CN101927191B - Hydrogenation catalyst carrier with acid additive concentration in gradient increasing distribution and preparation method thereof - Google Patents

Abstract

The invention relates to a hydrogenation catalyst carrier with the concentration of an acid additive in gradient increasing distribution and a preparation method thereofPreparing a method; with Al₂O₃Or containing SiO₂、TiO₂、ZrO₂Al of (2)₂O₃The carrier is soaked by deionized water, and in the process of soaking the carrier, a solution with high concentration of the acid additive is gradually added to saturate the carrier, or the carrier is soaked on the carrier in a gradient distribution from inside to outside in a low-to-high manner by preparing at least two solutions with different concentrations of the acid additive and spraying the solutions on the carrier from low to high in sequence according to the concentration of the acid additive; drying at 80-150 ℃ for 1-8 hours, and roasting in air at 300-650 ℃ for 2-6 hours; the preparation method is simple, the manufacturing cost is low, the physical and chemical properties of the acidity and the pore structure of the carrier can be effectively modulated, the acidity of the catalyst can be further effectively modulated, the interaction between the active component and the carrier can be further improved, and the stable operation period and the activity of the catalyst can be effectively increased.

Description

A kind of acidic assistant concentration increases catalyst carrier for hydrgenating of distribution and preparation method thereof in gradient

Technical field

The present invention relates to a kind of acidic assistant concentration and increase catalyst carrier for hydrgenating that distributes and preparation method thereof from the inside to the outside in gradient.

Background technology

Along with crude oil heaviness, poor qualityization aggravation in the world wide; The increasingly stringent of environmental regulation; Market but increases the demand of light-end products year by year simultaneously; The deep processing of development heavy oil is petroleum refining industry's task of top priority, and the heavy-oil hydrogenation technology is faced with great challenge as main manufacturing process, presses for to develop better heavy oil hydrogenation process and heavy-oil hydrogenation catalyst active, that stability is higher.Catalyst carrier can regulating catalyst acid and/or improve the interaction between active component and carrier, therefore, it is especially crucial that the exploitation of carrier material seems.

The hydrotreatment and the reforming catalyst of modern petroleum refining industry almost all adopt alumina support.Because the irregular condensation of surface hydroxyl, alumina support all has certain acidity, and these acid centres cause the hydro carbons condensation easily and form carbon deposit, cause catalysqt deactivation.Especially the mink cell focus hydrotreatment process that very easily causes carbon deposit for some, catalyst carrier surface acidity strong and weak directly determine the length that catalyst can stable operation cycle.At present, hydrotreating catalyst is all with aluminium oxide or contain one or more other elements such as the aluminium oxide of Si, Ti, P, B, F etc. is a carrier.In catalyst preparation process, can in system, introduce above-mentioned element in different phase, its purpose is the acidity of regulating catalyst, and improves the interaction between active component and carrier.

In the support material building-up process as prepare aluminium hydroxide with the precipitation method; Add multiple above-mentioned element simultaneously; Because each material addition sequence changes; Cause very big-difference at the residing position of alumina surface and with the effect degree of catalyst surface can for certain element, thereby catalyst property is produced bigger influence.US4; 629; 716 described with in phosphorus-containing compound, the bialuminate aqueous solution (adding phosphoric acid) like alchlor and alkali aluminate soln (like sodium metaaluminate) preparation alumina support prepare process, the hole of this carrier radius＜5nm accounts for more than 80% specific area＞300m²/ g, phosphorus content are 0.1m%～4.5m%.Because phosphorus is to add in the alumina support with the precipitation method, therefore, not only there is part phosphorus to get into the alumina body phase, reduced the utilization rate of phosphorus, the structure of aluminium oxide there is adverse influence.

At present, adding preparation catalyst needed certain or multiple auxiliary agent after the carrier moulding is way relatively more commonly used.This method is the acidity and the pore structure of modulation carrier effectively, improves the interaction between active component and carrier.

