CN1339562A - Hydrogenating denitrification catalyst and its preparing method - Google Patents
Hydrogenating denitrification catalyst and its preparing method Download PDFInfo
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- CN1339562A CN1339562A CN 00122919 CN00122919A CN1339562A CN 1339562 A CN1339562 A CN 1339562A CN 00122919 CN00122919 CN 00122919 CN 00122919 A CN00122919 A CN 00122919A CN 1339562 A CN1339562 A CN 1339562A
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Abstract
The hydrogenating and denitrification catalyst has aluminium oxide or silicon-containing aluminium oxide as carrier, Mo and Ni as active components and B as assistant. By compounding stable alkali Mo-Ni-B solution and adopting co-soaking technology, the catalyst has raised hydrogenating and denitrification activity.
Description
The present invention relates to a kind of hydrodenitrogenation catalyst and preparation method thereof.
Typical Hydrobon catalyst is a carrier with aluminum oxide or siliceous aluminum oxide often, is active ingredient with VIII family and group vib metallic element.In order to improve activity of such catalysts and stability, often adopt multiple improved method, as to support modification, optimize the preparation method, add auxiliary agent etc.Auxiliary agent commonly used has P, F, B, Ti, Zr etc., and for hydrodenitrification, interpolation boron additive effect is remarkable.But there are the following problems to add boron with pickling process: boron compound commonly used is a boric acid, and the meltage of boric acid aqueous solution mesoboric acid is very little under the room temperature, at room temperature sprays preparation during catalyzer, on the catalyzer boron oxide level general＜2w%, do not have the effect that improves catalyst activity, B on the general catalyzer
2O
3Content is 3～6w%.
Japanese Patent 54-096489 adopts following method to address this problem: spray the ammonium aluminate ammonia soln earlier, drying and roasting, soak nickel aqueous solution after drying and roasting again, soak catalyzer, by heating the moisture evaporation in the solution is fallen again with excessive boric acid aqueous solution.
Chinese patent CN1019502B has made stable Mo-B solution, than simpler the executing of preparation method of Japanese Patent 54-096489 announcement.Method is: spray the W-Ni aqueous solution earlier, spray the Mo-B ammonia soln after the drying roasting again.Because joining, B can improve active ingredient uniformly dispersed on carrier in the carrier, B and metal component add simultaneously can produce mutual synergy, and this patent is when spraying the W-Ni aqueous solution, do not add the B auxiliary agent, thereby the nonactive species mutually of W and Ni can appear in work in-process when roasting, thereby the activity of W and Ni is not fully exerted, has limited the further raising of catalyst activity.
The object of the invention provides a kind of distillate hydrogenation denitrification catalyst and preparation method thereof, further improves the hydrodenitrogenationactivity activity of catalyzer.
The composition and the physico-chemical property of catalyzer of the present invention are as follows:
With aluminum oxide or siliceous aluminum oxide is carrier, is active ingredient with Mo, Ni, and for helping catalyst component, by catalyst weight, each component concentration is respectively MoO with B
320～30%, NiO2～7%, B
2O
32～7%; MoO preferably
322～25%, NiO3.0～5%, B
2O
33～5%; Described active ingredient and to help catalyst component be that mode by graded impregnation supports on the support of the catalyst, promptly with the co-impregnated solution that contains Mo-Ni-B at twice or twice above dip loading active ingredient with help catalyst component.
0.25～0.40 milliliter/gram of catalyzer pore volume, 120～200 meters of specific surface areas
2/ gram.
Preparation of catalysts method of the present invention is as follows:
Catalyzer of the present invention is a carrier with aluminum oxide or siliceous aluminum oxide, with Mo, Ni is active ingredient, add boron additive, at first make stable Mo-Ni-B and/or Mo-Ni steeping fluid, be dipped into above-mentioned steeping fluid gradation on the carrier altogether then, each dipping is after 90～150 ℃ of dryings 2～6 hours, and 450～550 ℃ of roastings made described catalyzer in 2～5 hours, had at least once during described gradation is soaked altogether and with the Mo-Ni-B co-impregnated solution described carrier were soaked altogether.
