CN1019502B - Hydrofined catalyst and preparing process thereof - Google Patents
Hydrofined catalyst and preparing process thereofInfo
- Publication number
- CN1019502B CN1019502B CN 89109140 CN89109140A CN1019502B CN 1019502 B CN1019502 B CN 1019502B CN 89109140 CN89109140 CN 89109140 CN 89109140 A CN89109140 A CN 89109140A CN 1019502 B CN1019502 B CN 1019502B
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Abstract
The present invention relates to a hydrofining catalyst and a preparation method thereof. The catalyst uses silicon oxide and alumina as a carrier and metallic elements of the VIII group and the VIB group as active components, adds a boron auxiliary agent and particularly contains three active components of W, Mo and Ni and the boron auxiliary agent. In the preparation method of the catalyst, the active components and the auxiliary agent are added to the carrier by spraying and immersing solution, and the auxiliary agent boron is added to the carrier by that orthoboric acid and ammonia water solution is sprayed and immersed to the carrier.
Description
The present invention relates to a kind of Hydrobon catalyst and preparation thereof, particularly fraction oil hydrodenitrogenation catalyst and preparation thereof.
Typical Hydrobon catalyst is a carrier with aluminum oxide or siliceous aluminum oxide, is active constituent with VIII family and VI B family metallic element.In order further to improve the activity and the activity stability of Hydrobon catalyst, adopted various methods, as carrier is carried out modification, improve preparation condition, add auxiliary agent etc.Wherein selected auxiliary agent has P, F, B, Tl, Zr etc.The method of adding auxiliary agent has coprecipitation method, mechanical kneading method and pickling process.For hydrodenitrification, add boron as the auxiliary agent best results, and support that to add effect of boron again behind the hydrogenation component better.But there are the following problems to add boron with pickling process: the most frequently used boron-containing compound is a boric acid when adding boron, and boric acid solubleness in water is very low under the room temperature, and 100 ml waters can only dissolve the boric acid about 6 grams.So when at room temperature using the boric acid aqueous solution impregnated catalyst, the boron loading does not seldom have the effect that improves catalyst activity on the catalyzer.B on the general requirement catalyzer
2O
3Content is at 2-6%.
In order to address this problem, Japanese Patent 54-096489 adopts following method: soak catalyzer with excessive boric acid aqueous solution, by heating solution moisture content is evaporated.
But this method also has certain shortcoming.During heating evaporation solution moisture content the operating time oversize, be unfavorable for the suitability for industrialized production of catalyzer, and evaporate to dryness solution causes catalyzer outside surface metal enrichment, the intensity of catalyzer is subjected to certain influence.
Another kind of solution is to add organic cosolvents such as quadrol, solubleness and the stability of solution of raising boric acid in ammoniacal liquor.But so, the catalyzer manufacturing cost is improved, and quadrol is poisonous, Working environment is worsened.
The purpose of this invention is to provide a kind of fraction oil hydrodenitrogenation catalyst, and add the existing problem of boron, provide a kind of quick and convenient, the practicable boron method that adds at catalyzer in the prior art.
The present invention is a kind of employing silica-alumina carrier, be active constituent with VIII family and VI B family metal, and add the catalyzer of boron additive.Its reactive metal component and auxiliary agent all are to spray by the mixing solutions that contains above-mentioned active constituent and auxiliary agent, are added on the carrier of moulding, and the drying roasting makes catalyzer then.
One, the preparation of support of the catalyst
Someone reasons out in the hydrodenitrification reaction of research quinoline: desire to make the C-N bond rupture, the strength of acid of aluminum oxide is not enough, and stronger acidity need be arranged.The present invention introduces small amounts silicon in aluminum oxide, make the silica-alumina carrier.Concrete preparation process is to be mixed with mixed acid solution with aluminum chloride and acidified sodium silicate, wherein (SiO
2)/(SiO
2+ Al
2O
2) * 100%=5-10%(is heavy), this solution and the ammonia soln that contains ammonia 10% under pH value 7-9 and temperature 15-40 ℃ condition, become glue continuously, control 8-12 minute duration of contact, 90 minutes assembly glue time.Colloid separated after aging half an hour, colloid is kneaded into false colloidal sol with mineral acid after water purification washs 3-4 time, again through the oil column balling-up, the ammonia post solidifies, wet rubber ball is through the steam oven drying, 500-700 ℃ was decomposed 3-4 hour and obtains support of the catalyst in stoving oven, and its physico-chemical property is as follows: specific surface 240-280 rice
2/ gram, pore volume 0.40-0.70 milliliter/gram are concentrated aperture 40-80A, and dioxide-containing silica 5-10%(is heavy), particle diameter 1.3-2.8 millimeter.
