CN1053458C - Catalyzer for hydrotreating residuum and its prepn. method - Google Patents
Catalyzer for hydrotreating residuum and its prepn. method Download PDFInfo
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- CN1053458C CN1053458C CN96120423A CN96120423A CN1053458C CN 1053458 C CN1053458 C CN 1053458C CN 96120423 A CN96120423 A CN 96120423A CN 96120423 A CN96120423 A CN 96120423A CN 1053458 C CN1053458 C CN 1053458C
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Abstract
The present invention relates to a hydrotreating catalyst for residual oil and a preparation method thereof. The catalyst uses metallic elements of the VIII group and the VIB group as active components, and is loaded on an alumina carrier of a metal oxide of the IVB group. In the carrier, the pore volume with the pore diameter from 7.0 nm to 13.0 nm accounts for higher than 80% of the total pore volume. In the method of the present invention, in the process that alumina dried glue powder is pugged, a certain amount of alkaline solution is firstly added, a certain amount of acidic solution is added after the mixed solution is sufficiently pugged, plastic bodies are then pugged, and the carrier is manufactured after extrusion forming, drying and calcining.
Description
The present invention relates to a kind of residual hydrocracking, particularly Hydrobon catalyst and preparation method thereof.
The residuum hydrodesulfurization catalyzer is carrier usually with the porous alumina, or pure aluminum oxide, or contains a small amount of SiO
2Or B
2O
3Aluminum oxide, be active ingredient with VIII family and group vib metallic element.Usually, the residuum hydrodesulfurization catalyzer must have proper pore structure, could guarantee good activity and stable; Three basic demands to its pore structure are:
(1) pore distribution will be concentrated, and the pore volume of aperture in 7.0-13.0nm accounts for the ratio of total pore volume at least greater than 80%;
(2) mean pore size is moderate, generally between 9.0～13.0nm;
(3) have big as far as possible pore volume and specific surface area.
As everyone knows, hydrotreatment particularly the load hydrogenation pore structure of handling catalyzer determined by the pore structure of its carrier that basically therefore, development person adopt various methods to attempt the pore structure of improved carrier.For the carrier of extruded moulding, at first to select proper raw material, promptly raw material will have concentrated pore distribution; Next be mix pinch or roasting process in carry out suitable processing, have proper pore structure to guarantee carrier.
For example, at US 4,066,574, US 4,113, and 661 and US 4, introduced a kind of preparation method of carrier in 341,625 3 pieces of patents, its technical essential is that (1) adds earlier aqueous nitric acid in a water Alpha-alumina (being boehmite) raw material, and its equivalence ratio with aluminum oxide is 0.08～0.12, fully mixed pinching; (2) in above-mentioned material, add NH again
3The aqueous solution, the equivalence ratio of itself and nitric acid is 0.6～1.2, fully mixes and pinches; (3) make carrier through extrusion, drying and roasting.In this carrier, the aperture be the pore volume of 8.0～15.0nm account for total pore volume 70～85%, the ratio that the aperture accounts for total pore volume greater than the pore volume of 100.0nm is less than 3%, total pore volume is 0.64～0.82ml/g.
And different being (1) raw material of the preparation method of the carrier of introducing and aforesaid method is the mixture of two kind of one water Alpha-alumina among the US 5,177,047; (2) the neutral alkali number is reduced to 0.3～0.5 equivalent by 0.6～1.2 equivalent; (3) in this carrier, the ratio that the pore volume of 7.0～13.0nm accounts for total pore volume is no less than 70%, and total pore volume is 0.62ml/g.
