CN1088093C - Process for preparing hydrorefining catalyst - Google Patents

Abstract

The present invention relates to a preparation method for hydrorefining catalysts. In the method, Gamma -Al2O3 carrying titanium and phosphor is used as a carrier, and one or the combination of the elements of group VIII ,and one or the combination of the elements of group VIB are used as active components. The gamma-Al2O3 carrier containing the titanium and the phosphor is prepared by a pugging method, and the active components are added by an immersion method. The method has the advantages of short flow path and simple technology. The obtained catalyst is particularly suitable for the hydrotreatment of hydrocarbon containing high sulfur and nitrogen, and has high activity and stability. The nitrogen content and the sulfur content of hydrocarbon products treated by using the catalyst are lower than 1 mu g/g, and bromine values are lower than or equal to 0.1 gram bromine /100 gram oil.

Description

A kind of preparation method of Hydrobon catalyst

The present invention relates to a kind of preparation method of Hydrobon catalyst, more particularly, relate to a kind of to support the γ-Al of the two auxiliary agents of titanium and phosphorus₂O₃Be carrier, active ingredient is the Preparation of catalysts method of tungsten (or molybdenum), nickel (or cobalt).

The hydrofining of the petroleum products important process process that is absolutely necessary in petrochemical complex its objective is in order to remove organic nitrogen compound contained in the stock oil and organic sulfide, to improve the quality of products and to satisfy environmental requirement.Need a kind of effective catalyzer in this process, used catalyzer is the catalyzer that is loaded with molybdenum (or/and tungsten), cobalt (or/and nickel) on the aluminum oxide in the traditional technology.

United States Patent (USP) 4,465,790 disclose a kind of Mo-Ni-P-Ti catalyzer, and this catalyzer contains two auxiliary agent P and Ti.Its preparation method is: earlier with a certain amount of Al₂(SO₄)₃14H₂O, Ti (SO₄)₂H₂SO₄Solution and water mix, and make the solution of sulfur acid aluminium and titanium.Again with a certain amount of NaOH, Al₂O₃3H₂The mixed sodium aluminate solution that gets of O and water.Above-mentioned two kinds of solution join in the flask that contains certain water gaging, 50% gluconic acid and Tai-Ace S 150 simultaneously, and the beginning temperature is 54 ℃, and keeping the pH value during adding solution is 8.5; Add excessive sodium aluminate solution at last and make the pH value rise to 10.2, obtain the soup compound precipitation.After filtration, wash 2 times, carry out spraying drying, make the dried glue of Ti-Al.Get same gauge water of the dried glue of a certain amount of Ti-Al and concentrated nitric acid and ground 50 minutes, be squeezed into cloverleaf pattern, the drying roasting obtains the Ti-Al carrier.Soak solution impregnation altogether with what contain Mo-Ni-P again, Ni-P-Ti-Mo/ γ-Al is made in the drying roasting₂O₃Catalyzer.It is active and stable that this catalyzer has higher hydrodesulfurizationof of hydrocarbons, but many shortcomings are also arranged: 1, the preparation flow of Ti-Al carrier is long, complex process, production cost height; 2, adopt that the Mo-Ni-P's contain the high density molybdenum soak solution impregnation Ti-Al carrier altogether, because the acidity of co-impregnated solution is stronger, making the specific surface area of catalyzer compare with carrier in steeping process has bigger loss, and the use properties of catalyzer is adversely affected; 3, hydrocarbons hydrogenation denitrification activity and the stability that adopts this method to make catalyzer can also further improve.

Purpose of the present invention is the deficiency that overcomes hydrorefining catalyst for hydrocarbon preparation method in the prior art, provide that a kind of preparation flow is short, technology is simple, specific surface area of catalyst has the preparation method of the hydrorefining catalyst for hydrocarbon of high hydrodenitrogenationactivity activity, high hydrodesulfurization activity and high stability more greatly, simultaneously.