Two, the selection of catalyst metal components
As everyone knows, for hydrodenitrification, W-Nl type catalyzer is than Mo-Nl type catalyst activity height, and our result of study also further shows, under the suitable condition of metal content, W-Mo-Nl three component catalyst denitrification activities are high (comparative result sees Table 1) than W-Nl two components.
Table 1 pair component and three components (the metal total content is identical)
Catalyst activity relatively
Evaluating apparatus: 100ml fixed bed
Stock oil: grand celebration coker gas oil
Appreciation condition: 360 ℃ of hydrogen pressure 2.94MPa, temperature
Air speed 1.0h
-1, hydrogen-oil ratio 600
Metal component W-Nl W-Mo-Nl
Bulk density 0.95 0.95
Denitrification percent % 63 71
Three, the selection of auxiliary agent
On three component catalysts, add auxiliary agent boron, catalyst activity is further improved, but add-on can not be too low, generally should be heavy at 2-6%() in the scope.
The W-Mo-Nl catalyzer denitrification activity of table 2 different boron content relatively
Stock oil: grand celebration coker gas oil
Condition: hydrogen pressure 2.94MPa, 360 ℃ of temperature, air speed 1.0h
-1
Catalyzer a b c d
Pore volume ml/g 0.36 0.35 0.33 0.32
Bulk density g/ml 1.02 1.03 1.06 1.08
B
2O
3%(is heavy) 0 1.32 2.92 4.55
Denitrification percent % 75 75 83 81
Four, the adding of reactive metal component and auxiliary agent
Because catalyzer of the present invention adopts the silica-alumina carrier,, carrier is broken if, will emit a large amount of heats of adsorption with normal pressure supersaturation dipping.Can adopt vacuum supersaturation dipping so prepare catalyzer of the present invention.The adding method that the present invention proposes a kind of more effective metal component and auxiliary agent is that normal pressure sprays, and promptly the support of the catalyst of preparation is put into a rotating container (rotary drum), and the dipping solution with saturated extent of adsorption under rotating sprays smile lentamente to carrier.
For W-Mo-Nl-B catalyzer of the present invention, can adopt three sections solution to spray and make, its first section sprays and contains W solution and spray for second section and contain Mo-Nl solution, the 3rd section sprays and contains B solution, also can first section spray and contain Mo-Nl solution, first section sprays and contains W solution, and the 3rd section sprays and contain B solution.The method of simplifying is two sections and sprays, and first section sprays and contain W-Nl solution, and second section sprays and contain Mo-B solution.
Preparation of catalysts process of the present invention is: (1) sprays previously prepared silica-alumina carrier with containing the W-Nl aqueous solution, dry then, roasting.(2) spray catalyzer work in-process with containing the Mo-B ammonia soln, dry then, roasting by (1) gained.Also can be that (1) sprays previously prepared silica-alumina carrier with containing the W aqueous solution, dry then, roasting.(2) spray work in-process with the ammonia soln that contains Mo-Nl by (1) gained.(3) spray work in-process with the ammonia soln of boracic again, make catalyzer by (2) gained.
In the Preparation of catalysts process of the present invention, the used W aqueous solution that contains can be ammonium metatungstate aqueous solution, containing the Mo-Nl ammonia soln can be Ammonium Heptamolybdate and nickelous nitrate or single nickel salt ammonia soln, containing the B ammonia soln can be the boric acid ammonia soln, containing W-Nl water-soluble can be ammonium metawolframate and nickel nitrate aqueous solution, and containing the Mo-B ammonia soln can be Ammonium Heptamolybdate and boric acid ammonia soln.Add ammoniacal liquor can make boric acid at room temperature the solubleness in the water improve greatly, and solution becomes must be stablized through heating, both having made be Ammonium Heptamolybdate with the ammonia soln that mixes of boric acid also is extremely stable.
The preparation of the used W-Nl of the containing aqueous solution of the present invention: take by weighing a certain amount of ammonium metawolframate and nickelous nitrate, get final product with water dissolution.The solution of making contains WO for per 100 milliliters
3The 32-48 gram, the Nl7-14 gram.
