12.0MPa, 500～600 ℃ of following roastings 3～4 hours, obtains white powder then at 2 hours time; With the white powder that obtains in retort furnace in 500～600 ℃ of roastings 3 hours, compression molding grinds the particle of the getting particle diameter 3～3.6mm carrier as the preparation catalyzer, is expressed as CTS.

Specific surface and pore volume that the method for employing BET records the CTS carrier are respectively 310m ²/ g and 0.55ml/g.The feed molar proportioning of optimizing is: (butyl (tetra) titanate+tetraethoxy): ethanol: water: acetic acid=1: 13: 2.5: 1.8, and the content of titanium and silicon is converted to the molar content of its oxide compound respectively in 20～80% scopes in the carrier of formation.

Embodiment 2

Solution containing phosphate pickling process modification CTS carrier

Under 60 ℃ of constant temperature water bath conditions, with CTS carrier and the equal-volume (NH of embodiment 1 ₄) ₂HPO ₄Mixed dipping 2h is dried 4h for 120 ℃ then in the solution, and 550 ℃ of roasting 2h are according to the consumption of carrier and the (NH of P loading (P introducing amount) preparation different concns ₄) ₂HPO ₄(or ammonium phosphate) steeping fluid, can make the P loading and be 1～4% modification CTS carrier (representing) of (mass content, below identical) with P-CTS.Adopt the specific surface area and the pore volume data of the method mensuration gained carrier of BET to list in table 1.

The specific surface area and the pore volume data of table 1P modification CTS carrier

Carrier	CTS	1％P-CTS	2％P-CTS	3％P-CTS	4％P-CTS
						Specific surface area, m 2/g	310	233	217	173	172
Pore volume, ml/g	0.55	0.55	0.58	0.47	0.45

Embodiment 3

Agent prepares phosphorous CTS carrier as the hydrolysis pH regulator with phosphoric acid

Prepare TiO at embodiment 1 with sol-gel method ₂-SiO ₂In the composite oxide carrier CTS process, with the phosphoric acid instead of part or all acetic acid is as the agent of hydrolysis pH regulator, the dosage of phosphoric acid is decided with the content of phosphorus in the CTS carrier, and other preparation conditions are same as embodiment 1, obtain phosphorated CTS carrier (representing with CTS+P).The specific surface area and the pore volume data of the method mensuration gained carrier of employing BET are as shown in table 2.

The specific surface area of the phosphorous CTS carrier of table 2 and pore volume data

Carrier	CTS	CTS+1％P	CTS+2％P	CTS+3％P	CTS+4％P
						Specific surface area, m 2/g	310	335	325	289	275
Pore volume, ml/g	0.55	0.62	0.59	0.54	0.51

Embodiment 4

The molecular sieve modified CTS carrier of HY

The tetraethoxy that takes by weighing 34.0g tetrabutyl titanate and 20.8g is dissolved in behind the ethanol more respectively, and uniform mixing gets solution A; With water, 41.2ml acetic acid and the 40ml dehydrated alcohol of 19ml mix solution B.Under violent stirring, in solution A, add 3g HY molecular sieve, after stirring solution B dropwise splashed among the A and react, obtain colloidal sol behind the reaction 15min, the aging under field conditions (factors) 24h～48h of colloidal sol just obtains gel; Further treatment condition are with embodiment 1.The gained carrier is designated as CTS-Y, and the introducing amount of molecular sieve is 10%.Adopt the specific surface area and the pore volume of the method mensuration carrier of BET to be respectively 298m ²/ g and 0.89ml/g.

Embodiment 5

Molecular sieve CY modification CTS preparing carriers

The 0.05mol citric acid is dissolved in the 80ml distilled water, 25g HY molecular sieve is joined in this citric acid solution, reacting about 2h under 35 ℃ of conditions.After filtering, washing, roasting is 2 hours in 2 hours, 500 ℃ air atmosphere of 120 ℃ of oven dry, gets the molecular sieve CY of modification.With embodiment 4 identical step and condition, substitute wherein HY molecular sieve with this molecular sieve CY, make the CTS carrier of molecular sieve CY modification, be designated as CTS-CY.The introducing amount of molecular sieve is 10%.Adopt specific surface area, the pore volume of the method mensuration carrier of BET to be respectively 258m ²/ g and 0.71ml/g.