The carrier of the catalyzer that the inventive method obtains is the γ-Al that is loaded with titanium and the two auxiliary agents of phosphorus₂O₃, carrier can be expressed as Ti-P-γ-Al₂O₃Active ingredient can be tungsten, nickel, and this catalyzer can be expressed as: W-Ni/Ti-P-γ-Al₂O₃

Ti-P-γ-Al of the present invention₂O₃Carrier and W-Ni/Ti-P-γ-Al₂O₃The Preparation of catalysts method is as follows:

1, Ti-P-γ-Al₂O₃The preparation of carrier

The mixing solutions of one water alumina dry glue and titanium chloride and P contained compound fully mixed pinch, moulding, carry out drying, washing, calcination steps then and obtain Ti-P-γ-Al of the present invention₂O₃Carrier.

Wherein titanium chloride can be titanous chloride or titanium tetrachloride.P contained compound can be phosphoric acid, Hypophosporous Acid, 50, tetra-sodium, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate etc.Support of the catalyst can be made various suitable shapes, as cloverleaf pattern, bar shaped, sphere etc.Above-mentioned drying step was dried 2～10 hours down at 120～350 ℃ then for to dry in the shade prior to room temperature, and drying temperature is preferably 200～350 ℃.Washing step uses the ammonia scrubbing of 5～20% (volumes), and the ammoniacal liquor of preferred 10～20% (volumes) is then in 120～150 ℃ of oven dry 2～10 hours.The temperature of calcination steps is 450～650 ℃, and the time is 5～10 hours.

Prepared Ti-P-γ-Al₂O₃Carrier contains titanium oxide (TiO by weight₂) 2～45%, be preferably 5～25%, contain Vanadium Pentoxide in FLAKES (P₂O₅) 1～10%, be preferably 3～8%.The specific surface area of measuring this carrier with nitrogen absorption BET method is 100～350m²/ g, pore volume are 0.1～1.5ml/g, and mean pore size is 4～17nm.

2, W-Ni/Ti-P-γ-Al₂O₃The Preparation of catalysts method:

W-Ni/Ti-P-γ-Al of the present invention₂O₃Catalyzer can adopt traditional immersion process for preparing, as soaking method or step impregnation method altogether.

It is as follows to soak the method step altogether:

(1), preparation ammonium metawolframate and nickelous nitrate soak solution altogether: ammonium metawolframate and six water nickelous nitrates are put into same beaker, add deionized water, the elimination mechanical impurity is standby after the dissolving.

(2), ammonium metawolframate and nickelous nitrate soak solution impregnation altogether: with the equivalent impregnation method with the above-mentioned solution spraying that soaks altogether to above-mentioned carrier, in 120～150 ℃ of oven dry 2～10 hours, in 450～650 ℃ of roastings 5～10 hours, can make the catalyzer W-Ni/Ti-P-γ-Al of oxidation state again₂O₃Resultant catalyzer contains WO by weight₃10～30%, be preferably 15～25%, contain NiO 2～8%, be preferably 3～6%.

The step impregnation method is as follows:

(1) tungstate solution dipping: for example ammonium tungstate solution is sprayed on the above-mentioned carrier that makes,, in 450～650 ℃ of roastings 5～10 hours, can make WO again in 120～150 ℃ of oven dry 2～10 hours with the equivalent impregnation method₃Content is 10～30% (weight), is preferably the catalyst precursor WO of 15～25% (weight)₃/ Ti-P-γ-Al₂O₃

(2) nickel salt solution dipping: for example nickel nitrate solution is sprayed on the above-mentioned catalyst precursor with the equivalent impregnation method, in 120～150 ℃ of oven dry 2～10 hours, 450～650 ℃ of roastings 5～10 hours, can make NiO content was 2～8% (weight), is preferably the catalyzer of 3～6% (weight).