It both can be with the Mo-Ni steeping fluid described carrier to be flooded earlier that described gradation is soaked altogether, and then described carrier is soaked altogether with the Mo-Ni-B co-impregnated solution, also with the Mo-Ni-B co-impregnated solution described carrier is soaked altogether earlier, and then with the Mo-Ni steeping fluid described carrier is flooded, preferably soak altogether all at every turn and described carrier is soaked altogether with the Mo-Ni-B co-impregnated solution.
Described gradation is soaked number of times altogether and is at least 2 times, also can be to adopt 2-4 time, and preferably the catalyst-loaded active ingredient of the mode of 2 saturated dippings and help catalyst component all needs drying and roasting after flooding at every turn.
The preparation of described aluminum oxide or siliceous alumina supporter can be that aluminum oxide is added peptizing agent and extrusion aid or silicon sol, mixes to be extruded into bar shaped or to drip globulate after pinching, and through 90～150 ℃ of dryings 2～8 hours, 500～750 ℃ of roastings made in 2～5 hours.
Described aluminum oxide can be the macropore aluminium hydrate powder that adopts aluminum chloride-ammoniacal liquor method, Tai-Ace S 150-sodium metaaluminate method, carborization and alkyl aluminum hydrolysis method to make.
The compound method of Mo-Ni-B co-impregnated solution is as follows: molybdenum compound, nickel compound and boron compound are joined in the ammoniacal liquor stir, be heated to 50～70 ℃ then, and kept 0.5～3 hour, make stable co-impregnated solution.
The preparation of described Mo-Ni steeping fluid can be carried out as follows: molybdenum compound and nickel compound are joined be stirred to whole dissolvings in the ammoniacal liquor, obtain stable Mo-Ni steeping fluid.
Above-mentioned molybdenum compound is that ammonium molybdate, nickel compound are that nickelous nitrate, boron compound are boric acid.
Each component concentrations is in the described Mo-Ni-B co-impregnated solution:
MoO
3:/100 milliliters of 13～30 grams, NiO:2～7 restrain/100 milliliters, B
2O
3:/100 milliliters of 2～7 grams.
Each component concentrations is in the described Mo-Ni steeping fluid: MoO
3:/100 milliliters of 13～30 grams, NiO:2～7 restrain/100 milliliters.
Described extrusion aid can be: one or more in sesbania powder, citric acid, the acetic acid.
Above-mentioned peptizing agent is: one or more in nitric acid, hydrochloric acid and the deionized water.
Compared with prior art, catalyzer of the present invention not only overcomes the shortcoming that the prior art graded impregnation brings, and the catalyzer that adopts the inventive method to prepare, when handling Saudi Arabia's coker gas oil, its hydrodenitrogenationactivity activity is higher by about 30% than commercial catalyst general on the market.This catalyzer has very high hydrofining activity to distillate, is specially adapted to 80～370 ℃ straight run oil, the hydrodenitrification and the hydrogenating desulfurization of secondary processing oil.
Following example is further illustrated feature of the present invention.
Embodiment 1
(pore volume is 0.86 a milliliter/gram to the carborization aluminium hydrate powder, and specific surface area is 290 meters
2/ g) 2200 grams add 65w% nitric acid 88 grams, 1320 milliliters of deionized waters and extrusion aid sesbania powder 55 grams through mix pinch even after, be extruded into bar shaped, made carrier ZT-1 in 3 hours through the roasting in 4 hours 550 of 150 ℃ of dryings.0.62 milliliter/gram of this carrier pore volume, 260 meters of specific surface areas
2/ gram.
Embodiment 2
(pore volume is 0.87 a milliliter/gram to Tai-Ace S 150 method aluminium hydrate powder, and specific surface area is 320 meters
2/ g) 500 grams add 65w% nitric acid 20 grams, 300 milliliters of deionized waters, silicon sol 60 grams and extrusion aid sesbania powder 13 grams, citric acid 15 grams through mix pinch even after, be extruded into bar shaped, made carrier ZT-1 in 3 hours through the roasting in 4 hours 550 of 150 ℃ of dryings.0.64 milliliter/gram of this carrier pore volume, 300 meters of specific surface areas
2/ gram.
