CN102049264A - Hydrodesulphurization catalyst and preparation method thereof - Google Patents
Hydrodesulphurization catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hydrodesulphurization catalyst and a preparation method thereof. In the hydrodesulphurization catalyst, boron and silicon are taken as auxiliary agents, and tungsten (W), molybdenum (Mo) and nickel (Ni) are taken as active metal ingredients. The preparation method comprises the following steps of: preparing a catalyst carrier from modified alumina which contains the boron and the silicon and is taken as a raw material, and impregnating into solution which contains the W, the Mo and the Ni so as to obtain the catalyst, wherein the boron and the silicon serving as the auxiliary agents are added in the process of preparing the alumina. The catalyst auxiliary agent prepared by the method can be uniformly dispersed into the whole carrier, so the hydrodesulphurization activity of the catalyst can be greatly improved, and carbon deposit on the catalyst is reduced; and the catalyst can be used for the hydrodesulphurization process of multiple kinds of distillate oil, particularly the hydrodesulphurization of coking naphtha.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst and preparation method thereof.Catalyst of the present invention is suitable for the hydrodesulfurization of various fraction oil, especially the hydrodesulfurization of coking naphtha.
Background technology
Along with sulfur content in the fuel oil for vehicles standard descends year by year, hydrodesulfurization has become the main path that the processing inferior raw material is produced clean fuel oil.The activity of Hydrobon catalyst has determined the economic benefit of whole hydrodesulfurization.Highly active Hydrobon catalyst can be produced the product of low-sulfur under the condition that relaxes, thereby prolongs service cycle and save operating cost.The big approach that the processing heavy charge is produced light-end products is a coking, and coking produces a large amount of coking naphthas.Coking naphtha contains easily coking material such as a large amount of alkene, colloid, is easy to produce carbon deposit and coking and causes catalysqt deactivation in process; And the coking naphtha of delayed coking also contains the silicon that can cause the catalyst permanent deactivation in a large number, and removing of silicon is not the major function of Hydrobon catalyst of the present invention, can be with reference to other pertinent literatures.
It is active component that Hydrobon catalyst adopts group vib and VIII family metal usually, and can add multiple auxiliary agent and improve catalyst activity.In the Preparation of catalysts process, the even dispersion of each component produces significant effects to the performance of catalyst.
CN1597869 discloses a kind of oil wax material Hydrobon Catalyst And Its Preparation Method, this catalyst is to be reactive metal with tungsten, molybdenum and nickel (or cobalt), with siliceous and aluminium oxide two kinds of auxiliary agents of phosphorus is carrier, and its preparation method is to flood the tungstenic-nickel or the cobalt aqueous solution respectively, contain molybdenum-the boron aqueous solution and making by siliceous and alumina support phosphorus.In this Preparation of catalysts process, auxiliary agents of silicon and boron are that substep adds, and cause them at the catalyst surface skewness easily, and therefore cause catalyst surface acid site skewness and reactive metal skewness.
Method and the CN1597869 of CN1289830 are similar, and catalyst is carrier (adding silicon when the moulding) with siliceous aluminium oxide, and the method that adopts a solution impregnation is load active component and auxiliary agent boron simultaneously, and dry then, roast makes catalyst.Therefore this catalyst also exists and CN1597869 catalyst similar problem.
CN101015805 discloses a kind of catalyst for hydrorefining distillate oil.This catalyst consists of W/Mo/Ni/SiO
2/ A1
2O
3, add the B auxiliary agent.This catalyst carrier is that the mixed kneading of siliceous aluminium oxide and boric acid forms fully, so the dispersiveness of boron is also undesirable.
CN1302848 relates to a kind of hydrogenation catalyst and preparation method thereof, this catalyst is supported on a kind of aluminium oxide by the specific process preparation by W, Ni and prepares, the aluminium oxide of specific process preparation is by adding the fluorine modification, adds one or more oxide preparation of boron, silicon, phosphorus, magnesium, titanium, zirconium, gallium simultaneously.Add fluorine in this Preparation of catalysts process, fluorine runs off easily, causes catalysqt deactivation rapidly and the corrosion of upstream device.
