CN1123309A - Hydrodemetalation catalyst and preparation method thereof - Google Patents
Hydrodemetalation catalyst and preparation method thereof Download PDFInfo
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- CN1123309A CN1123309A CN94118334A CN94118334A CN1123309A CN 1123309 A CN1123309 A CN 1123309A CN 94118334 A CN94118334 A CN 94118334A CN 94118334 A CN94118334 A CN 94118334A CN 1123309 A CN1123309 A CN 1123309A
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- catalyzer
- phosphorus
- potassium
- alkali metal
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Abstract
The hydrogenation demetalization catalyst whose pore volume is 0.45-0.80 ml/g, specific surface is 100-230m2/g contains 1-3w% of metallic elements of family VIB and/or 0.5-3w% of metallic elements of family VIII. Said catalyst edge contains 0.01-0.8w% of alkali metal element passivant, at the same time also contains a certain quantity of phosphorus or silicon element. Because of the presence of phosphorus or silicon the alkali metal passivant is not easily lost, and has the stabilization function. ADVANTAGE-. the method is simple and easy to implement.
Description
The present invention relates to a kind of Hydrodemetalation catalyst and preparation method thereof, particularly a kind of Hydrodemetalation catalyst that contains the grain edges passivation layer and preparation method thereof.
Along with the change day by day of crude oil is heavy, metallic impurity in the heavy distillate are also increasing, as Fe, Ca, Ni, V etc., they mainly exist with the form of organic compound, under hydroconversion condition, they are deposited on the aperture and outside surface of catalyzer, not only cause the quick decline of catalyst activity, the rapid rising that also causes the reactor beds stressor layer to fall.
In recent years, the oil refining worker has researched and developed multiple Hydrodemetalation catalyst, and their common feature is to have large pore volume and wide aperture, is beneficial to metallic impurity and enters in the catalyzer duct.On this basis, K.W.Limbach and JamesWei[AICh E Journal, 34 (2), 305 (Feb, 1988)] find to reduce Hydrodemetalation catalyst particulate edge activity, can significantly improve the appearance amount of metal of catalyzer.But what adopt usually is the method for properties-correcting agent with the alkalimetal oxide, there is very big shortcoming, because being in the alkalimetal oxide of Hydrodemetalation catalyst grain edges very easily runs off under the industrial operation condition, Hydrodemetalation catalyst after apparent properties-correcting agent runs off will lose the effect of its modification, and the basic metal that runs off will pollute downstream catalyst.
The purpose of this invention is to provide Hydrodemetalation catalyst of a kind of edge passivation and preparation method thereof.Specifically, provide a kind of basic metal passivator that prevents and run off, performance is more stable, and effectively prevents Hydrodemetalation catalyst that pollutes downstream catalyst and preparation method thereof.
Hydrodemetalation catalyst of the present invention is introduced another nonmetallic ingredient when using alkali metals modified, this component can be phosphorus or silicon, phosphorus preferably, basic metal comprises potassium and sodium, is preferably potassium, its objective is by phosphorus or silicon alkali-metal constraint is reached the effect that prevents its loss.
The feature of Hydrodemetalation catalyst of the present invention is, contain basic metal (especially potassium) and phosphorus simultaneously at the granules of catalyst edge, the average content of basic metal potassium in catalyzer is 0.01-0.8w%, is preferably 0.05-0.3w%, P/K (atomic ratio) is at least 0.5, is preferably more than or equal to 1.0; VIII family metal (Ni or Co) content is 0.5-3.0w%, is preferably 1.0-2.0w%, and/or group vib metal (W or Mo) 1-3W%, and VIII family metal and group vib metal are evenly distributed in catalyzer.
Catalyzer pore volume (low temperature N of the present invention
2Absorption) 0.45-0.80ml/g, specific surface (BET) 100-230m
2/ g, the edge of catalyzer contains potassium element, can bring into play its modifying function for making this part potassium, again can be securely attached to the edge of catalyzer, introduced phosphorus or silicon components, particularly phosphorus component, this part phosphorus or silicon components can only exist only in the edge of catalyzer, also may reside in the integral body of whole catalyzer, so P/K (atomic ratio) is 0.5-40 in the catalyzer.Contained VIII family metallic element nickel preferably in the catalyzer of the present invention, the group vib metallic element is molybdenum preferably.