Comparative example 1
92 gram ammonium metawolframates, 65 gram nickelous nitrates and 142 ml deionized water are mixed to and all are dissolved as the transparent W-Ni aqueous solution, 200 gram carrier ZT-1 with this W-Ni aqueous solution after flooding under the room temperature, made work in-process CB-1A in 3 hours through the roasting in 4 hours 450 of 120 ℃ of dryings, stay with standby.Ammonium molybdate 43 grams, the ammoniacal liquor of boric acid 29 grams and proportion 0.960 mixes stirring for 175 milliliters, be warming up to 55 ℃ of dissolvings 2.5 hours then, obtain the Mo-B ammonia soln, above-mentioned work in-process CB-1A with this Mo-B ammonia soln under the room temperature dipping after, obtained reference catalyst in 2 hours through the roasting in 5 hours 550 of 80 ℃ of dryings, the reference agent is numbered CB-1B.
Comparative example 2
Ammonium molybdate 102 grams, the ammoniacal liquor of nickelous nitrate 60 grams and proportion 0.940 mixes to dissolving for 340 milliliters, obtains stable Mo-Ni ammoniacal liquor co-impregnated solution.200 gram carrier ZT-1 with this co-impregnated solution after flooding under the room temperature, flood under room temperature with above-mentioned Mo-Ni ammoniacal liquor co-impregnated solution again after 2 hours through the 500 ℃ of roastings in 4 hours of 110 ℃ of dryings, through 120 ℃ of dryings 3 hours, 520 ℃ of roastings made final catalyzer in 2 hours again, and this catalyzer is numbered CB-2B.
Embodiment 3
Ammonium molybdate 54 grams, the ammoniacal liquor of nickelous nitrate 31 grams and proportion 0.940 mixes stirring for 170 milliliters, in obtaining the Mo-Ni ammonia soln after the dissolving under the room temperature.200 gram carrier ZT-1 behind dipping under the room temperature, 2 hour obtain work in-process SC-1A through the roasting in 2 hours 500 of 150 ℃ of dryings with this Mo-Ni ammonia soln.Ammonium molybdate 54 grams, nickelous nitrate 31 grams, boric acid 27 restrain and the ammoniacal liquor of proportion 0.940 mixes stirring for 155 milliliters, are warming up to 65 ℃ of dissolvings 2 hours then, obtain the Mo-Ni-B ammonia soln again.Behind dipping under the room temperature, through 100 ℃ of dryings 5 hours, 500 ℃ of roastings obtained final catalyzer in 3 hours to above-mentioned work in-process SB-1A with this Mo-Ni-B ammonia soln, and this catalyzer is numbered SC-1B.
Embodiment 4
Ammonium molybdate 54 grams, nickelous nitrate 31 grams, the ammoniacal liquor of boric acid 27 grams and proportion 0.935 mixes stirring for 155 milliliters, be warming up to 70 ℃ of dissolvings 25 minutes, obtain the Mo-Ni-B ammonia soln, 200 gram carrier ZT-1 behind dipping under the room temperature, 3 hour obtain work in-process SC-2A through the 450 ℃ of roastings in 3 hours of 120 ℃ of dryings with this Mo-Ni-B ammonia soln.Ammonium molybdate 54 grams, the ammoniacal liquor of nickelous nitrate 31 grams and proportion 0.940 mixes stirring for 170 milliliters, dissolves under room temperature, obtains the Mo-Ni ammonia soln again.Above-mentioned work in-process SC-2A behind dipping under the room temperature, 4 hour obtains catalyzer finished product through the 450 ℃ of roastings in 5 hours of 95 ℃ of dryings with this Mo-Ni ammonia soln, and this catalyzer is numbered SC-2B.