The preparation of the used Mo-B of containing ammonia soln: take by weighing a certain amount of Ammonium Heptamolybdate and boric acid, add concentration 6-15%(and weigh) ammonia solvent at 40-90 ℃ of following heated mixt 2-10 hour, makes it to become stable solution, and its concentration is per 100 milliliters and contains MoO
3The 17-27 gram, B
2O
3The 8-16 gram.
The compound concentration of above-mentioned various solution, the active constituent that should require according to catalyzer and the content of auxiliary agent and the water-intake rate of carrier are determined.
Catalyst preparation step of the present invention: take by weighing a certain amount of aforesaid silica-alumina carrier (the dry mistake), according to the carrier water-intake rate, measure a certain amount of W-Nl of containing aqueous solution, carrier granule is placed rotary drum, rotate rotary drum, spray with the W-Nl aqueous solution, then being lower than 130 ℃ of dryings down, again at 380-420 ℃ of following roasting 2-6 hour.The work in-process of getting after the roasting place rotary drum, rotate rotary drum, according to its water-intake rate, measure a certain amount of Mo-B of containing ammonia soln and spray, and then 100-130 ℃ of drying, at 460-550 ℃ of following roasting 2-5 hour, make product catalyst.In the preparation process, the speed that sprays should be controlled effectively, otherwise the intensity of catalyzer will be destroyed.
Catalyzer of the present invention also can adopt the mode that sprays for three times or four times to prepare.Soon W, Mo, Nl, B are made into three kinds or four kinds of solution, and (wherein boron-containing solution is that process adds thermally-stabilised boric acid ammonia soln, and all the other are water or ammonia soln) sprays support of the catalyst respectively, all needs drying and roasting after every kind of solution sprays.The compound concentration of various solution is that each component concentration that requires according to catalyzer and the water-intake rate of carrier are determined equally.Dry identical with preceding a kind of preparation method with the process conditions of roasting.
Catalyzer of the present invention has following feature: pore volume 0.22-0.35 milliliter/gram, ratio table 130-160 rice
2/ gram, SlO
2/ (SlO
2+ Al
2O
3) * 100%=5-10%(is heavy), contain in catalyst weight: WO
313-25%, MoO
36-14%, NlO2-6%, B
2O2-7%.WO preferably
317-19%, MoO
38-10%, NlO3-5%, B
2O
33-5%.
Adopt catalyzer of the present invention, for being the unifining process of raw material, at hydrogen pressure 1.45-8.0MPa, temperature of reaction 320-400 ℃, during liquid hourly space velocity 0.5-6.0 with fraction oil
-1Under hydrogen-oil ratio 400-1000 condition, can obtain good refining effect.With the grand celebration coker gas oil is raw material, when hydrogen pressure 2.94MPa, 360 ℃ of temperature of reaction, air speed 1.0
-1Under hydrogen-oil ratio 600 conditions, its dealkalize nitrogen activity is typical industry catalyzer Mo-Nl/Al
2O
3-SlO
21.7 times, and used continuously 1000 hours, reactive behavior does not reduce.
Compared with prior art, catalyzer of the present invention has the active and satisfactory stability of high dealkalize nitrogen, adopts the new method that adds boron and reactive metal component, has avoided the influence of steeping process to the carrier physical strength, and method is simple, has also saved the surplus liquid treating processes of conventional dipping.
Example 1
(1) tungstenic, the preparation of the nickel aqueous solution
Take by weighing 549 gram ammonium metawolframates and 469 gram nickelous nitrates, add 780 milliliters in water, stirring and dissolving, last strength of solution is per 100 milliliters and contains WO
345 grams, the NlO12 gram.
(2) contain the preparation of molybdenum boron ammonia soln
Measure that to contain ammonia 9%(heavy) 810 milliliters of ammonia solns, add 235 gram Ammonium Heptamolybdates and 160 gram boric acid, mixture places 50 ℃ of water-baths heating after 4 hours, naturally cooling.Final solution concentration, per 100 milliliters contain MoO
319 grams, B
2O
39 grams.
(3) as follows with the silica-alumina bead physico-chemical property that becomes the preparation of glue method continuously:
Dioxide-containing silica %(is heavy) 7.5
Granularity millimeter φ 1.5-2.5
Specific surface rice
2/ gram 256
Pore volume milliliter/gram 0.58
Physical strength kilogram/grain 8.5
Total acid (chromatography) millimole/gram
360℃ 0.126
400℃ 0.089
Acid distribution Ho＜-8.2 0.45
-8.2--5.6 0.05
-5.6--3.0 0.05
-3.0-3.3 0.10
Get above-mentioned carrier 1000 grams and place rotary drum, get above-mentioned (1) made solution and 700 milliliters carrier is sprayed.Control sprays speed, makes carrier absorbent solution and do not influence physical strength equably.Sprayed the back and taken out the nature airing, then 400 ℃ of following roastings 3 hours.