Method for preparing catalyst flow process of the present invention is short, and technology is simple, can reduce investment of production equipment and process cost greatly, and the catalyzer cost is greatly reduced.Use the inventive method in addition, in the Catalyst Production process, the loss of specific surface area is less, the catalyzer finished product is compared with its carrier, and the specific surface area rate of loss only is 10～20%, and with United States Patent (USP) 4,465,790 catalyzer that make, rate of loss is up to about 50%.The catalyzer of the inventive method preparation simultaneously has the active and stable of higher hydrodenitrification and hydrogenating desulfurization, and every performance all is better than the catalyzer that existing method makes.

The purposes of the catalyzer that the present invention makes is in hydrocarbons hydrogenation transforms HDN and HDS process to be played katalysis simultaneously.This catalyzer needs to carry out prevulcanized before use.The typical catalyzer that uses the inventive method acquisition is to 80～300 ℃ of boiling ranges, nitrogen content 5～500 μ g/g, sulphur content 5～1000 μ g/g, the stock oil that the bromine valency is less than or equal within 20 gram bromines/100 gram oil all can transform under the effect of this catalyzer, and can make nitrogenous in the products obtained therefrom, sulfur content all be less than or equal to 1 μ g/g, the bromine valency is less than or equal to 0.10 gram bromine/100 gram oil.

Catalyst system therefor of the present invention needs prevulcanized before use, and its prevulcanized condition is: 200～400 ℃ of temperature, 10%H₂S-90%H₂Mixture pressure is 5MPa, and airshed is 12 ml/min/gram catalyzer, and the prevulcanized time is 4～8 hours.After the prevulcanized, cool the temperature to 200 ℃, feed stock oil (boiling range is within 80～300 ℃, sulphur content 5～1000 μ g/g, nitrogen content 5～500 μ g/g, bromine valency 20 gram bromines/100 gram oil).The hydrofining condition is as follows: 255～300 ℃ of temperature, pressure 5MPa, air speed 2～4h^-1, hydrogen-oil ratio (volume) is 400: 1.

In order to further specify the present invention, enumerate following examples and the contrast experiment is as follows.

Embodiment 1

1, the preparation of carrier

With 133 grams, one water alumina dry glues and 32.5 gram titanium tetrachlorides, 19.5 gram phosphoric acid with 90 the gram water mixed solutions are fully mixed pinches, be extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, after 4 hours, the ammonia scrubbing with 20% in 120 ℃ of oven dry 4 hours, progressively is warming up to 500 ℃ 350 ℃ of oven dry, and roasting 6 hours makes and is loaded with TiO₂And P₂O₅γ-Al₂O₃Carrier (Ti-P-γ-Al₂O₃), titanium oxide (TiO wherein₂) be 8.5% (weight), phosphorus oxide (P₂O₅) be 7.4% (weight), specific surface area is 280m²/ g.

2, Preparation of catalysts

(1) preparation ammonium metawolframate and nickelous nitrate soak solution altogether: 47.1 gram ammonium metawolframates and 26.3 grams, six water nickelous nitrates are put into same beaker, add 70 gram deionized waters, and dissolving back elimination mechanical impurity, standby.

(2) ammonium metawolframate and nickelous nitrate soak solution impregnation altogether: with the equivalent impregnation method this is soaked solution spraying altogether to above-mentioned carrier, in 120 ℃ of oven dry 4 hours, 500 ℃ of roastings 5 hours, can make the catalyzer W-Ni/Ti-P-γ-Al of oxidation state₂O₃, WO wherein₃Content is 22.5% (weight), and NiO content is 4% (weight), and specific surface area is 220m²/ g, this catalyzer is represented with A.