The present invention includes following several preparation method:
1, earlier to support modification, supports reactive metal again
Take by weighing a certain amount of anhydrous r-Al
2O
3Carrier is put in to spray and rolls in the pot, and the salt of the phosphorous and potassium of usefulness carrier saturated water adsorptive value 2-10% (V) is (as KH
2PO
4) or the aqueous solution of phosphoric acid, sylvite (as saltpetre or Repone K), spray alumina supporter with atomizing type, after solution has sprayed, it is paved into skim on enamel tray, then at 100-120 ℃ of dry 1-15h down; Put into stoving oven after the drying, rise to 700-1100 ℃, roasting 1-5h with the heat-up rate of 150-250 ℃/h.With the phosphorus after the roasting, potassium/Al
2O
3Put into and roll pot, spray into the VIII family and/or the group vib metal component of saturated water adsorptive value with atomizing type, behind 100-120 ℃ of dry 1-5h, the heat-up rate with 100-200 ℃/h in stoving oven rises to 450-550 ℃, constant temperature calcining 1-5h.
2, soak active ingredient earlier, soak properties-correcting agent again
Take by weighing a certain amount of anhydrous r-Al
2O
3Carrier is put in to spray and rolls in the pot, with the solution sprayed carrier that contains VIII family and/or group vib metal component of carrier saturated water adsorptive value 90-98% (V), and then with the salt of phosphorous, the potassium of carrier saturated water adsorptive value 2-10% (V) (as KH
2PO
4) or phosphoric acid, the solution of sylvite (as saltpetre, Repone K) continues to spray.After solution has sprayed, the moist catalysis of gained at 100-120 ℃ of dry 1-15h, is moved in the stoving oven, rise to 700-1100 ℃ with 150-250 ℃ heat-up rate, roasting 1-5h.
3, use phosphorous carrier, soak the hydrogenation activity component earlier, soak properties-correcting agent again
Take by weighing content of phosphorus-containing r-Al
2O
3Carrier places to spray and rolls pot, the solution sprayed carrier that contains VIII family and/or group vib metal component with phosphorous carrier saturated water adsorptive value 90-98% (V), slowly spray into sylvite (as saltpetre, the Repone K) solution of carrier saturated water adsorptive value 2-10% (V) then, after solution has sprayed, put into baking oven.At 100-120 ℃ of dry 1-15h, dried catalyzer is moved in the stoving oven, rise to 700-1100 ℃, constant temperature 1-5h with the speed of 150-250 ℃/h.
Said VIII family metal component is a nickel in above-mentioned three kinds of methods, and the group vib metal component is a molybdenum.
Modified solution spray the 2-10% (V) that consumption is generally the carrier saturated water adsorptive value, be preferably 4-7% (V).Reduce its consumption, the passivation layer thickness at granules of catalyst edge is attenuation, but causes the maldistribution of properties-correcting agent on the catalyzer outside surface easily.
Below further specify catalyzer of the present invention and preparation method with embodiment.
Embodiment 1
Get the anhydrous r-Al that 200g Fushun No.3 Petroleum Factory produces
2O
3Carrier is put in to spray and rolls in the pot, and its pore volume is 0.85ml/g, and specific surface is 249m
2/ g.8ml is contained 1gKH
2PO
4Solution, evenly spray with time of at least 10 minutes carrier in rolling with atomizing type, after having sprayed, continue to roll 20 minutes, and put into 110 ℃ dry 5 hours of loft drier then, move in the stoving oven, heat-up rate with 200 ℃/h rises to 950 ℃, constant temperature 3 hours.Naturally after the cooling, the carrier after the modification is reentered into to spray rolls in the pot, with containing 20g nickelous nitrate [Ni (NO
3)
2.6H
2O] 170ml solution, spray modified support with atomizing type, after solution has sprayed, continue to roll 30 minutes, then moist catalysis is placed in the steel disk, be paved into skim (less than 3cm), in 110 ℃ loft drier dry 10 hours; Move in the stoving oven, rise to 480 ℃ with the speed of 160 ℃/h, constant temperature 3 hours, the present embodiment catalyst A.
Embodiment 2
Get embodiment 1 used same vehicle 200g, be put in to spray and roll in the pot, with the 162ml solution that contains the 7.5g ammonium molybdate, spray to the carrier that rolls with atomizing type, after solution has sprayed, continue to roll 30 minutes, and then slowly spray into the 8ml solution that contains 0.50g phosphoric acid and 0.51g saltpetre, guarantee that the time of spraying was at least 10 minutes for the second time with atomizing type, after solution has sprayed, the moist catalysis taking-up is put in the white steel disk, and thickness is no more than 3cm, and drying is 10 hours in 110 ℃ loft drier, move in the stoving oven, speed with 200 ℃/h rises to 950 ℃, and constant temperature 3h under this temperature promptly gets the present embodiment catalyst B;
Embodiment 3
Get the industrial phosphorous r-Al of 200g
2O
3Carrier is put in to spray and rolls in the pot, and this carrier pore volume is 0.521ml/g, and specific surface is 379m
2/ g, phosphorus content are 2.7w%.With containing 20g nickelous nitrate [Ni (NO
3)
2.6H
2O] 99ml solution, spray this carrier with atomizing type, sprayed solution after, be rotated further 30 minutes, and then get the solution that 5.2ml contains 0.52g saltpetre, with atomizing type, evenly spray to the carrier that is rolling with times of at least 10 minutes.After solution has sprayed, handle, promptly obtain present embodiment catalyzer C by the post-treating method of embodiment 2.