Embodiment 5
Ammonium molybdate 100 grams, nickelous nitrate 61 grams, the ammoniacal liquor of boric acid 27 grams and proportion 0.940 mixes stirring for 320 milliliters, is warming up to 50 ℃ of dissolvings 3 hours then, obtains Mo-Ni-B ammoniacal liquor co-impregnated solution, 200 gram carrier ZT-1 with this co-impregnated solution after flooding under the room temperature, through 130 ℃ of dryings, 450 ℃ of roastings in 2 hours 3 hours, and then with Mo-Ni-B ammoniacal liquor co-impregnated solution behind dipping under the room temperature, through 140 ℃ of dryings 2 hours, 550 ℃ of roastings obtained final catalyzer in 2 hours, and this catalyzer is numbered SC-3B.
Embodiment 6
Ammonium molybdate 100 grams, nickelous nitrate 61 grams, the ammoniacal liquor of boric acid 27 grams and proportion 0.940 mixes stirring for 320 milliliters, is warming up to 50 ℃ of dissolvings 3 hours then, obtain Mo-Ni-B ammoniacal liquor co-impregnated solution, 200 gram carrier ZT-2 flood under room temperature with this co-impregnated solution, then through 100 ℃ of dryings 5 hours, and 450 ℃ of roastings 3 hours, and then under room temperature, flood with Mo-Ni-B ammoniacal liquor co-impregnated solution, through 100 ℃ of dryings 3 hours, 550 ℃ of roastings obtained final catalyzer in 3 hours then, and this catalyzer is numbered SC-4B.
Embodiment 7
Ammonium molybdate 108 grams, nickelous nitrate 61 grams, the ammoniacal liquor of boric acid 27 grams and proportion 0.940 mixes stirring for 530 milliliters, be warming up to 60 ℃ of dissolvings 2 hours then, obtain Mo-Ni-B ammoniacal liquor co-impregnated solution, 200 gram carrier ZT-1 with this co-impregnated solution after flooding under the room temperature, through 150 ℃ of dryings, 450 ℃ of roastings in 2 hours 3 hours, and then under room temperature, flood with above-mentioned Mo-Ni-B ammoniacal liquor co-impregnated solution, through 100 ℃ of dryings 5 hours, 450 ℃ of roastings 3 hours, again with above-mentioned Mo-Ni-B ammoniacal liquor co-impregnated solution behind dipping under the room temperature, obtained final catalyzer in 2 hours through 120 ℃ of dryings 3 hours and 500 ℃ of roastings, this catalyzer is numbered SC-5B.
Embodiment 8
Ammonium molybdate 89 grams, nickelous nitrate 43 grams, the ammoniacal liquor of boric acid 27 grams and proportion 0.940 mixes stirring for 340 milliliters, be warming up to 50 ℃ of dissolvings 3 hours then, obtain Mo-Ni-B ammoniacal liquor co-impregnated solution, 200 gram carrier ZT-1 with this co-impregnated solution after flooding under the room temperature, through 130 ℃ of dryings, 450 ℃ of roastings in 3 hours 3 hours, and then flood under room temperature with Mo-Ni-B ammoniacal liquor co-impregnated solution, obtaining final catalyzer in 2 hours through 120 ℃ of dryings 3 hours and 500 ℃ of roastings then, this catalyzer is numbered SC-6B.
Embodiment 9
Ammonium molybdate 144 grams, nickelous nitrate 110 grams, the ammoniacal liquor of boric acid 30 grams and proportion 0.940 mixes stirring for 320 milliliters, is warming up to 65 ℃ of dissolvings 1 hour then, obtains Mo-Ni-B ammoniacal liquor co-impregnated solution, 200 gram carrier ZT-1 flood under room temperature with this co-impregnated solution, through 120 ℃ of dryings, 450 ℃ of roastings in 4 hours 3 hours, and then under room temperature, flood, again through 110 ℃ of dryings 3 hours with Mo-Ni-B ammoniacal liquor co-impregnated solution, 510 ℃ of roastings obtained final catalyzer in 3 hours, and this catalyzer is numbered SC-7B.
Embodiment 10
With Saudi Arabia's coker gas oil is raw material, at hydrogen pressure 6.0Mpa, and hydrogen to oil volume ratio 300: 1, air speed 2.0h
-1, under the condition that temperature of reaction is 355 ℃, catalyzer of the present invention and comparative catalyst are carried out the activity rating contrast, stock oil character and evaluation result see Table 1 and table 2 respectively.