For the catalyst carrier for hydrgenating that conventional method obtains, the acidic assistant concentration on its particle distributes often comparatively even.At present, it is less to be preparation method's the report of catalyst carrier for hydrgenating of uneven distribution about acidic assistant concentration.

Summary of the invention

The purpose of this invention is to provide a kind of acid concentration increases catalyst carrier for hydrgenating that distributes and preparation method thereof from the inside to the outside in gradient, uses as hydrotreatment and catalyst for hydro-upgrading carrier.

The concrete preparation process that acid concentration increases the catalyst carrier for hydrgenating of distribution in gradient is:

Select Al for use₂O₃Or contain SiO₂, TiO₂, ZrO₂Al₂O₃As carrier, acid compound is made into maceration extract, adopt the method for saturated dipping to prepare catalyst carrier for hydrgenating.

Earlier use deionized water, in the carrier impregnation process, progressively add the saturated sprayed carrier of method of the high solution of acid concentration; Or through preparing the solution of at least two kinds of different acid concentrations, spray from low to high on carrier by acid concentration, make acid concentration on carrier, form the Gradient distribution that is from inside to outside from high to low.Again 80-150 ℃ dry 1～8 hour down, then at 300～650 ℃, be preferably in 400～550 ℃ the air roasting 2～6 hours.Here, acid additive refers to contain one or more of compound of P, B, F, preferably phosphoric acid, boric acid, ammonium phosphate, ammonium dihydrogen phosphate (ADP) or ammonium fluoride.Need to prove in the preparation process and can add an amount of organic acid, optimization citric acid, oxalic acid, nitrilotriacetic acid, tartaric acid etc. as required.

A kind of catalyst carrier for hydrgenating by the inventive method preparation is characterized in that:

1) selects Al for use₂O₃Or contain SiO₂, TiO₂, ZrO₂Al₂O₃As carrier;

2) pore volume is 0.2～3.0mL/g, is preferably 0.45～1.3mL/g;

3) specific surface is 20～400m²/ g is preferably 100～240m²/ g;

4) carrier contains vehicle weight 0.5～10%, is preferably 1～5% F, P and/or B;

5) acidic assistant concentration distribution gradient in the carrier granular increases to outer surface from the particle center gradually.The carrier granular center is 0.05～0.70 with the ratio of outer surface acid concentration weight; Be preferably 0.15～0.45; 0.33R the ratio that (the carrier granular center is an initial point, and R is the carrier granular radius) located with outer surface acid concentration weight is 0.21～0.80, is preferably 0.32～0.65; 0.66R the ratio that (R is the carrier granular radius) located with outer surface acid concentration weight is 0.40～0.92, is preferably 0.50～0.85.

Fig. 1, Fig. 2 are the acidic assistant concentration distribution map of carrier granular center to face.In carrier granular, acidic assistant concentration can exist with the distribution form of Fig. 1, also can exist with the distribution form of Fig. 2.Fig. 2 can find: from the carrier granular center to face, acidic assistant concentration distributes and three platforms, two steps have occurred.Here need to prove that the distribution of acidic assistant concentration on carrier granular can exist with one or more stepped form.But total trend is: from the carrier granular center to face, acid concentration increases in gradient.

The initial carrier that catalyst carrier of the present invention is used can be to drip ball forming, spin granulation, extrusion modling, compression molding etc., is best to drip ball forming and extrusion modling.The catalyst carrier shape can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape.With spherical and bar shaped is best.

The effect of invention

Preparation method provided by the invention is simple, low cost of manufacture.This method is the physicochemical properties such as acidity, pore structure of modulation carrier effectively, and then regulating catalyst acid and/or improve the interaction between active component and carrier more effectively, can effectively increase catalyst stable operation cycle and activity.The resulting carrier of the present invention can be used for the mink cell focus field of hydrogenation, is particularly useful for the carrier use as the hydrotreating catalyst of deasphalted oil, reduced crude and decompression residuum.