CN1853773 discloses alumina dry glue of a kind of siliceous and boron and preparation method thereof, employing is carried out aluminium oxide earlier and is become glue, introduces auxiliary agents of silicon then, introduces auxiliary agent boron at last, this method also is unfavorable for the even distribution of auxiliary agent on alumina support, and this alumina dry glue is suitable for the hydrodenitrogeneration reaction.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of Hydrobon catalyst and preparation method thereof.Hydrobon catalyst auxiliary agent of the present invention is evenly distributed, and acid centre is evenly distributed, and acid strength is moderate, the hydrodesulfurization activity height.Catalyst of the present invention is fit to the hydrodesulfurization of various fraction oil, especially is fit to the hydrodesulfurization of coking naphtha, and can reduce the carbon deposit in the coking naphtha unifining process.
Hydrobon catalyst of the present invention is carrier with the aluminium oxide, with boron and silicon is auxiliary agent, with W, Mo, Ni is active metal component, boron content accounts for the 2wt%-30wt% of alumina weight, dioxide-containing silica accounts for the 1wt%-10wt% of alumina weight, preferred 1wt%-5wt%, in final catalyst weight, WO in the catalyst
3Content is 2wt%-18wt%, MoO
3Content is that 4wt%-20wt%, NiO content are 1wt%-4wt%.
The pore volume of Hydrobon catalyst of the present invention is 0.2-0.6mL/g, and specific area is 150-360m
2/ g.
Hydrobon catalyst NH of the present invention
3-TPD method characterizes acidity of catalyst.Catalyst absorption NH
3After, desorption under different temperatures, the record desorption rate is to weigh acidity of catalyst center intensity and quantity.The NH of 150-250 ℃ of desorption
3Be to be adsorbed on the more weak acid site, and 250-400 ℃ of desorption be adsorbed in than on the strong acid center NH of 400-500 ℃ of desorption
3Then be adsorbed on the strong acid center.Hydrobon catalyst total acid content 0.5-1.5mmol/g of the present invention, wherein 150-250 ℃ accounts for 40%-70%, and 250-400 ℃ accounts for 30%-60%, and 400-500 ℃ accounts for below 10%.
In the Hydrobon catalyst of the present invention, auxiliary agent boron becomes in the glue process to introduce at aluminium oxide, and auxiliary agents of silicon is introduced after aluminium oxide becomes glue.
Hydrobon catalyst of the present invention is suitable for using in the coking naphtha hydrogenation most.
The preparation method of Hydrobon catalyst of the present invention comprises following process:
1. adopt cocurrent process to prepare the homodisperse aluminium hydroxide rubber powder of B.With aluminum sulfate, sodium metaaluminate, three kinds of aqueous solution of boric acid ammonia, carry out three bursts of modes that also flow and become glue.Control final aluminium oxide boron content 2wt%-30wt%.Become 15-45 ℃ of glue process temperature control, become the glue process pH value to be controlled at 6-11.5.
The above-mentioned aluminium hydroxide gel powder of 2 usefulness adds silicon-containing compound and peptizing agent, mixes aftershaping, obtains catalyst carrier after drying and the roasting.The silicon-containing compound consumption is introduced by the 1%-10% that accounts for alumina weight with the titanium dioxide silica.The drying condition of carrier is generally at 80～200 ℃ to descend dry 3～10 hours, and roasting condition is generally 400～800 ℃ of following roastings 1～6 hour.
3 usefulness contain the above-mentioned carrier of solution impregnation of W, Mo, Ni three component composition, and dry then and selectable calcination steps obtains final catalyst.The drying condition of catalyst is generally at 80～200 ℃ to descend dry 1～10 hour, and roasting condition is generally 350～550 ℃ of following roastings 1～6 hour.
In the inventive method, become the glue process can adopt conventional method and apparatus, when becoming the glue reaction, carry out stirring operation.
In the inventive method, peptizing agent preferably uses salpeter solution.Silicon-containing compound comprise white carbon, Ludox, estersil etc. one or more.
Forming process of the present invention can be the ripe forming process of any industry, as compressing tablet, patter, spin, extrude, oil column etc.
