CN1175481A - Co-impregnation liquid for preparing hydrocracking catalyst - Google Patents
Co-impregnation liquid for preparing hydrocracking catalyst Download PDFInfo
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- CN1175481A CN1175481A CN 96109702 CN96109702A CN1175481A CN 1175481 A CN1175481 A CN 1175481A CN 96109702 CN96109702 CN 96109702 CN 96109702 A CN96109702 A CN 96109702A CN 1175481 A CN1175481 A CN 1175481A
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Abstract
A co-impregnating liquid for preparing high-activity hydrocracking catalyst contains W, Ni and impregnating assistant (organic acid or ammonium slat). If it is used t oimpregnate the carrier containing Y-type molecular sieve and refractory inorganic oxide, obtained catalyst has high specific surface area increased by 10-25%, high catalytic activity increased obviously and low reaction temp decreased by 3-6 deg. C.
Description
The present invention relates to a kind of co-impregnated solution for preparing high-activity hydrocracking catalyst.
Along with the crude oil heaviness with to the increase of light-end products demand, and the appearance of recently new environmental regulation, become increasingly conspicuous as the importance of the hydrocracking technology of one of heavy oil lighting important means.The key of hydrocracking technology is a hydrocracking catalyst, only improves constantly the performance of hydrocracking catalyst, and the hydrocracking level is improved.
Hydrocracking catalyst is a dual-function catalyst, promptly has hydrogenation activity and cracking activity simultaneously, and both complement each other, and has only the hydrogenation and the cracking activity that improve catalyzer simultaneously, just can make catalyzer still have selectivity preferably when having greater activity.The hydrogenation activity of hydrocracking catalyst derives from hydrogenation metal, adopts the catalyst prepared hydrogenation activity higher usually.The hydrogenation activity of catalyzer and the composition of steeping fluid and compound method are closely related.
CN86107828 has introduced the steeping fluid that a kind of Mo-Ni-W-P forms, and its main purpose is to introduce W in Mo-Ni-P solution, and improving with the aluminum oxide is the denitrification activity of the Hydrobon catalyst of carrier.Prepare the temperature higher (90～120 ℃) that this co-impregnated solution needs.
The objective of the invention is to find suitable leaching agent with the preparation steeping fluid, improve the hydrogenation metal component and on catalyzer, disperse, improve the effective ratio area of catalyzer, improve its hydrogenation activity, make the catalyzer that makes that higher activity and selectivity be arranged.
Consisting of of co-impregnated solution of the present invention: 25～65gWO
3/ 100ml solution, 3～20gNiO/100ml solution, 0.5～15g leaching agent/100ml solution.The selected leaching agent of the present invention is organic acid or ammonium salt, and they can be acetate, propanedioic acid, citric acid or its ammonium salt and ammonium nitrate, preferably propanedioic acid, ammonium citrate or ammonium nitrate.The preparation condition of co-impregnated solution of the present invention relaxes especially, only needs under the room temperature solubility W salt, Ni salt and leaching agent is common or join in the WATER AS FLOW MEDIUM with any order and to get final product, and joins to such an extent that co-impregnated solution is a clear and stable.
The present invention compared with prior art, because the raising of hydrogenation metal component dispersity on catalyzer, when hydrogenation activity improves, the specific surface area of catalyzer is also obviously improved, thereby more cracking activity center is provided, has so just made prepared catalyzer when having greater activity, also have selectivity preferably.Table 1 has been listed the result of flooding the identical carrier prepared catalyst with steeping fluid of the present invention and traditional W-Ni steeping fluid under the same conditions.