Description of drawings

The acidic assistant concentration of Fig. 1 carrier granular center to face distributes.

The acidic assistant concentration of Fig. 2 carrier granular center to face distributes.

Specific embodiment

Embodiment 1

Present embodiment is with Al₂O₃Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier, spray the 60mL deionized water, the aqueous solution that contains 10.0g 85% phosphoric acid (Beijing chemical reagents corporation, down with) that in the process of spraying, at the uniform velocity splashes into 105mL is in dipping solution and stir, and sprays while splashing into, and sprays in 5 minutes.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, then 120 ℃ dry 5 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-1.

Embodiment 2

Present embodiment is to contain 1.5m%SiO₂Al₂O₃Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method that sprays to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier; Spray 105mL and contain the aqueous solution of 2g 50% ammonium fluoride (Beijing chemical reagents corporation, down with), spray and at the uniform velocity splash into the aqueous solution that 60mL contains 4.0g 50% ammonium fluoride in the process in dipping solution and stir; Spray while splashing into, sprayed in 15 minutes.Homogenizing is after 10 minutes in the equipment of spraying, in 120 ℃ dry 4 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-2.

Embodiment 3

Present embodiment is to contain 1.0m%SiO₂And 1.5m%TiO₂Al₂O₃Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier, spray 50mL contain 3.0g 85% boric acid (Beijing chemical reagents corporation, down with) and the aqueous solution; After having sprayed, then spray the aqueous solution that 50mL contains 6g 85% boric acid, spray 25mL after; Then spray 65mL and contain 16.0g 85% boric acid and 10.0g citric acid (Beijing chemical reagents corporation; The aqueous solution down together) also stirs in dipping solution, sprays while splashing into, and floods in 15 minutes.Homogenizing is after 30 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out the back 120 ℃ dry 5 hours down, then roasting 3 hours in 500 ℃ of air makes catalyst carrier, is numbered C-3.

Embodiment 4

Present embodiment is to contain 2.0m%ZrO₂Al₂O₃Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier; Spray the 82.5mL deionized water; In the process of spraying, at the uniform velocity splash into the aqueous solution that 82.5mL contains 10.0g ammonium dihydrogen phosphate (ADP) (Beijing chemical reagents corporation, down with) and 3.0g tartaric acid (Beijing chemical reagents corporation, down with) in dipping solution and stirring; Spray while splashing into, sprayed in 10 minutes.Homogenizing is after 20 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 6 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-4.

Embodiment 5

Present embodiment is with Al₂O₃Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier, spray the 35mL deionized water, spray and at the uniform velocity splash into the aqueous solution that 65mL contains 3.0g85% phosphoric acid and 3.0g 85% boric acid in the process in dipping solution and stir; Spray while splashing into; After having sprayed, and then spray the aqueous solution that 50mL contains 6.0g 85% phosphoric acid, 6.0g 85% boric acid and 12.0g acetate (Beijing chemical reagents corporation, down together) again; After spraying 15mL; At the uniform velocity splash into the aqueous solution that 15mL contains 6.0g85% phosphoric acid and 6.0g 85% boric acid in maceration extract and stir, spray, sprayed in 15 minutes while splashing into.Homogenizing is after 10 minutes in the equipment of spraying, 120 ℃ dry 7 hours down, roasting 6 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-5.

Embodiment 6

Present embodiment is to contain 1.5m%TiO₂And 1.0m%ZrO₂Al₂O₃Make carrier, water absorption rate is 1.10mL/g.Adopt the saturated method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier; Spray 75mL and contain the aqueous solution of 4.0g 85% phosphoric acid, in the process of spraying, at the uniform velocity splash into the aqueous solution that 50mL contains 8g 85% phosphoric acid in dipping solution and stir, spray while splashing into; Spray a half, at the uniform velocity splash into 40mL and contain 16.0g 85% phosphate aqueous solution.Sprayed in 10 minutes.Homogenizing is after 20 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 6 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-6.