In the described method of above-mentioned patent, the purpose that adds acid earlier is, make its with the alumina raw material thorough mixing to avoid in shaping carrier occurring too much hole greater than 100.0nm, eliminate a part of aperture simultaneously, make pore distribution be tending towards concentrated.But this method has following shortcoming: the one, and the nitric acid that adds directly contacts with the boehmite dry glue powder earlier, and it is stronger to interact, and it is serious that the pseudo-boehmite micropore is shunk, loss pore volume and specific surface; The 2nd, for the purpose that reaches pore distribution concentration must add excessive nitric acid, make the pore volume loss more serious, adding alkali number must increase with the acid amount, thereby increases manufacturing cost.
From the pore structure of its carrier, US 4,066, and 574, US 4,113,661 and US4, though 341625 carrier has bigger pore volume, it is higher that the pore volume of its 8.0～15.0nm accounts for total pore volume ratio, is unfavorable for hydrogenating desulfurization; And the carrier of US 5,177,047, though pore structure is comparatively suitable, its pore volume is lower, adopts the catalyzer of above-mentioned preparing carriers, and perhaps pore structure is improper, and perhaps pore volume is lower, influences activity of such catalysts and stability.
The objective of the invention is, at the problems referred to above, invention residuum hydrodesulfurization catalyzer, this catalyzer has good desulphurizing activated, further object of the present invention provides above-mentioned Preparation of catalysts method, not only pore distribution concentration, aperture are moderate to make the catalyzer made, and have bigger pore volume and specific surface.
The technical essential of the inventive method is: in the pseudo-boehmite dry glue powder, add an amount of basic solution earlier, after fully mixed the pinching, add a certain amount of acidic solution again, the mixed even back material of pinching is made carrier through extrusion, drying and roasting, support hydrogenation metal and dry, roasting then, make catalyzer.
The principle of the inventive method is: the basic solution that adds earlier in the pseudo-boehmite dry glue powder; adsorb and be covered in surfaces externally and internally formation one deck " protective membrane " of pseudo-boehmite; when adding the acidic solution peptization again; can slow down the strong interaction of acid and aluminum oxide greatly, reduce the loss of aluminum oxide pore volume and specific surface.Have bigger pore volume and specific surface by the made carrier of the inventive method, and pore distribution concentration, aperture are moderate.Adopt the catalyzer of this preparing carriers to have higher hydrodesulfurization activity and activity stability.
Preparation of catalysts process of the present invention is:
(1) take by weighing the pseudo-boehmite dry glue powder, if need and can mix earlier with an amount of extrusion aid, add alkaline aqueous solution, add-on is 20～60w% of pseudo-boehmite dry glue powder; Mix and pinched preferably 30～40 minutes 10～50 minutes.Add acidic aqueous solution again, add-on is 40～60w% of pseudo-boehmite dry glue powder, mixes and pinches preferably 60～70 minutes 30～80 minutes.
(2) by (1) gained material extruded moulding on banded extruder.
(3) by (2) gained material, 80～140 ℃ of temperature dry 1～5 hour down, preferably 100～120 ℃ dry 3～4 hours down.
(4) by (3) gained material, under 700～900 ℃ of temperature, preferably under 750～850 ℃, roasting 2～5 hours.
(5) with containing the saturated dipping of solution of molybdenum (or tungsten) and nickel and/or cobalt by (4) material of leading.
(6) by (5) gained material, under 80～140 ℃ of temperature, preferably 100～120 ℃ were descended dry 1～5 hour.
(7) by (6) gained material, under 420～580 ℃ of temperature, preferably 450～550 ℃ of following roastings are 1～4 hour.
Wherein alkaline aqueous solution described in the step (1) is for being selected from ammonia (NH
3), ammonium phosphate (NH
4)
3PO
4, ammonium hydrogen phosphate (NH
4)
2HPO
4, primary ammonium phosphate NH
4H
2PO
4At least a in the aqueous solution, acid solution described in the step (1) are to be selected from least a in formic acid, acetate, nitric acid and the hydrochloric acid.
Contain TiCl in the described acid solution
36～10w% or ZrOCl
28.0～12.0w%.