Following table is the physico-chemical property of above catalyzer
| Catalyzer | ????A | ??????B | ????C |
| Pore volume (low temperature N 2Absorption) ml/g | ????0.62 | ????0.68 | ????0.49 |
| Specific surface m 2/g(BET) | ????134 | ????138 | ????133 |
| Form: Ni w% Mo w% K w% P w% P/K (atomic ratio) | ????1.90 ????- ????0.138 ????0.110 ????1.00 | ????- ????1.98 ????0.095 ????0.076 ????1.01 | ????1.93 ????- ????0.098 ????2.64 ????34.0 |
Comparative example 1
Prepare 153g and contain the potassium oxide catalyzer by containing the potassium method for preparing catalyst in the Chinese patent application 90110192.3, promptly get this comparative example catalyzer D.
Comparative example 2
In Chinese patent application 90110192.3, will contain 12.1 used in potassium catalyst preparation process gram saltpetre and change the 16.8g potassium primary phosphate into, maturing temperature changes 950 ℃ into, and constant temperature 3 hours promptly gets this comparative example catalyzer E.
Comparative example 3
In the present invention, modifier content on the catalyzer is very low, therefore be difficult to detect the effect that proof the inventive method prevents potassium lost with common means, design two comparative example catalyzer (D and E) for this reason, make potassium content in the comparison catalyzer far above the optimum potassium content of wanting required for the present invention, by comparing two catalyzer potassium lost situation in use, prove the effect of method of modifying of the present invention.
Respectively get 150mlD and E catalyzer, in the small fixed hydrogenation unit, carry out 200 hours comparative evaluations's (seeing the following form) respectively
| Catalyzer | ????D | ???????????E |
| Catalyzer is formed w% K (plasma spectrum) P (colorimetry) loadings ml | ????2.8 ????- ????150 | ??????????2.9 ??????????2.3 ??????????150 |
| Operational condition | Hydrogen dividing potential drop 14.7MPa, 380 ℃ of temperature, liquid hourly space velocity 0.5h -1, hydrogen-oil ratio 1000 (v/v) | |
| Potassium content ppm in the raw material | ?????????????????0.87 | |
| Generate potassium content ppm in the oil | ????15.7 | ??????????3.1 |
By above comparing result as can be seen, by the potassium on the inventive method introducing catalyzer, its number of dropouts is starkly lower than with K
2The O form is present in the number of dropouts in the catalyzer, shows thus, and the present invention has the good effect that properties-correcting agent runs off that prevents to the grain edges method of modifying of Hydrodemetalation catalyst.
Claims (11)
1, a kind of Hydrodemetalation catalyst, with the macroporous aluminium oxide is carrier, support group vib metallic element and/or VIII family metallic element, catalyst edge contains alkali metal passivator, it is characterized in that catalyst edge or integral body also contain phosphorus or element silicon, catalyzer pore volume 0.45-0.80ml/g, specific surface 100-230m
2/ g contains group vib metallic element 1-3w% and/or the metallic element 0.5-3w% of VIII family, alkali metal containing element 0.01-0.8w%, and silicon or phosphorus are 0.5-40 with the alkali metal atom ratio.
2,, it is characterized in that alkali metal content is 0.05-0.30w% according to the catalyzer of claim 1.
3, according to the catalyzer of claim 1, it is characterized in that catalyst edge contains alkali metal and phosphorus or element silicon, phosphorus or silicon are 1-3 with the alkali metal atom ratio.
4, according to the catalyzer of claim 1, it is characterized in that catalyst edge contains alkali metal, integral body contains phosphorus or element silicon, and its phosphorus or silicon are 30-40 with the alkali metal atom ratio.
5,, it is characterized in that said basic metal is potassium element according to claim 1 catalyzer.
6, according to the catalyzer of claim 5, the atomic ratio that it is characterized in that phosphorus and potassium is 0.5-40.
7, a kind of preparation method of Hydrodemetalation catalyst, it is characterized in that spraying alumina supporter with the aqueous solution of the salt of the phosphorous and potassium of carrier saturated water adsorptive value 2-10V% or phosphoric acid, sylvite, dry back is at 700-1100 ℃ of roasting 1-5h, support VIII family and/or group vib metal component with pickling process then, again at 450-550 ℃ of roasting 1-5h.