Hydrobon catalyst of the present invention adopts suitable auxiliary agent and reactive metal to cooperate, and obtaining the highly active while, has reduced the carbon deposit in the use, has prolonged the service life of catalyst.Method for preparing catalyst of the present invention makes catalyst carrier have suitable surface acidity by the optimization of different auxiliary agents introducing modes, and particularly acid centre is evenly distributed, and the highly acid heart that easily causes the carbon deposit reaction is few.When this catalyst is used for the coking naphtha unifining process, in effective desulfurization, can obviously reduce carbon deposit.Because the coking naphtha raw material contains than easy carbon deposit, coking materials such as polyenes, when catalyst surface contains the acid site of higher-strength, be easy to carbon deposit and coking.These carbon deposits and coking and blocking catalyst duct, the covering catalyst surface causes rapid catalyst deactivation.Catalyst of the present invention adopts the equally distributed aluminium oxide of auxiliary agent B to prepare carrier, and it is few and catalyst that the total acid number is many can effectively be avoided excessive carbon deposit when improving catalyst hydrodesulfurization active to obtain strong acid center.
The specific embodiment
Characteristics of the present invention are to adopt three bursts of one-tenth glue modes that also flow to obtain the uniform high total acid content aluminium oxide in acid site, carrier and catalyst.Acid centre is even, has avoided the accumulation and the consequent strong acid center in acid site.
In the coking naphtha unifining process, because raw material contains a large amount of unsaturated materials such as alkene of coking easily, be easy to coking on the acid site of catalyst, cause the catalyst rapid deactivation.Adopt catalyst of the present invention,, can reduce carbon deposit and coking on the catalyst, prolong catalyst life because only contain the weak acid center of comparatively high amts.
And the interpolation of auxiliary agent B of the present invention helps to improve the total acid quantity of catalyst, and therefore obtains higher hydrodesulfurization activity.
To these problems be described with embodiment below, wherein unspecified percentage composition is a weight percentage.
Embodiment 1
Adopt cocurrent process to prepare the homodisperse aluminium hydroxide rubber powder of B.With aluminum sulfate, sodium metaaluminate, three kinds of aqueous solution of boric acid ammonia, carry out three strands of also one-tenth glue of stream.Control boron accounts for the 2wt% of alumina weight, becomes 20 ℃ of glue process temperature controls, becomes the glue process pH value to be controlled at 7.5.Filtration drying obtains boracic aluminium hydroxide rubber powder then.
Get this aluminium hydroxide rubber powder 100g, add nitric acid 3%, water purification 15%, mix 3h.Add Ludox then and in mixture, make SiO
2Content accounts for 5% of alumina weight, continues to mix 3h, is extruded into Φ 2mm cylinder with banded extruder.Extrudate in 500 ℃ of roasting 3h, obtains carrier behind 120 ℃ of dry 2h.
Get above-mentioned carrier, the aqueous solution of dipping ammonium metatungstate, ammonium molybdate, nickel nitrate mixture makes WO on the catalyst
3Content 8%, MoO
3Content 7%, NiO content 3%.Dipping is after 120 ℃ of dry 2h obtain catalyst A of the present invention.
Embodiment 2
Adopt cocurrent process to prepare the homodisperse aluminium hydroxide rubber powder of B.With aluminum sulfate, sodium metaaluminate, three kinds of aqueous solution of boric acid ammonia, carry out three strands of also one-tenth glue of stream.Control boron accounts for the 4wt% of alumina weight, becomes 40 ℃ of glue process temperature controls, becomes the glue process pH value to be controlled at 10.5.Filtration drying obtains boracic aluminium hydroxide rubber powder then.
Get this aluminium hydrate powder 100g, add nitric acid 3%, water purification 15%, mix 3h.Add Ludox then and in mixture, make SiO
2Content is 5% of alumina weight, continues to mix 3h, is extruded into Φ 2mm cylinder with banded extruder.Extrudate in 500 ℃ of roasting 3h, obtains carrier behind 120 ℃ of dry 2h.
Get above-mentioned carrier, the aqueous solution of dipping ammonium metatungstate, ammonium molybdate, nickel nitrate mixture makes WO on the catalyst
3Content 8%, MoO
3Content 7%, NiO content 3%.Dipping is after 120 ℃ of dry 2h obtain catalyst B of the present invention.