Embodiment 2

1, the preparation of carrier

With 133 grams, one water alumina dry glues and 16 gram titanium tetrachlorides, 19.5 gram phosphoric acid with 90 the gram water mixed solutions are fully mixed pinches, be extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, after 9 hours, the ammonia scrubbing with 15% in 120 ℃ of oven dry 4 hours, progressively is warming up to 480 ℃ 180 ℃ of oven dry, and roasting 8 hours makes and is loaded with TiO₂And P₂O₅γ-Al₂O₃Carrier (Ti-P-γ-Al₂O₃), titanium oxide (TiO wherein₂) be 4.2% (weight), phosphorus oxide (P₂O₅) be 7.4% (weight).Specific surface area is 290m²/ g.

2, Preparation of catalysts and embodiment 1 are together.The gained catalyzer contains WO₃Content is 22.5% (weight), and NiO content is 4% (weight), and specific surface area is 240m²/ g, this catalyzer is represented with B.

Embodiment 3

1, the preparation of carrier

With the titanium tetrachlorides of water alumina dry glues of 133 grams and one 49 grams, 19.5 gram phosphoric acid with 90 the gram water mixed solutions are fully mixed pinches, be extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, after 7 hours, the ammonia scrubbing with 18% in 120 ℃ of oven dry 4 hours, progressively is warming up to 500 ℃ 300 ℃ of oven dry, and roasting 7 hours makes and is loaded with TiO₂And P₂O₅γ-Al₂O₃Carrier (Ti-P-γ-Al₂O₃), titanium oxide (TiO wherein₂) be 12.6% (weight), phosphorus oxide (P₂O₅) be 7.4% (weight).Specific surface area is 240m²/ g.

2, Preparation of catalysts and embodiment 1 are together.The gained catalyzer contains WO₃Content is 22.5% (weight), and NiO content is 4% (weight), and specific surface area is 198m²/ g, this catalyzer is represented with C.

Embodiment 4

1, the preparation of carrier

With 133 grams, one water alumina dry glues and one 65 gram titanium tetrachlorides, 19.5 gram phosphoric acid with 90 the gram water mixed solutions are fully mixed pinches, be extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, after 6 hours, the ammonia scrubbing with 12% in 120 ℃ of oven dry 4 hours, progressively is warming up to 500 ℃ 320 ℃ of oven dry, and roasting 8 hours makes and is loaded with TiO₂And P₂O₅γ-Al₂O₃Carrier (Ti-P-γ-Al₂O₃), titanium oxide (TiO wherein₂) be 16.6% (weight), phosphorus oxide (P₂O₅) be 7.2% (weight).Specific surface area is 220m²/ g.

2, Preparation of catalysts and embodiment 1 are together.The gained catalyzer contains WO₃Content is 22.5% (weight), and NiO content is 4% (weight), and specific surface area is 180m²/ g, this catalyzer is represented with D.

Embodiment 5

1, the preparation of carrier

With 133 grams, one water alumina dry glues and one 96 gram titanium tetrachlorides, 19.5 gram phosphoric acid with 90 the gram water mixed solutions are fully mixed pinches, be extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, after 6 hours, the ammonia scrubbing with 16% in 120 ℃ of oven dry 4 hours, progressively is warming up to 600 ℃ 270 ℃ of oven dry, and roasting 5 hours makes and is loaded with TiO₂And P₂O₅γ-Al₂O₃Carrier (Ti-P-γ-Al₂O₃), titanium oxide (TiO wherein₂) be 25% (weight), phosphorus oxide (P₂O₅) be 7% (weight).Specific surface area is 200m²/ g.

2, Preparation of catalysts and embodiment 1 are together.The gained catalyzer contains WO₃Content is 22.5% (weight), and NiO content is 4% (weight), and specific surface area is 165m²/ g, this catalyzer is represented with E.