Embodiment 6

The Ni-W/CTS Preparation of catalysts

Making concentration with deionized water is 0.8823g WO ₃The ammonium metatungstate solution of/ml moves into the 45ml ammonium metatungstate solution in the 100ml volumetric flask, add Ni (NO ₃) ₂6H ₂O 17g is diluted to scale with deionized water, shakes up and promptly gets nickel-tungsten activity component impregnation liquid.The CTS that makes with embodiment 1 is a carrier, under the room temperature condition with itself and isopyknic nickel-tungsten activity component impregnation liquid hybrid infusion 4～5 hours, then 110～120 ℃ of dryings 4～6 hours, 500～600 ℃ of roastings 3～4 hours.Get 3～3.6mm after sieving and partly be the Ni-W/CTS catalyzer, specific surface area, pore volume that the method for employing BET is measured this catalyzer are respectively 201m ²/ g and 0.41ml/g.Through atomic absorption analysis, the active component content in the prepared catalyst is in its oxide amount, and NiO is 2.57wt%, WO ₃Be 24.0wt%.

The CTS that adopts identical preparation method can make with above-mentioned different methods modification is that carrier, Ni-W are the catalyzer of active metal component.

Embodiment 7

The Co-Mo/CTS Preparation of catalysts

Take by weighing 14.7g Ammonium Molybdate Tetrahydrate ((NH ₄) ₆Mo ₇O ₂₄4H ₂O), be dissolved in the 20mL deionized water and be prepared into steeping fluid, taking by weighing the CTS that embodiment 1 makes is carrier 10g, join in the steeping fluid, and hybrid infusion 4～5 hours, then 110～120 ℃ of dryings 4～6 hours, 450～800 ℃ of roastings 3～4 hours.Take by weighing Cobaltous nitrate hexahydrate (Co (NO again ₃) ₂6H ₂O) 1.42g is dissolved in the 20mL deionized water and is prepared into steeping fluid, and the carrier behind the above-mentioned dipping molybdenum was joined in the cobalt steeping fluid hybrid infusion 4～5 hours, then 110～120 ℃ of dryings 4～6 hours, and 500～600 ℃ of roastings 3～4 hours.Get 3～3.6mm after sieving and partly be CATALYST Co-Mo/CTS, the specific surface area and the pore volume of catalyzer are respectively 126.3m ²/ g and 0.23ml/g.Through the atomic adsorption analysis, the active component content in the prepared catalyst is in its oxide amount, and CoO is 3.02wt%, MoO ₃Be 14.21wt%.

The CTS that adopts identical preparation method can make with above-mentioned different methods modification is that carrier, Co-Mo are the catalyzer of active metal component.

Embodiment 8

With modification CTS is the hydrodesulfurization activity of the catalyzer of carrier

With certain diesel oil from the heavy catalytic cracking 1 is raw material (S=1377 μ g.g ^-1), at loaded catalyst the hydrodesulfurization performance evaluation of carrying out catalyzer on the hydrogenation micro-reactor of 2ml, 360 ℃ of temperature of reaction, reaction pressure 4.0MPa, air speed 2.0h ^-1, hydrogen to oil volume ratio 600.The Ni-W that is able to is that the catalyzer of different carriers of active metal component is to the table 3 that the results are shown in of the desulfurization performance of this diesel oil from the heavy catalytic cracking.

Sulfidizing before catalyzer uses, sulfuration liquid is CS ₂Cyclohexane solution, concentration 2～3%, 300 ℃ of curing temperatures, sulfide stress 4.0MPa, curing time 4 hours, sulfuration liquid charging air speed 2h ^-1, hydrogen is 600 with the volume ratio of sulfuration liquid charging.