Described alkaline aqueous solution is that ammoniacal liquor contains NH
34～8w% in the acidic aqueous solution, contains acetate 3～8w%, contains TiCl
36～10w% or ZrOCl
28.0～12.0w%.
The described dipping solution of step (5) is to be selected from a kind of in Mo-Ni-P, Mo-Ni-Co-P, Mo-Co-P, the W--Ni solution.
Extrusion aid described in the step (1) is the blue or green powder in field, starch, polyvinyl alcohol, methylcellulose gum, the blue or green powder in field preferably, and its add-on is 2～8w% of pseudo-boehmite dry glue powder, preferably 4～6w%.
Extruded moulding process described in the step (2), the extrusion orifice plate can be selected as required, and support shapes is generally cylindrical or the cross section is the strip of three (four) leaves grass shape, and diameter or equivalent diameter are 0.8～1.6mm.
Solution described in the step (5) is Mo-Ni-P or Mo-Ni-Co-P or Mo-Co-P or W--Ni solution, and the concentration of solution is determined by the water-intake rate of carrier and the metal component content of final catalyzer.
Catalyzer of the present invention is formed, and in catalyst weight, is MoO
3Or WO
314～24w%, preferably 16～20w%; CoO and/or NiO 2.0～6.0w%, preferably 3.0～5.0w%; P is 1.0～3.0w%, preferably 1.7～2.1w%; TiO
2And/or ZrO
22.0～12.0w%, preferably 3.0～8.0w%.
Catalyst for hydrotreatment of residual oil of the present invention is with γ-Al
2O
3Be carrier, support VIII family and group vib metallic element, the pore volume of catalyzer is 0.30～0.60ml/g, and specific surface is 120～200m
2/ g, mean pore size is 9.0～13.0nm.
Catalyst for hydrotreatment of residual oil of the present invention is with γ-Al
2O
3Be carrier, support VIII family and group vib metallic element, the pore volume of catalyzer is 0.30～0.60ml/g, and specific surface is 120～200m
2/ g, mean pore size is 9.0～13.0nm.
Contain group vib metal oxide 14～24w% and VIII family metal oxide 2.0～6.0w% in the catalyzer of the present invention.Preferably contain group vib metal oxide 16～20w% and VIII family metal oxide 3.0～5.0w%.
Catalyzer of the present invention can also contain IVB family metal oxide 2.0～12.0w%, preferably 3.0～8.0w%.
Described VIII family metal oxide is selected from CoO, NiO; The group vib metal oxide is selected from MoO
3, WO
3The IVB family metal oxide is selected from TiO
2, ZrO
2
Catalyzer of the present invention under the hydrocracking condition, is handled High Sulfur Vacuum Residue after sulfuration, show higher desulphurizing activated and moderate denitrification activity.
The technical characterictic that the invention is further illustrated by the following examples.
Embodiment 1
With pseudo-boehmite dry glue powder (salic 73%) 300g that Qilu Petrochemical company produces, add the blue or green powder 18g in field, mix.Is concentration that the ammoniacal liquor 60g of 4w% adds in the aforesaid material, fully mixes and pinches, then the aqueous solution 152g that contains acetate 8w%, add in the above-mentioned material, after fully mixed the pinching, on preceding crowded formula twin screw banded extruder, be extruded into the cylinder bar that diameter is 0.84mm, the gained bar that wets is 100 ℃ of dryings 3 hours, 750 ℃ of roastings 3 hours, get carrier A, its character sees Table 1, respectively through Mo-Ni-P, Mo-Co-P solution impregnation, through 100 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyst A
1, A
2, its character sees Table 2.