Embodiment 6

1, the preparation of carrier

With 133 grams, one water alumina dry glues and one 145 gram titanous chlorides, 19.5 gram primary ammonium phosphates with 90 the gram water mixed solutions are fully mixed pinches, be extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, after 6 hours, the ammonia scrubbing with 20% in 120 ℃ of oven dry 4 hours, progressively is warming up to 500 ℃ 250 ℃ of oven dry, and roasting 4 hours makes and is loaded with TiO₂And P₂O₅γ-Al₂O₃Carrier (Ti-P-γ-Al₂O₃), titanium oxide (TiO wherein₂) be 35% (weight), phosphorus oxide (P₂O₅) be 7% (weight).Specific surface area is 180m²/ g.

2, Preparation of catalysts and embodiment 1 are together.The gained catalyzer contains WO₃Content is 22.5% (weight), and NiO content is 4% (weight), and specific surface area is 148m²/ g, this catalyzer is represented with F.

Comparative Examples

Press US4,465,790 patents prepare carrier and catalyzer is as follows: with 113 parts of Al₂(SO₄)₃14H₂O, 130 parts of Ti (SO₄)₂H₂SO₄Solution (contains 8.3%TiO₂) and 147 parts of water mix, make the solution of sulfur acid aluminium and titanium.With 90 parts of NaOH, 152 parts of Al₂O₃3H₂O and 120 parts of mixed sodium aluminate solutions that get of water.Above-mentioned two kinds of solution join simultaneously and contain 640 parts of water, and in the flask of 2.4 part 50% gluconic acid and 20 parts of Tai-Ace S 150, the beginning temperature is 54 ℃, and keeping the pH value during adding solution is 8.5; Add excessive sodium aluminate solution at last and make the pH value rise to 10.2, obtain the soup compound precipitation.After filtration, wash 2 times, carry out spraying drying.Get 1 kilogram of spray-dired powder and ground 50 minutes with 0.7 kg water and 22.5ml concentrated nitric acid, be squeezed into cloverleaf pattern, the drying roasting obtains desired pore structure.The specific surface area of carrier is 290m²/ g.Soak solution impregnation altogether with what contain Mo-Ni-P again, the catalyzer of drying roasting contains MoO by weight₃18%, NiO 3%, P₂O₅3%, TiO₂7%, all the other are γ-Al₂O₃, the specific surface area of catalyzer is 149m²/ g.This catalyzer is represented with G.

The application of embodiment 7 catalyzer in the hydrocarbon conversion

Catalyst A, B, C, D, E, F and G are tested as hydrogenating desulfurization and denitrogenation.Catalyzer G is as the contrast experiment.Catalyst A, B, C, D, E, F and G operation condition are identical.

Get catalyzer 5.0 gram and pack into and carry out prevulcanized in the fixed-bed reactor, its prevulcanized condition is: 370 ℃ of temperature, 10%H₂S-90%H₂Mixture pressure is 5MPa, and airshed is 12 ml/min/gram catalyzer, and the prevulcanized time is 8 hours.After the prevulcanized, cool the temperature to 200 ℃, feed stock oil (boiling range is within 80～300 ℃, sulphur content 1000 μ g/g, nitrogen content 500 μ g/g, bromine valency 20 gram bromines/100 gram oil).300 ℃ of temperature, pressure 5MPa, air speed is 2.5h^-1, hydrogen-oil ratio (volume) is to react under 400: 1 the condition.

Active comparing result is as shown in table 1.

Table 1

Catalyzer	Runtime (hour)	Product nitrogen content (μ g/g)	Product sulphur content (μ g/g)	Product bromine valency (gram bromine/100 gram oil)
					A	200	1.0	1.0	0.05
B	200	5.0	3.0	0.1
					C	200	1.0	1.0	0.1
D	200	5.0	10.0	0.2
					E	200	5.0	5.0	0.1
F	200	5.0	5.0	0.2
					G	200	5.0	2.0	0.2

From table 1 data as can be seen, under the close situation of each component concentration, hydrogenating desulfurization, denitrification activity and the hydrogenation saturated activity of the catalyst A that the inventive method obtains all is higher than the catalyzer G that control methods obtains.Stability experiment is as shown in table 2.