Hydrodesulfurization performance evaluation result (NiO:2.57wt%, the WO of table 3 catalyzer ₃: 24.0wt%)

Carrier	CTS	1％P-CTS	2％P-CTS	3％P-CTS	4％P-CTS	CTS-Y
							Desulfurization degree, %	92.8	93.5.	94.1	94.7	95.0	96.2
Carrier		CTS+1％P	CTS+2％P	CTS+3％P	CTS+4％P	CTS-CY
							Desulfurization degree, %		94.3	95.9	96.7	93.3	98.8

As can be seen, carrier being carried out catalyzer after the modification has for the deep desulfuration effect of diesel oil and significantly improves.

Embodiment 9

The catalyst hydrogenation desulfurization performance that different carriers makes relatively

Select for use a kind of diesel oil hydrofining catalyst of industrial practical application to be the comparative catalyst, the carrier of this catalyzer is the aluminum oxide of 3%P modification, and metal component is Ni-W, claims Ni-W/Al ₂O ₃-3P.With diesel oil from the heavy catalytic cracking 1 is raw material (S=1377 μ g.g ^-1), at 360 ℃ of temperature of reaction, reaction pressure 4.0MPa, air speed 2.0h ^-1, under hydrogen to oil volume ratio 600 conditions, the desulfurization degree data of catalyzer that with CTS and modification body thereof are carrier shown in embodiment 8 tables 3, catalyst n iW/Al ₂O ₃The desulfurization degree of-3P is 84.6%.To show with CTS and modifier thereof be that the hydrodesulfurization activity of the catalyzer of carrier significantly is better than with the aluminum oxide under equal contrast condition is the catalyzer of carrier.

Embodiment 10

Catalyzer is to the hydrodesulfurization activity of different material

Embodiment 8 has illustrated the hydrogenating desulfurization effect of catalyst towards heavy oil catalytic cracking diesel oil, and it is raw material (S=667 μ g.g that present embodiment is selected the diesel oil from the heavy catalytic cracking with another kind of attribute production ^-1), at 360 ℃ of temperature of reaction, reaction pressure 6.0MPa, air speed 2.0h ^-1, under hydrogen to oil volume ratio 600 conditions, described catalyst n i-W/CTS desulfurization degree is 97.8%, the desulfurization degree of Ni-W/CTS+3%P and Ni-W/CTS-CY is respectively 98.6% and 99.2% during same active ingredient loading.Show that catalyzer of the present invention all has hydrodesulfurization activity preferably to the diesel oil of different sources.

Embodiment 11

The hydrodenitrogenationactivity activity of catalyzer

With diesel oil from the heavy catalytic cracking 1 is raw material (N=1805mg.L ^-1), under the experiment condition identical, be several catalyzer (catalyzer among the embodiment 8 and 7) of making of active metal component, different carriers to the table 4 that the results are shown in of the nitrogen removal performance of diesel oil from the heavy catalytic cracking 1 with Ni-W, Co-Mo with embodiment 8.

The hydrodenitrification performance evaluation result of table 4 catalyzer

Embodiment 12

The hydrogenation aromatics-removing activity of catalyzer

With the diesel oil from the heavy catalytic cracking is raw material (aromatic hydrocarbons volume content 59.7%), under the experiment condition identical with embodiment 8, the aromatic hydrocarbons rate of taking off of Ni-W/CTS catalyzer is 7.0%, the aromatic hydrocarbons rate of taking off of Ni-W/CTS+3%P catalyzer is 18.2%, the aromatic hydrocarbons rate of taking off of Ni-W/CTS-CY catalyzer is 39.4%, illustrates with modification CTS to be that the aromatic hydrocarbons performance of taking off of the catalyzer of carrier is greatly improved.

In sum, catalyst towards heavy of the present invention oil catalytic cracking diesel oil not only has hydrogenating desulfurization effect preferably, and also has good hydrodenitrification effect and certain aromatic hydrocarbons performance of taking off, and is a kind of novel diesel Hydrobon catalyst of complete function.