Embodiment 2
With the pseudo-boehmite dry glue powder 300g that Qilu Petrochemical company produces, add the blue or green powder 18g in field, mix.Is concentration that the ammoniacal liquor 150g of 6w% adds in the aforesaid material, fully mixes and pinches, then containing acetate 4w%, TiCl
3The acidic aqueous solution 141g of 8w% adds in the above-mentioned material, according to the identical method of example 1, obtains carrier B.Carrier B is respectively through Mo-Ni-P, Mo-Co-P solution impregnation, through 100 ℃ of dryings 5 hours, 450 ℃ of roastings 2 hours, catalyst B
1, B
2, its character sees Table 2.
Embodiment 3
The pseudo-boehmite dry glue powder 300g identical with example 1 adds the blue or green powder in 18g field, mixes.Concentration is that the ammoniacal liquor 160g of 6w% adds in the aforesaid material, mixes and pinches evenly, contains acetate 8w%, ZrOCl
2The acidic solution 141g of 9.0w% adds in the above-mentioned material, according to the identical method of example 1, obtains support C.Support C is respectively through Mo-Ni-P, Mo-Co-P solution impregnation, through 100 ℃ of dryings 5 hours, 500 ℃ of roastings 2 hours, catalyzer C
1, C
2, its character sees Table 2.
Comparative example 1
This comparison example is by US 4,066,574, the carrier and the catalyzer of the method preparation described of US 4,113,661, US 4,341625.Because the method that these three pieces of patents are described is basic identical, therefore, only list a Comparative Examples.
The pseudo-boehmite dry glue powder 300g identical with embodiment 1 adds 11.6g nitric acid and 200g water purification mixture, mixes, again with 2.5gNH
3Mix with the 123g water purification, add above-mentioned material, press the identical method of example 1 then, obtain carrier D and catalyzer D
1And D
2, its character sees Table 1 and table 2.
Comparative example 2
This comparison example is by US 5,177, the carrier and the catalyzer of the preparation of 047 described method.
The pseudo-boehmite dry glue powder 300g identical with embodiment 1 adds 33g nitric acid and 216g water purifying mixture, behind the thorough mixing, adds the ammoniacal liquor 171g of 2.6w% again, according to the identical method of embodiment 1, obtains carrier E and catalyzer E
1, E
2, its character sees Table 1 and table 2 respectively.
Embodiment 4 under identical processing condition, comparative catalyst A
1, A
2, B
1, B
2, C
1, C
2, D
1, D
2, E
1And E
2, handle desulfurization and nitrogen removal performance that isolated island vacuum residuum shows.Estimate stock oil character and estimate processing condition and see Table 3 and table 4 respectively, evaluation result sees Table 5.Table 1 carrier character
As seen from Table 1, carrier A of the present invention, B and C have concentrated pore distribution, moderate mean pore size and bigger pore volume and specific surface; Though and comparison vehicle D pore volume and mean pore size are also comparatively suitable, relatively disperse of its pore distribution; Though and comparison vehicle E mean pore size and pore distribution are comparatively suitable, its pore volume and specific surface are lower.Table 2 catalyst property
| Project | A | B | C | D | E | |
| Pore volume ml/g specific surface m 2/ g mean pore size nm | 0.68 258 10.5 | 0.73 266 11.3 | 0.78 268 11.6 | 0.65 236 11.5 | 0.62 236 11.8 | |
| Pore distribution | ＜7nm 7～13nm ＞13nm | 9 90 1 | 4 93 3 | 10 87 3 | 6 67 27 | 7 90 3 |
| Project | A 1 | A 2 | B 1 | B 2 | C 1 | C 2 | D 1 | D 2 | E 1 | E 2 |