Table 1.
| The catalyzer numbering | CA A B C D (comparative example 1) |
| Steeping fluid is formed catalyst property WO 3, the dispersity of the dispersity nickel of w% NiO.w% tungsten | W-Ni W-Ni-W-Ni-W-Ni-W-Ni-acetoxymalonic acid ammonium citrate ammonium nitrate 19.70 19.71 20.05 19.15 19.65 4.59 4.40 4.51 4.13 4.23 100 118 120 108 120 100 120 135 173 150 |
Carrier with co-impregnated solution dipping of the present invention is made up of Y zeolite and refractory inorganic oxides.The content of Y zeolite is 20～85w% in the carrier, the content of refractory inorganic oxides is 15～80w%, wherein refractory inorganic oxides can be little porous aluminum oxide, macroporous aluminium oxide, amorphous aluminum silicide or their mixture, the content of little porous aluminum oxide is 15～25w%, the content of macroporous aluminium oxide is 10～50w%, and the content of amorphous aluminum silicide is 15～50w%.The characteristics of flooding this carrier are: leaching agent does not remain on the hydrocracking catalyst; The specific surface area of gained hydrocracking catalyst obviously improves, and has higher activity, compares with direct W-Ni dipping, and temperature of reaction can reduce by 3～6 ℃, and selectivity also increases.
Further describe the embodiment of the invention 1 below by specific examples
Under the room temperature, with 1130 gram ammonium metawolframate (WO
3Content is more than 85%) and 800 gram nickelous nitrate (Ni (NO
3)
26H
2O＞99%) is dissolved in the 1700ml deionized water 10～20 minutes, makes W-Ni solution-1.
Under the room temperature, with 820 gram ammonium metawolframate (WO
3Content is more than 85%) and 1200 gram nickelous nitrate (Ni (NO
3)
26H
2O＞99%) is dissolved in the 1550ml deionized water 10～20 minutes, makes W-Ni solution-2.
Under the room temperature, with 1420 gram ammonium metawolframate (WO
3Content is more than 85%) and 400 gram nickelous nitrate (Ni (NO
3)
26H
2O＞99%) is dissolved in the 1850ml deionized water 10～20 minutes, makes W-Ni solution-3.Embodiment 2
18 gram acetate are joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-1.
12 gram propanedioic acid are joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-2.
6 gram ammonium citrates are joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-3.
6 gram ammonium nitrate are joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-4.
3 gram ammonium citrates are joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-5.
0.75 gram ammonium citrate is joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-6.
3 gram ammonium citrates are joined in the 150ml example 1 described W-Ni solution-1, dissolved 5 minutes, obtain co-impregnated solution-7.
18 gram propanedioic acid are joined in the 150ml example 1 described W-Ni solution-2, dissolved 5 minutes, obtain co-impregnated solution-8.
3 gram ammonium nitrate are joined in the 150ml example 1 described W-Ni solution-3, dissolved 5 minutes, obtain co-impregnated solution-9.Embodiment 3
325.6 grams are pressed CN90102645.X method synthetic high-Si Y-type molecular sieve (lattice constant 2.452nm, relative crystallinity 100, sial molecular ratio 9.87), by 79.9 gram pseudo-boehmite (pore volume 0.5ml/g, specific surface area 210m
2/ the tackiness agent (method for making of adhesive therefor is identical therewith in following each example) that g) makes with 113ml0.2M nitric acid peptization, together place rolling machine, roll, extrusion, drying, then with dried strip 0.1MPa, 550 ℃ of following hydrothermal treatment consists 1 hour, make carrier-1.
With above-mentioned high-Si Y-type molecular sieve 108.5 grams, amorphous aluminum silicide 45.3 gram (pore volume 0.64ml/g, specific surface area 310m
2/ g), macroporous aluminium oxide 65.4 gram (pore volume 0.9ml/g, specific surface area 350m
2/ g), tackiness agent 133.3 gram together places rolling machine, makes carrier-2 by the method for example 1.
With above-mentioned high-Si Y-type molecular sieve 108.5 grams, amorphous aluminum silicide 113.2 gram (pore volume 0.64ml/g, specific surface area 310m
2/ g), tackiness agent 133.3 gram together places rolling machine, makes carrier-3 by the method for example 1.