Embodiment 3
Adopt cocurrent process to prepare the homodisperse aluminium hydroxide rubber powder of B.With aluminum sulfate, sodium metaaluminate, three kinds of aqueous solution of boric acid ammonia, carry out three strands of also one-tenth glue of stream.Control boron accounts for the 8wt% of alumina weight, becomes 35 ℃ of glue process temperature controls, becomes the glue process pH value to be controlled at 8.Filtration drying obtains boracic aluminium hydroxide rubber powder then.
Get this aluminium hydrate powder 100g, add nitric acid 3%, water purification 15%, mix 3h.Add Ludox then and in mixture, make SiO in the final products
2Content reaches 5%, continues to mix 3h, is extruded into Φ 2mm cylinder with banded extruder.Extrudate in 500 ℃ of roasting 3h, obtains carrier behind 120 ℃ of dry 2h.
Get above-mentioned carrier, the aqueous solution of dipping ammonium metatungstate, ammonium molybdate, nickel nitrate mixture makes WO on the catalyst
3Content 8%, MoO
3Content 7%, NiO content 3%.Dipping is after 120 ℃ of dry 2h obtain catalyst C of the present invention.
Comparative example 1
Get commercial alumina powder 100g, add nitric acid 3%, water purification 15%, mix 3h.Add Ludox then and in mixture, make SiO
2Content accounts for 5% of aluminium oxide, continues to mix 3h, is extruded into Φ 2mm cylinder with banded extruder.Extrudate in 500 ℃ of roasting 3h, obtains carrier behind 120 ℃ of dry 2h.
Get above-mentioned carrier, the aqueous solution of dipping ammonium metatungstate, ammonium molybdate, nickel nitrate mixture makes WO on the catalyst
3Content 8%, MoO
3Content 7%, NiO content 3%.Dipping is after 120 ℃ of dry 2h obtain catalyst D of the present invention.
Comparative example 2
Get commercial alumina powder 100g, add nitric acid 3%, water purification 15%, mix 3h.Add Ludox then and in mixture, make SiO
2Content accounts for 5% of alumina weight, adds boric acid and makes B content account for 2% of alumina weight in mixture, continues to mix 3h, is extruded into Φ 2mm cylinder with banded extruder.Extrudate in 500 ℃ of roasting 3h, obtains carrier behind 120 ℃ of dry 2h.
Get above-mentioned carrier, the aqueous solution of dipping ammonium metatungstate, ammonium molybdate, nickel nitrate mixture makes WO on the catalyst
3Content 8%, MoO
3Content 7%, NiO content 3%.Dipping is after 120 ℃ of dry 2h obtain catalyst E of the present invention.
Comparative example 3
Get commercial alumina powder 100g, add nitric acid 3%, water purification 15%, mix 3h.Add Ludox then and in mixture, make SiO
2Content accounts for 5% of oxidation aluminium weight, adds boric acid and makes B content account for 4% of alumina weight in mixture, continues to mix 3h, is extruded into Φ 2mm cylinder with banded extruder.Extrudate in 500 ℃ of roasting 3h, obtains carrier behind 120 ℃ of dry 2h.
Get above-mentioned carrier, the aqueous solution of dipping ammonium metatungstate, ammonium molybdate, nickel nitrate mixture makes WO on the catalyst
3Content 8%, MoO
3Content 7%, NiO content 3%.Dipping is after 120 ℃ of dry 2h obtain catalyst E of the present invention.
Adopt NH
3-TPD method is analyzed analysis result such as table 1 to the acid matter of above-mentioned catalyst.
The acid matter of table 1 embodiment and comparative example catalyst surface
| Numbering | 150-250℃，％ | 250-400℃，％ | 400-500℃，％ | Total acid, mmol/g |
| A | 65.1 | 33.2 | 1.7 | 0.621 |
| B | 63.2 | 34.6 | 2.2 | 0.759 |
| C | 47.3 | 43.6 | 9.1 | 0.773 |
| D | 66.3 | 32.1 | 1.6 | 0.502 |
| E | 60.7 | 36.2 | 4.82 | 0.514 |
| F | 59.2 | 37.1 | 5.18 | 0.637 |
Adopt little opposition catalyst activity to estimate.Raw material is a coking naphtha, and reaction condition is: reaction pressure 5.0MPa, hydrogen to oil volume ratio 300, volume space velocity 5.0h
-1, 280 ℃ of reaction temperatures.Hydrodesulfurization activity is got preceding 10 days average activity.The relative volume activity is meant the activity contrast when using the equal volume catalyst to estimate.