| Pore volume ml/g specific surface m 2/ g heap is than g/ml MoO 3 w％ NiO w％ CoO w％ P w％ TiO 2 w％ ZrO 2 w％ | 0.39 153 0.89 19.37 4.65 0 1.67 0 0 | 0.40 166 0.83 17.5 3.8 0 1.7 0 0 | 0.39 163 0.90 18.8 4.52 0 1.60 0 3.3 | 0.49 140 0.83 16.0 0 3.10 1.56 0 2 | 0.58 160 0.87 18.5 4.40 0 1.70 6.0 0 | 0.54 163 0.80 15.8 0 3.76 1.69 6.3 0 | 0.36 140 0.90 19.4 4.65 0 1.67 0 0 | 0.35 146 0.89 18.7 0 4.12 1.86 0 0 | 0.30 120 0.90 18.5 4.2 0 1.66 0 0 | 0.34 125 0.89 16.9 0 3.85 1.86 0 0 |
As seen from Table 2, catalyst A of the present invention
1, A
2, B
1, B
2, C
1And C
2All have bigger pore volume and specific surface, and under the essentially identical condition of metal component content, comparative catalyst D
1And D
2, E
1And E
2Pore volume and specific surface all less.Table 3 stock oil character
| Density (20 ℃) g/cm 3 S w％ N w％ Ni+V g/g | 1.018 2.56 0.76 42 |
Table 4 is estimated processing condition
Table 5 activity rating is * as a result
*Sampling analysis result after turning round 300 hours
| Catalyzer loading amount ml pressure Mpa air speed h -1Temperature ℃ hydrogen-oil ratio (v) | 185 14.7 0.54 400 1000 |
| Project | A 1 | A 2 | B 1 | B 2 | C 1 | C 2 | D 1 | D 2 | E 1 | E 2 |
| Generate oily sulphur content w% desulfurization degree % and generate oily nitrogen content w% denitrification percent % | 0.44 83 0.39 47 | 0.43 84 0.42 45 | 0.44 83 0.39 48 | 0.43 83 0.41 46 | 0.42 84 0.39 49 | 0.44 83 0.40 47 | 0.58 77 0.42 44 | 0.55 79 0.45 40 | 0.54 79 0.43 43 | 0.52 80 0.46 39 |
As seen from Table 5, catalyst A of the present invention
1, A
2, B
1, B
2, C
1And C
2All show higher desulphurizing activated and denitrification activity, and comparative catalyst D
1, and D
2, E
1And E
2Desulphurizing activated and denitrification activity all lower.
Claims (10)
1. catalyst for hydrotreatment of residual oil is with γ-Al
2O
3Be carrier, support VIII family and group vib metallic element, consist of group vib metal oxide 14～24w%, group VIII metal oxide 2.0～60w%, surplus is a carrier, and the pore volume that it is characterized in that catalyzer is 0.30～0.60ml/g, and specific surface is 120～200m
2/ g, mean pore size is 9.0～13.0nm.
2. according to the described catalyzer of claim 1, it is characterized in that containing group vib metal oxide 16～20w% and VIII family metal oxide 3.0～5.0w%.
3. according to the described catalyzer of claim 1, it is characterized in that containing IVB family metal oxide 2.0～12.0w%.
4. according to the described catalyzer of claim 3, it is characterized in that containing IVB family metal oxide 3.0～8.0w%.
5. according to the described catalyzer of claim 3, it is characterized in that the VIII family metal oxide is selected from CoO, NiO; The group vib metal oxide is selected from MoO
3, WO
3The IVB family metal oxide is selected from TiO
2, ZrO
2
6. a catalyst for hydrotreatment of residual oil preparation method is characterized in that the steps include:
(1) taking by weighing pseudo-boehmite is γ-Al
2O
3The precursor dry glue powder, add alkaline aqueous solution, add-on is 20～60w% of pseudo-boehmite dry glue powder, mixes and pinches 10～50 minutes, adds acidic aqueous solution again, add-on is 40～60w% of pseudo-boehmite dry glue powder, mixes and pinches 30～80 minutes;
(2) by (1) gained material extruded moulding on banded extruder;
(3), following dry 1～5 hour 80～140 ℃ of temperature by (2) gained material;
(4) by (3) gained material, under 700～900 ℃ of temperature, roasting 2～5 hours;
(5) with containing the saturated dipping of solution of molybdenum or tungsten and nickel and/or cobalt by (4) gained material;
(6), following dry 1～5 hour 80～140 ℃ of temperature by (5) gained material;
(7) by (6) gained material, under 420～580 ℃ of temperature, roasting 1～4 hour.