With example 1 described Y zeolite 108.5 grams, macroporous aluminium oxide 109.0 gram (pore volume 0.9ml/g, specific surface area 350m
2/ g), tackiness agent 133.3 gram together places rolling machine, makes carrier-4 by the method for example 1.Embodiment 4
With 70 gram carrier-1 usefulness co-impregnated solution-1 dippings.Immersion condition is: room temperature, liquid-solid ratio 2: 1,2 hours.Separate then, dry, 500 ℃ of roastings 4 hours, make catalyst A.Embodiment 5
With 70 gram carrier-1 usefulness co-impregnated solution-2 dippings, prepare catalyst B by example 4 conditions.Embodiment 6
With 70 gram carrier-1 usefulness co-impregnated solution-3 dippings, prepare catalyzer C by example 4 conditions.Embodiment 7
With 70 gram carrier-1 usefulness co-impregnated solution-4 dippings, prepare catalyzer D by example 4 conditions.Embodiment 8
With 70 gram carrier-1 usefulness co-impregnated solution-5 dippings, prepare catalyzer E by example 4 conditions.Embodiment 9
With 70 gram carrier-1 usefulness co-impregnated solution-6 dippings, prepare catalyzer F by example 4 conditions.Comparative example 1
With W-Ni solution-1 direct impregnation of 70 gram carrier-1 use-cases 1, prepare catalyzer CA by example 4 conditions.Embodiment 10
With 70 gram carrier-2 usefulness co-impregnated solution-7 dippings, prepare catalyzer G by example 4 conditions.Comparative example 2
With W-Ni solution-1 direct impregnation in 70 gram carrier-2 use-cases 1, prepare catalyzer CB by example 4 conditions.Embodiment 11
With 70 gram carrier-3 usefulness co-impregnated solution-8 dippings, prepare catalyzer H by example 4 conditions.Comparative example 3
With W-Ni solution-2 direct impregnation in 70 gram carrier-3 use-cases 1, prepare catalyzer CC by example 4 conditions.Embodiment 12
With 70 gram carrier-4 usefulness co-impregnated solution-9 dippings, prepare catalyst I by example 4 conditions.Comparative example 4
With W-Ni solution-3 direct impregnation in 70 gram carrier-4 use-cases 1, prepare catalyzer CD by example 4 conditions.
The character of comparative example 1～4 and embodiment 4～12 prepared catalyst is listed in table 2.
Table 2.
| The catalyzer numbering | CA comparative example 1 | A | B | C | D | E | F |
| WO 3，w％ | 19.70 | 19.71 | 20.05 | 19.15 | 19.60 | 20.63 | 19.35 |
| NiO，w％ | 4.59 | 4.40 | 4.51 | 4.13 | 4.30 | 4.61 | 4.23 |
| Pore volume, ml/g | 0.194 | 0.242 | 0.245 | 0.248 | 0.246 | 0.241 | 0.224 |
| Specific surface area, m 2/g | 350 | 399 | 420 | 431 | 428 | 414 | 385 |
Continuous table 2.
| The catalyzer numbering | CB comparative example 2 | G | CC comparative example 3 | H | CD comparative example 4 | I |
| WO 3，w％ | 22.9 9 | 22.3 5 | 17.1 7 | 17.0 1 | 30.2 5 | 29.8 9 |
| NiO，w％ | 5.37 | 5.16 | 7.36 | 7.28 | 2.52 | 2.49 |
| Pore volume, ml/g | 0.26 7 | 0.29 4 | 0.27 9 | 0.31 8 | 0.25 5 | 0.30 2 |
| Specific surface area, m 2/g | 257 | 283 | 270 | ?310 | 245 | 289 |
As can be seen from Table 2, the specific surface area with the co-impregnated solution dipping preparation catalyzer that contains leaching agent obviously improves.Embodiment 13
On packaged unit, adopt the one-pass technical process of one-stage serial, be raw material with the vacuum distillate, catalyzer CA (comparative example 1), C and D are carried out activity rating.Stock oil character sees Table 3.Processing condition are: hydrogen dividing potential drop 14.7MPa, and hydrogen to oil volume ratio 1500: 1, refining section and cracking zone air speed are respectively 1.0h
-1And 1.67h
-1Evaluation result sees Table 4.