(4) get (3) gained catalyzer work in-process 1000 and restrain, place rotary drum, spray for 500 milliliters with (2) made solution, control sprays speed, has sprayed the back taking-up and has dried 3 hours down at 120 ℃, then 480 ℃ of following roastings 3 hours.Analyze the gained catalyzer, contain WO
3The 19.8%(weight), MoO
3The 7.8%(weight), B Nl5.0%(weight),
2O
33.5%(is heavy), 0.30 milliliter/gram of pore volume, 150 meters of specific surfaces
2/ gram.
Comparative example 1
(1) contains the preparation of molybdenum, nickel ammonia soln
It is heavy to measure 11%() 820 milliliters of ammoniacal liquor, add Ammonium Heptamolybdate 284 grams, stir and make it dissolving, add nickelous nitrate 389 grams again, stirring and dissolving, the strength of solution of making, per 100 ml solns contain MoO
323 grams contain the NlO10 gram.
(2) preparation of boracic ammonia soln
Measure that to contain ammonia 8%(heavy) 920 milliliters of ammoniacal liquor, add boric acid 213 grams, place solution 60 ℃ of water-baths heating after 4 hours, naturally cooling.Last strength of solution is that per 100 milliliters contain B
2O
312 grams.
(3) get carrier 1000 grams in the example 1, place rotary drum, spray for 700 milliliters, descended dry 3 hours at 120 ℃ then, 540 ℃ of following roastings 4 hours with (1) made solution.
(4) weighing (3) gained catalyzer work in-process 1000 grams place rotary drum, spray for 500 milliliters with (2) made solution, descend dry 3 hours at 120 ℃ then, 540 ℃ of following roastings 3 hours.The gained catalyzer contains MoO
312.5%(is heavy), NlO5.0%(is heavy), B
2O
34.8%(is heavy).
Comparative example 2
In comparative example 1, economize step (2) and (4), i.e. the cost example.This is typical industrial Hydrobon catalyst.
Comparative example 3
In example 1, step (2) does not add boric acid, i.e. the cost example.
Example 2
Contain the preparation of molybdenum, B solution:
Measure that to contain ammonia 11%(heavy) 780 milliliters of ammonia solns, add 309 gram Ammonium Heptamolybdates and 249 gram boric acid, mixture is placed 80 ℃ of heating after 3 hours down, naturally cooling, its concentration is that per 100 milliliters contain MoO
325 grams, B
2O
314 grams.
All the other are identical with example 1.The catalyzer that makes contains WO
3The 18.8%(weight), MoO
3The 8.8%(weight), B NlO4.4%(weight),
2O
34.9%(is heavy), 132 meters of 0.28 milliliter/gram of pore volume, specific surfaces
2/ gram.
Example 3
The preparation of tungstenic, the nickel aqueous solution
Take by weighing 416 gram ammonium metawolframates and 313 gram nickelous nitrates, add 850 milliliters in water, stirring and dissolving, the strength of solution that makes are per 100 milliliters and contain WO
334 grams and NlO8 gram.
All the other are identical with example 2.Catalyzer contains WO
3The 15.0%(weight), MoO
3The 10.5%(weight), B NlO3.5%(weight),
2O
3The 5.2%(weight), 0.29 milliliter/gram of pore volume, specific surface are 148 meters
2/ gram.
Example 4
(1) preparation of tungsten, nickel solution
Take by weighing 488 gram ammonium metawolframates and 391 gram nickelous nitrates, add 820 milliliters in water, stirring and dissolving, the concentration that makes solution are that per 100 milliliters contain WO
340 grams, the NlO10 gram.
(2) preparation of molybdenum, B solution
Measure that to contain ammonia 9%(heavy) 800 milliliters of ammonia solns, add 284 gram Ammonium Heptamolybdates and 160 gram boric acid, mixture places 65 ℃ of water-baths heating after 2 hours, naturally cooling, last strength of solution is per 100 milliliters and contains MoO
323 grams, B
2O
39 grams.