Result such as table 2.
Table 2 embodiment and the contrast of comparative example catalyst hydrogenation activity
| Numbering | Hydrodesulfurization relative volume activity, % |
| A | 100 |
| B | 181 |
| C | 215 |
| D | 70 |
| E | 85 |
| F | 106 |
Above-mentioned running rear catalyst is carried out the carbon content analysis.The running activity is to get preceding 10 days mean value, but is accurate that coke content is analyzed in the assurance present embodiment, has proceeded 15 days running again.
Analysis result such as table 3.
Table 3 embodiment and the contrast of comparative example catalyst carbon deposit situation
| Numbering | Running rear catalyst carbon content accounts for catalyst weight % |
| A | 3.79 |
| B | 4.63 |
| C | 6.17 |
| D | 3.65 |
| E | 4.82 |
| F | 5.18 |
From above evaluating data as can be seen, when Hydrobon catalyst of the present invention was used in coking naphtha hydrogenation process, coke content was close with existing catalyst, but hydrodesulfurization activity obviously improves.
Claims (10)
1. Hydrobon catalyst, with the aluminium oxide is carrier, it is characterized in that: with boron and silicon is auxiliary agent, with W, Mo, Ni is active metal component, boron content accounts for the 2wt%-30wt% of alumina weight, dioxide-containing silica accounts for the 1wt%-10wt% of alumina weight, in final catalyst weight, and WO in the catalyst
3Content is 2wt%-18wt%, MoO
3Content is that 4wt%-20wt%, NiO content are 1wt%-4wt%.
2. according to the described catalyst of claim 1, it is characterized in that: the pore volume of Hydrobon catalyst is 0.2-0.6mL/g, and specific area is 150-360m
2/ g.
3. according to the described catalyst of claim 1, it is characterized in that: the NH of Hydrobon catalyst
3-TPD acid amount is as follows: total acid content 0.5-1.5mmol/g, and wherein 150-250 ℃ accounts for 40%-70%, and 250-400 ℃ accounts for 30%-60%, and 400-500 ℃ accounts for below 10%.
4. according to the described catalyst of claim 1, it is characterized in that: in the Hydrobon catalyst, auxiliary agent boron becomes in the glue process to introduce at aluminium oxide, and auxiliary agents of silicon is introduced after aluminium oxide becomes glue.
5. the application of the described Hydrobon catalyst of the arbitrary claim of claim 1 to 4 in the coking naphtha hydrogenation.
6. described Preparation of catalysts method of claim 1 comprises following process:
(1) adopts cocurrent process to prepare the homodisperse aluminium hydroxide rubber powder of B,, carry out three bursts of modes that also flow and become glue with aluminum sulfate, sodium metaaluminate, three kinds of aqueous solution of boric acid ammonia;
(2) with above-mentioned aluminium hydroxide gel powder, add silicon-containing compound and peptizing agent, mix aftershaping, obtain catalyst carrier after drying and the roasting;
(3) with the above-mentioned carrier of solution impregnation that contains W, Mo, Ni three component composition, dry then and selectable calcination steps obtains final catalyst.
7. in accordance with the method for claim 6, it is characterized in that: step (1) becomes the glue process temperature to be controlled to be 15-45 ℃, becomes the glue process pH value to be controlled to be 6-11.5.
8. in accordance with the method for claim 6, it is characterized in that: the drying condition of carrier is to descend dry 3～10 hours at 80～200 ℃ in the step (2), and roasting condition is 400～800 ℃ of following roastings 1～6 hour.
9. in accordance with the method for claim 6, it is characterized in that: the drying condition of catalyst is to descend dry 1～10 hour at 80～200 ℃ in the step (3), and roasting condition is 350～550 ℃ of following roastings 1～6 hour.
10. it is characterized in that in accordance with the method for claim 6: the silicon-containing compound in the step (2) comprises one or more in white carbon, Ludox and the estersil.
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