Comparative example 1

Present embodiment is with Al₂O₃Make carrier, water absorption rate is 1.10mL/g, adopts the saturated method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier, spray the aqueous solution that 165mL contains 10.0g 85% phosphoric acid.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-7.

Comparative example 2

Present embodiment is with Al₂O₃Make carrier, water absorption rate is 1.10mL/g, adopts the supersaturation method of spraying to prepare the catalyst carrier of acidic assistant concentration distribution gradient.

Take by weighing the 150g carrier, spray the aqueous solution that 185mL contains 10.0g 85% phosphoric acid.Homogenizing is after 10 minutes in the equipment of spraying, 60 ℃ dry 2 hours down, take out back 120 ℃ dry 3 hours down, roasting 3 hours in 500 ℃ of air again makes catalyst carrier, is numbered C-8.

Embodiment 7

Adopt characterization methods such as BET, EDX that catalyst carrier C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8 are characterized, physico-chemical property is seen table 1 in detail.

The physico-chemical property of table 1 catalyst carrier

Annotate: R is the carrier granular radius, is starting point with the carrier granular center.

Can find out from table 1, catalyst carrier C-1, C-2, C-3, C-4, C-5, C-6 particle from interior to outside, acidic assistant concentration increases trend in gradient.And support C-7 is comparatively even with C-8 acidic assistant concentration substep.

Embodiment 8

Choose the carrier 150g of embodiment 1,embodiment 2, Comparative Examples 1 preparation, contain the 59.6g ammonium molybdate with 330mL respectively and (contain MoO₃82m%), the ammoniacal liquor mixed solution of 54.0g nickel nitrate (containing NiO 25.2m%) dipping 1 hour, after the filtration, dried 2 hours, roasting is 4 hours in 500 ℃ of air atmospheres, makes catalyst.Be numbered C1, C2, C7.Molybdenum oxide, the nickel oxide content of the catalyst that obtains are seen table 2.

Table 2 catalyst physical data

Embodiment 9

The hydrogenation performance of the various catalyst that following illustrative embodiment 8 prepares.Active appraisal experiment carries out on 100mL small fixed hydrogenation plant.Estimating feedstock oil is the normal slag of Saudi Arabia, and character is as shown in table 3.

Table 3 feedstock oil main character

Appreciation condition is as shown in table 4.

Table 4 process conditions

The activity rating result lists in table 5.Relatively metal removal rate, desulfurization degree, denitrification percent are that to take off percentage of admixture with the C1 catalyst be 1.00 to make benchmark and relatively get.By finding out in the table 5, the demetallization per of catalyst C1 and C2, desulfurization degree and denitrification percent all are higher than Comparative Examples catalyst C7.

Table 5 catalyst stability contrast experiment

Claims (1)

1. an acidic assistant concentration increases the catalyst carrier for hydrgenating of distribution in gradient, it is characterized in that:

1) with Al₂O₃Or contain SiO₂, TiO₂, ZrO₂Al₂O₃As carrier;

2) pore volume is 0.2～3.0mL/g;

3) specific surface is 20～400m²/ g;

4) carrier contains F, P and/or the B of vehicle weight 0.5～10%;

5) acidic assistant concentration distribution gradient in the carrier granular; Increase gradually to outer surface from the particle center; The carrier granular center is 0.05～0.70 with the ratio of outer surface acidity assistant concentration weight; 0.33R the ratio of locating with outer surface acidity assistant concentration weight is 0.21～0.80, the 0.66R place is 0.40～0.92 with the ratio of outer surface acidity assistant concentration weight;

R is for being the carrier granular radius of initial point with the carrier granular center,

The acid additive that uses in the preparing carriers process is meant phosphoric acid, boric acid, diammonium hydrogen phosphate, ammonium phosphate or ammonium fluoride.

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