All the other are identical with example 1.Catalyzer contains WO
3The 18.2%(weight), MoO
3The 9.4%(weight), B NlO4.4%(weight),
2O
33.1%(is heavy), 0.28 milliliter/gram of pore volume, than table 140 meter
2/ gram.
With the grand celebration coker gas oil is raw material, carries out hydrofining with each routine institute controlling catalyst.
Table 3 grand celebration coker gas oil character
Boiling range ℃ proportion d
20 40.8249
Initial boiling point 203 full nitrogen PPM 1149
10% 231 alkali nitrogen PPM 615
30% 258 sulphur PPM 961
50% 281 acidity mgKOH/100ml 2.2
70% 305
90% 331
95% 342
Do 350
Each routine catalyzer dealkalize nitrogen activity of table 4
During catalyst component reaction hydrogen pressure MPa volume space velocity
-3Dealkalize nitrogen rate %
Example 1 W-Mo-Nl-B 5.88 2.0 94
2.94 1.0 82
Example 2 W-Mo-Nl-B 5.88 2.0 95
2.94 1.0 83
Example 3 W-Mo-Nl-B 5.88 2.0 91
2.94 1.0 78
Example 4 W-Mo-Nl-B 5.88 2.0 95
2.94 1.0 83
Comparative example 1 Mo-Nl-B 5.88 2.0 80
2.94 1.0 56
Comparative example 2 Mo-Nl2.94 5.88 2.0 72
2.94 1.0 48
Comparative example 3 W-Mo-Nl 5.88 2.0 90
2.94 1.0 75
Hydrogen-oil ratio is 600,360 ℃ of temperature of reaction, and evaluating apparatus is the 100ml fixed bed.
Claims (4)
1, a kind of fraction oil Hydrobon catalyst is an active constituent with VIII family and VI B family metal, adds boron additive, is carrier with silicon oxide one aluminum oxide, it is characterized in that containing three kinds of active constituents of W-Mo-NI, (the SiO of carrier
2)/(SiO
2+ Al
2O
2) * 100%=5-10%, the pore volume 0.22-0.35 milliliter/gram of catalyzer, specific surface 120-160 rice
2/ gram contains in catalyst weight: WO
3L3-25%, MoO
36-14%, NiO
2-6%, B
2O
32-7%, preferably WO
3L7-19%, MoO
38-10%, NlO3-5%, B
2O
33-5%.
2, a kind of preparation method of fraction oil Hydrobon catalyst, it is characterized in that making respectively the W-Ni aqueous solution and Mo-B ammonia soln, and respectively in type carrier is carried out solution and spray, active constituent and auxiliary agent are added on the carrier, all through super-dry and roasting make catalyzer after spraying at every turn.
3, according to the method for claim 2, it is characterized in that also can adopting and spray for three times or four times, wherein boron-containing solution is that process adds thermally-stabilised boric acid ammonia soln, and the solution that contains W, Mo, Nl is water or ammonia soln, all needs drying and roasting after every kind of solution sprays.
4, according to the method for claim 3, it is characterized in that the W-Nl aqueous solution is the aqueous solution of ammonium metawolframate and nickelous nitrate, concentration is: WO
332-48 gram/(100 ml soln), NlO7-14 gram/(100 ml soln), the Mo-B ammonia soln is that Ammonium Heptamolybdate and boric acid are added 6-15%(is heavy) ammoniacal liquor in, 40-90 ℃ of heating 2-10 hour down, the stabilizing solution of making, its concentration is MoO
317-27 gram/(100 ml soln), B
2O
38-16% gram/(100 ml soln).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109140 CN1019502B (en) | 1989-12-11 | 1989-12-11 | Hydrofined catalyst and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89109140 CN1019502B (en) | 1989-12-11 | 1989-12-11 | Hydrofined catalyst and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1052501A CN1052501A (en) | 1991-06-26 |
| CN1019502B true CN1019502B (en) | 1992-12-16 |
Family
ID=4857884
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89109140 Expired CN1019502B (en) | 1989-12-11 | 1989-12-11 | Hydrofined catalyst and preparing process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019502B (en) |
Cited By (1)
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-
1989
- 1989-12-11 CN CN 89109140 patent/CN1019502B/en not_active Expired
Cited By (1)
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|---|---|---|---|---|
| CN1062583C (en) * | 1996-09-12 | 2001-02-28 | 抚顺石油化工公司石油三厂 | Preparation of ethylene cracking material |
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| Publication number | Publication date |
|---|---|
| CN1052501A (en) | 1991-06-26 |
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