Table 1 Saudi Arabia coker gas oil character
Density (20 ℃), g/cm
30.8657
Boiling range, ℃
IBP/10％???????????????????184/244
30％/50％??????????????????267/288
70％/90％??????????????????310/335
95％/EBP???????????????????345/357
Sulphur content, w% 1.67
The alkali nitrogen content, ppm 450
Table 2 catalyst activity comparative evaluation result
| The catalyzer numbering | Form w% | Corresponding carrier | The hydrodenitrification relative reactivity | |||
| ?WO 3 | ?MoO 3 | ?NiO | ?B 2O 3 | |||
| ?CB-1B | ?18.8 | ?9.2 | ?4.2 | ?3.8 | ?ZT-1 | ?100 |
| ?CB-2B | ?24.2 | ?4.3 | ?- | ?ZT-1 | ?99 | |
| ?SC-1B | ?24.1 | ?4.2 | ?4.0 | ?ZT-1 | ?109 | |
| ?SC-2B | ?24.2 | ?4.2 | ?4.1 | ?ZT-1 | ?112 | |
| ?SC-3B | ?24.1 | ?4.1 | ?4.0 | ?ZT-1 | ?130 | |
| ?SC-4B | ?24.3 | ?4.2 | ?4.1 | ?ZT-2 | ?134 | |
| ?SC-5B ?SC-6B ?SC-7B | ?23.9 ?21.2 ?28.9 | ?3.8 ?3.1 ?6.5 | ?4.2 ?4.5 ?3.9 | ?ZT-I ?ZT-1 ?ZT-1 | ?136 ?112 ?117 | |
As can be seen from Table 2, adopt gradation to soak the catalyzer of the present invention of technology preparation altogether, than dipping Mo-Ni behind the first dipping Mo-Ni-B and the catalyzer that dipping Mo-Ni-B makes behind the dipping Mo-Ni earlier have higher hydrodenitrogenationactivity activity, and active high more than 30% than reference agent.
Claims (14)
1, a kind of hydrodenitrogenation catalyst is a carrier with aluminum oxide or siliceous aluminum oxide, is active ingredient with Mo, Ni, for helping catalyst component, it is characterized in that by catalyst weight that with B each component concentration is respectively MoO
320～30%, NiO2～7%, B
2O
32～7%.
2, according to the described hydrodenitrogenation catalyst of claim 1, it is characterized in that described MoO
3Be 22～25%, NiO is 3.0～5%, B
2O
3Be 3～5%.
3, according to the described hydrodenitrogenation catalyst of claim 1, it is characterized in that described active ingredient and helping catalyst component is to support on the support of the catalyst by the mode that gradation is soaked altogether.
4, according to the described hydrodenitrogenation catalyst of claim 1, it is characterized in that described catalyzer pore volume is 0.25～0.40 a milliliter/gram, specific surface area is 120～200 meters
2/ gram.
5, a kind of preparation method of hydrodenitrogenation catalyst, with aluminum oxide or siliceous aluminum oxide is carrier, with Mo, Ni is active ingredient, add boron additive, comprise dipping, drying, calcination steps, it is characterized in that at first making stable Mo-Ni-B and/or the co-impregnated solution of Mo-Ni, be dipped into above-mentioned co-impregnated solution gradation on the carrier altogether then, soak altogether after 90～150 ℃ of dryings 2～6 hours at every turn, 450～550 ℃ of roastings made described catalyzer in 2～5 hours, and having at least during described gradation is soaked altogether once is to soak described carrier altogether with Mo-Ni-B solution.
6,, it is characterized in that it is to soak altogether all with the Mo-Ni-B co-impregnated solution described carrier to be soaked altogether that described gradation is soaked altogether at every turn according to the preparation method of the described hydrodenitrogenation catalyst of claim 5.
7, according to the preparation method of the described hydrodenitrogenation catalyst of claim 5, the preparation that it is characterized in that described aluminum oxide or siliceous alumina supporter is that aluminium hydroxide is added peptizing agent and extrusion aid or silicon sol, be extruded into bar shaped after mixed the pinching or drip globulate, through 90～150 ℃ of dryings 2～8 hours, 500～750 ℃ of roastings made in 2～5 hours.