8,, it is characterized in that said phosphorous and salt potassium is KH according to the method for claim 7
2PO
4, support VIII family and/the group vib metal component is with the method for spraying.
9, a kind of preparation method of Hydrodemetalation catalyst, it is characterized in that spraying alumina supporter with the solution that contains VIII family and/or group vib metal component of carrier saturated water adsorptive value 90-98V%, solution with the salt of phosphorous, the potassium of carrier saturated water adsorptive value 2-10V% or phosphoric acid, sylvite continues to spray then, catalyzer after spraying is at 100-120 ℃ of dry 1-15h, at 700-1100 ℃ of roasting 1-5h.
10, a kind of preparation method of Hydrodemetalation catalyst, it is characterized in that, the solution that contains VIII family and/or group vib metal component with carrier saturated water adsorptive value 90-98v% sprays the phosphorus-containing alumina carrier, use the potassium salt soln sprayed carrier of carrier saturated water adsorptive value 2-10V% again, catalyzer after spraying is at 100-120 ℃ of dry 1-15h, at 700-1100 ℃ of roasting 1-5h.
11, according to the method for claim 7-10, it is characterized in that said VIII family and/or group vib metal are nickel and/or molybdenum, said salt phosphorous, potassium is KH
2PO
4
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94118334A CN1046130C (en) | 1994-11-22 | 1994-11-22 | Hydrodemetalation catalyst and preparation method thereof |
| KR1019950042606A KR100246175B1 (en) | 1994-11-22 | 1995-11-21 | Hydrogenation catalyst and preparation method thereof |
| IT95MI002403A IT1279064B1 (en) | 1994-11-22 | 1995-11-21 | DEMETALLIZATION CATALYST FOR HYDROGENATION AND PREPARATION OF THE SAME |
| US08/696,387 US5759951A (en) | 1994-11-22 | 1995-11-21 | Hydrogenation demetalization catalyst and preparation thereof |
| JP30487795A JP3264813B2 (en) | 1994-11-22 | 1995-11-22 | Hydrodemetallation catalyst and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94118334A CN1046130C (en) | 1994-11-22 | 1994-11-22 | Hydrodemetalation catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1123309A true CN1123309A (en) | 1996-05-29 |
| CN1046130C CN1046130C (en) | 1999-11-03 |
Family
ID=5038768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94118334A Expired - Lifetime CN1046130C (en) | 1994-11-22 | 1994-11-22 | Hydrodemetalation catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046130C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053458C (en) * | 1996-10-28 | 2000-06-14 | 中国石油化工总公司 | Catalyzer for hydrotreating residuum and its prepn. method |
| CN1058982C (en) * | 1997-12-24 | 2000-11-29 | 中国石化齐鲁石油化工公司 | Catalyst for heavy oil hydrogenation demetal and preparation method |
| CN102784655A (en) * | 2012-07-31 | 2012-11-21 | 宁波市化工研究设计院有限公司 | Coal tar hydrodemetallization catalyst and preparation method of catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4741821A (en) * | 1986-10-06 | 1988-05-03 | Chevron Research Company | Catalyst system for removal of calcium from a hydrocarbon feedstock |
| CN1020282C (en) * | 1990-05-11 | 1993-04-14 | 中国石油化工总公司石油化工科学研究院 | Catalyst for hydrogenation treatment of heavy fraction oil |
-
1994
- 1994-11-22 CN CN94118334A patent/CN1046130C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053458C (en) * | 1996-10-28 | 2000-06-14 | 中国石油化工总公司 | Catalyzer for hydrotreating residuum and its prepn. method |
| CN1058982C (en) * | 1997-12-24 | 2000-11-29 | 中国石化齐鲁石油化工公司 | Catalyst for heavy oil hydrogenation demetal and preparation method |
| CN102784655A (en) * | 2012-07-31 | 2012-11-21 | 宁波市化工研究设计院有限公司 | Coal tar hydrodemetallization catalyst and preparation method of catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1046130C (en) | 1999-11-03 |
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| C14 | Grant of patent or utility model | ||
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Owner name: CHINA PETROCHEMICAL CORPORATION; CHINA PETROLEUM & Free format text: FORMER NAME OR ADDRESS: CHINA PETRO-CHEMICAL CORP.; FUSHUN PETROCHEMICAL INSTITUTE., CHINA PETROCHEMICAL CORP. |
|
| CP01 | Change in the name or title of a patent holder |
Patentee after: China Petrochemical Group Corp. Patentee after: Sinopec Group Fushun Research Institute of Petroleum and Petrochemicals Patentee before: China Petrochemical Corporation Patentee before: Fushun Research Inst. of Petroleum Processing, China Petro-chem. Corp. |
|
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20141122 Granted publication date: 19991103 |