Table 2

Catalyzer	Runtime (hour)	Product nitrogen content (μ g/g)	Product sulphur content (μ g/g)	Product bromine valency (gram bromine/100 gram oil)
					C	1000	1.0	1.0	0.1
G	1000	7.0	4.0	0.2

From table 2 data as can be seen, the catalyzer that uses the inventive method to obtain still has higher activity after long-time running, illustrate that it has good stability, and the comparative catalyst is after the identical time of running, active existing obviously decline is so the stability of the catalyzer that the inventive method obtains is better than the prior art catalyzer.

Claims (9)

1, a kind of preparation method of Hydrobon catalyst, comprise the preparing carriers step and use the immersion process for preparing catalyzer, the preparation method who it is characterized in that carrier is: the mixing solutions of a water alumina dry glue and titanium chloride and P contained compound is fully mixed pinch, moulding, carry out drying, washing, calcination steps then and obtain Ti-P-γ-Al₂O₃Carrier, wherein said drying process is for to dry in the shade prior to room temperature, dried 2～10 hours down at 120～350 ℃ then, described washing step is for using the ammonia scrubbing of 5～20v%, then in 120～150 ℃ of oven dry 2～10 hours, the temperature of described calcination steps is 450～650 ℃, and the time is 5～10 hours.

2, by the method for claim 1, it is characterized in that described titanium chloride is selected from titanous chloride, titanium tetrachloride.

3, by the method for claim 1, it is characterized in that described P contained compound is selected from phosphoric acid, Hypophosporous Acid, 50, tetra-sodium, phosphorous acid, ammonium phosphate, ammonium hydrogen phosphate, primary ammonium phosphate.

4, by the method for claim 1, it is characterized in that described drying temperature is 200～350 ℃.

5, the method for claim 1 is characterized in that described washing ammonia concn is 10～20v%.

6, the method for claim 1 is characterized in that prepared Ti-P-γ-Al₂O₃Carrier contains TiO by weight₂2～45%, contain P₂O₅1～10%, the specific surface area of measuring this carrier with nitrogen absorption BET method is 100～350m²/ g, pore volume are 0.1～1.5ml/g, and mean pore size is 4～17nm.

7, by the method for claim 6, it is characterized in that prepared Ti-P-γ-Al₂O₃Carrier contains TiO by weight₂Be 5～25%, contain P₂O₅Be 3～8%.

8, by the method for claim 1, it is characterized in that the Preparation of catalysts method is as follows:

(1), preparation ammonium metawolframate and nickelous nitrate soak solution altogether: ammonium metawolframate and six water nickelous nitrates are put into same beaker, add deionized water, the elimination mechanical impurity is standby after the dissolving;

(2), ammonium metawolframate and nickelous nitrate soak solution impregnation altogether: with the equivalent impregnation method with the above-mentioned solution spraying that soaks altogether to above-mentioned carrier, in 120～150 ℃ of oven dry 2～10 hours, in 450～650 ℃ of roastings 5～10 hours, can make the catalyzer W-Ni/Ti-P-γ-Al of oxidation state again₂O₃, resultant catalyzer contains WO by weight₃10～30%, contain NiO 2～8%.

9, by the method for claim 1, it is characterized in that the Preparation of catalysts method is as follows:

(1) tungstate solution dipping: with the equivalent impregnation method ammonium tungstate solution is sprayed on the above-mentioned carrier that makes,, in 450～650 ℃ of roastings 5～10 hours, can make WO again in 120～150 ℃ of oven dry 2～10 hours₃Content is the catalyst precursor WO of 10～30w%₃/ Ti-P-γ-Al₂O₃

(2) nickel salt solution dipping: with the equivalent impregnation method nickel nitrate solution is sprayed on the above-mentioned catalyst precursor,,, can make the catalyzer that NiO content is 2～8w% 450～650 ℃ of roastings 5～10 hours in 120～150 ℃ of oven dry 2～10 hours.