Table 3.
| Density (20 ℃) g/cm 3Sulphur, w% nitrogen, the w% boiling range, ℃ initial boiling point 10V%/30V% 50V%/70V% 90V%/do | ????0.9078 ????0.56 ????0.16 ????340 ????392/413 ????431/446 ????476/511 |
Table 4.
| The catalyzer numbering | CA (comparative example 1) | C | D |
| The treated oil nitrogen content, μ g/g | 2 | 3 | 6 |
| Catalyst activity *, ℃ | Benchmark | Benchmark-5 | Benchmark-4 |
| Selectivity * *, % | 89 | 91 | 91 |
Temperature of reaction is represented when * being 60v% with engler's fractionation＜185 a ℃ cut yield
* selectivity (%)=(60～177 ℃ of cut yield/＜177 ℃ cut yields) * 100
By table 4 as seen, obviously improve with co-impregnated solution dipping preparation activity of such catalysts of the present invention, temperature of reaction can reduce by 4～5 ℃, and selectivity is also better.
Claims (3)
1. co-impregnated solution that is used to prepare hydrocracking catalyst, it consists of: 25～65gWO
3/ 100ml solution, 3～20gNiO/100ml solution is characterized in that also containing at least a kind of organic acid or ammonium salt, and content is 0.5～15g/100ml solution.
2. by the described co-impregnated solution of claim 1, it is characterized in that said organic acid is acetate, propanedioic acid.
3. by the described co-impregnated solution of claim 1, it is characterized in that said ammonium salt is ammonium acetate, propanedioic acid ammonium, ammonium citrate and ammonium nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109702A CN1063104C (en) | 1996-09-04 | 1996-09-04 | Co-impregnation liquid for preparing hydrocracking catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109702A CN1063104C (en) | 1996-09-04 | 1996-09-04 | Co-impregnation liquid for preparing hydrocracking catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN1175481A true CN1175481A (en) | 1998-03-11 |
| CN1063104C CN1063104C (en) | 2001-03-14 |
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ID=5120534
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109702A Expired - Lifetime CN1063104C (en) | 1996-09-04 | 1996-09-04 | Co-impregnation liquid for preparing hydrocracking catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006116913A1 (en) * | 2005-04-29 | 2006-11-09 | China Petroleum & Chemical Corporation | A catalyst for hydrocracking process, the preparing method and the use thereof |
| CN101462078B (en) * | 2007-12-18 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
| US8883669B2 (en) | 2005-04-29 | 2014-11-11 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, a process for producing the same, and the use of the same |
| CN105080554A (en) * | 2014-05-09 | 2015-11-25 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst, preparation method therefor and applications thereof |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1006202B (en) * | 1984-05-18 | 1989-12-27 | 国际壳牌研究有限公司 | Process for preparing supported hydroconversion catalysts and catalysts thus prepared |
| CN1004192B (en) * | 1986-11-07 | 1989-05-17 | 中国石油化工总公司长岭炼油厂 | Co-impregnating liquor used for preparing highly active hydrogenant catalys |
| 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 |
-
1996
- 1996-09-04 CN CN96109702A patent/CN1063104C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006116913A1 (en) * | 2005-04-29 | 2006-11-09 | China Petroleum & Chemical Corporation | A catalyst for hydrocracking process, the preparing method and the use thereof |
| US8883669B2 (en) | 2005-04-29 | 2014-11-11 | China Petroleum & Chemical Corporation | Hydrocracking catalyst, a process for producing the same, and the use of the same |
| CN101462078B (en) * | 2007-12-18 | 2011-08-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst steeping fluid composition and preparation method of hydrogenation catalyst |
| CN105080554A (en) * | 2014-05-09 | 2015-11-25 | 中国石油化工股份有限公司 | Sulfurized hydrogenation catalyst, preparation method therefor and applications thereof |
| CN105080554B (en) * | 2014-05-09 | 2017-11-03 | 中国石油化工股份有限公司 | A kind of sulphided state hydrogenation catalyst and its preparation method and application |
| CN105817259A (en) * | 2016-04-15 | 2016-08-03 | 中国海洋石油总公司 | Productive naphtha type hydrocracking catalyst and preparation method thereof |
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|---|---|
| CN1063104C (en) | 2001-03-14 |
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