8, according to the preparation method of the described hydrodenitrogenation catalyst of claim 5, the compound method of co-impregnated solution that it is characterized in that described Mo-Ni-B is as follows: molybdenum compound, nickel compound and boron compound are joined in the ammoniacal liquor stir, be heated to 50～70 ℃ then, and kept 0.5～3 hour, make stable co-impregnated solution.
9, according to the preparation method of the described hydrodenitrogenation catalyst of claim 5, it is characterized in that the method that carrier is soaked in described co-impregnated solution gradation altogether is: at room temperature, adopt the catalyst-loaded active ingredient of the saturated mode that sprays and help catalyst component.
10,, it is characterized in that the number of times that carrier is soaked in described co-impregnated solution gradation altogether is 2 times according to the preparation method of the described hydrodenitrogenation catalyst of claim 5.
11,, it is characterized in that each component concentrations is in the described co-impregnated solution: MoO according to the preparation method of the described hydrodenitrogenation catalyst of claim 5
3:/100 milliliters of 13～30 grams, NiO:2～7 restrain/100 milliliters, B
2O
3:/100 milliliters of 2～8 grams.
12,, it is characterized in that described aluminium hydroxide is to be selected from aluminum chloride-ammoniacal liquor method, Tai-Ace S 150-sodium metaaluminate method, carborization or the prepared macropore aluminium hydrate powder of alkyl aluminum hydrolysis method according to the preparation method of the described hydrodenitrogenation catalyst of claim 7.
13, according to the preparation method of the described hydrodenitrogenation catalyst of claim 7, it is characterized in that described extrusion aid is: one or more in sesbania powder, citric acid, the acetic acid, described peptizing agent are one or more in nitric acid, hydrochloric acid and the deionized water.
14,, it is characterized in that described molybdenum compound is that ammonium molybdate, nickel compound are that nickelous nitrate, boron compound are boric acid according to the preparation method of the described hydrodenitrogenation catalyst of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00122919A CN1101453C (en) | 2000-08-22 | 2000-08-22 | Hydrogenating denitrification catalyst and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00122919A CN1101453C (en) | 2000-08-22 | 2000-08-22 | Hydrogenating denitrification catalyst and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1339562A true CN1339562A (en) | 2002-03-13 |
| CN1101453C CN1101453C (en) | 2003-02-12 |
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ID=4589411
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|---|---|---|---|
| CN00122919A Expired - Lifetime CN1101453C (en) | 2000-08-22 | 2000-08-22 | Hydrogenating denitrification catalyst and its preparing method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101332424B (en) * | 2007-06-28 | 2011-04-06 | 长春融成环保科技有限公司 | Denitrification catalyst and its preparing method |
| WO2018019203A1 (en) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | Boron-modified hydrofining catalyst having high loading amount and preparation method therefor |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4139492A (en) * | 1977-08-10 | 1979-02-13 | American Cyanamid Company | Hydrotreating catalysts |
| CN1019502B (en) * | 1989-12-11 | 1992-12-16 | 中国石油化工总公司抚顺石油化工研究院 | Hydrofined catalyst and preparing process thereof |
| CN1039592C (en) * | 1995-07-14 | 1998-08-26 | 中国石油化工总公司 | Process for producing hydrogenating catalyst |
| CN1045305C (en) * | 1995-12-20 | 1999-09-29 | 中国石油化工总公司石油化工科学研究院 | Saturation hydrogenating process for removing olefines from reforming produced oil |
-
2000
- 2000-08-22 CN CN00122919A patent/CN1101453C/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101332424B (en) * | 2007-06-28 | 2011-04-06 | 长春融成环保科技有限公司 | Denitrification catalyst and its preparing method |
| WO2018019203A1 (en) * | 2016-07-29 | 2018-02-01 | 武汉凯迪工程技术研究总院有限公司 | Boron-modified hydrofining catalyst having high loading amount and preparation method therefor |
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| Publication number | Publication date |
|---|---|
| CN1101453C (en) | 2003-02-12 |
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