Claims (17)

1, a kind of diesel oil hydrofining catalyst, its carrier is the product that the composite oxides of titanium dioxide and silicon-dioxide are handled through the phosphorus modification, active ingredient is two kinds of metallic combinations in cobalt, molybdenum, nickel and the tungsten, and the pore volume of this catalyzer is 0.4～0.7ml/g, and specific surface area is 150～350m ²/ g.

2, the described catalyzer of claim 1, wherein, the mass content of phosphorus is 1～5% in this carrier.

3, the described catalyzer of claim 1, wherein, the particle diameter of this catalyzer is 3～3.6mm.

4, the described catalyzer of claim 1, wherein, the content of active ingredient is in its oxide amount: NiO 1～3%, WO ₃10～20%, CoO 3～5%, MoO ₃10～15%.

5, prepare the method for each described diesel oil hydrofining catalyst of claim 1～4, it comprises:

Adopt sol-gel method to prepare colloidal sol the salt or the ester of titanium and silicon, and make its aging gel, dry roasting of obtaining;

To predetermined phosphorus content, dry roasting obtains the titania-silica composite oxide carrier of phosphorus modification to this product of roasting with solution containing phosphate dipping;

Adopt solution dipping method determined active metal component to be supported on this composite oxide carrier dry roasting.

6, the described preparation method of claim 5, wherein, described solution containing phosphate comprises: Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid or ammonium phosphate.

7, the described preparation method of claim 5 wherein, adopts supercritical carbon dioxide fluid drying, heated drying or lyophilize during the preparation composite oxide carrier.

8, the described preparation method of claim 5, wherein, described solution dipping method is synchronous pickling process, composite oxide carrier be impregnated in the mixing solutions of active metal salt the dipping time under the room temperature 4～6 hours.

9, the described preparation method of claim 5, wherein, when supporting one of active metal component on carrier and being molybdenum, adopt step impregnation method, composite oxide carrier floods wherein a kind of solution of active metal salt earlier, flood solution, after drying and the roasting of another kind of active metal salt after drying, the roasting again.

10, prepare the method for each described diesel oil hydrofining catalyst of claim 1～4, it comprises:

Adopt sol-gel method to prepare colloidal sol the salt of titanium and silicon or ester, in this process with solution containing phosphate as partly or entirely hydrolysis pH regulator agent adding, dry roasting obtains the titania-silica composite oxide carrier of phosphorus modification;

Adopt solution dipping method determined active metal component to be supported on this composite oxide carrier dry roasting.

11, the described preparation method of claim 10, wherein, described solution containing phosphate comprises: Secondary ammonium phosphate, primary ammonium phosphate, phosphoric acid or ammonium phosphate.

12, the described preparation method of claim 10 wherein, adopts supercritical carbon dioxide fluid drying, heated drying or lyophilize during the preparation composite oxide carrier.

13, the described preparation method of claim 10, wherein, described solution dipping method is synchronous pickling process, composite oxide carrier be impregnated in the mixing solutions of active metal salt the dipping time under the room temperature 4～6 hours.

14, the described preparation method of claim 10, wherein, when supporting one of active metal component on carrier and being molybdenum, adopt step impregnation method, composite oxide carrier floods wherein a kind of solution of active metal salt earlier, flood solution, after drying and the roasting of another kind of active metal salt after drying, the roasting again.

15, the hydrofinishing process of catalytic cracking diesel oil adopts each described diesel oil hydrofining catalyst of claim 1～4 to contact the hydrofining reaction of catalytic diesel oil with treating the purified catalytic cracking diesel oil after prevulcanized is handled.

16, the described method of claim 15, wherein, it is to use CS that prevulcanized is handled ₂Cyclohexane solution handle described catalyzer, CS ₂Cyclohexane solution concentration be 2～6wt%, 260～360 ℃ of curing temperatures, sulfide stress 2～6MPa, curing time 2～10 hours, solution feed volume space velocity 2～10h ^-1, hydrogen to oil volume ratio is 300～800.

17, the described method of claim 15, wherein, described hydrofining comprises hydrogenating desulfurization, hydrodenitrification and/or hydrogenation aromatics-removing.