7. preparation method according to claim 6 is characterized in that alkaline aqueous solution is for being selected from ammonia NH described in the step (1)
3, ammonium phosphate (NH
4)
3PO
4, ammonium hydrogen phosphate (NH
4)
2HPO
4, primary ammonium phosphate NH
4H
2PO
4At least a in the aqueous solution, acid solution described in the step (1) are to be selected from least a in formic acid, acetate, nitric acid and the hydrochloric acid.
8. preparation method according to claim 6 is characterized in that containing TiCl in the described acid solution
36～10w% or ZrOCl
28～12w%.
9. according to the described preparation method of claim 7, it is characterized in that described alkaline aqueous solution is that ammoniacal liquor contains NH
34～8w% in the acidic aqueous solution, contains acetate 3～8w%, contains TiCl
36～10w% or ZrOCl
28～12w%.
10. according to the described preparation method of claim 6, it is characterized in that solution described in the step (5) is to be selected from a kind of in Mo-Ni-P, Mo-Ni-Co-P, Mo-Co-P, the W--Ni solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120423A CN1053458C (en) | 1996-10-28 | 1996-10-28 | Catalyzer for hydrotreating residuum and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96120423A CN1053458C (en) | 1996-10-28 | 1996-10-28 | Catalyzer for hydrotreating residuum and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1181409A CN1181409A (en) | 1998-05-13 |
| CN1053458C true CN1053458C (en) | 2000-06-14 |
Family
ID=5126316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96120423A Expired - Lifetime CN1053458C (en) | 1996-10-28 | 1996-10-28 | Catalyzer for hydrotreating residuum and its prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1053458C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073616C (en) * | 1998-11-13 | 2001-10-24 | 中国石油化工集团公司 | Preparation method of hydrogenation catalyst |
| CN1072705C (en) * | 1998-12-16 | 2001-10-10 | 中国石油化工集团公司 | Process for preparing residuum hydrogenation catalyst |
| CN101618326B (en) * | 2008-06-30 | 2011-11-30 | 中国石油化工股份有限公司 | Heavy oil hydrogenation processing catalyst and method for preparing same |
| WO2016009333A1 (en) | 2014-07-17 | 2016-01-21 | Sabic Global Technologies B.V. | Upgrading hydrogen deficient streams using hydrogen donor streams in a hydropyrolysis process |
| CN114433111B (en) * | 2020-10-30 | 2023-08-25 | 宁波中金石化有限公司 | Heavy aromatic oil hydrofining catalyst and heavy aromatic oil processing method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066574A (en) * | 1973-08-09 | 1978-01-03 | Chevron Research Company | Hydrocarbon hydrotreating catalyst composition |
| CN1052501A (en) * | 1989-12-11 | 1991-06-26 | 中国石油化工总公司抚顺石油化工研究院 | Hydrobon catalyst and method for making |
| CN1123309A (en) * | 1994-11-22 | 1996-05-29 | 中国石油化工总公司抚顺石油化工研究院 | Hydrodemetalation catalyst and preparation method thereof |
-
1996
- 1996-10-28 CN CN96120423A patent/CN1053458C/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4066574A (en) * | 1973-08-09 | 1978-01-03 | Chevron Research Company | Hydrocarbon hydrotreating catalyst composition |
| US4113661A (en) * | 1973-08-09 | 1978-09-12 | Chevron Research Company | Method for preparing a hydrodesulfurization catalyst |
| CN1052501A (en) * | 1989-12-11 | 1991-06-26 | 中国石油化工总公司抚顺石油化工研究院 | Hydrobon catalyst and method for making |
| CN1123309A (en) * | 1994-11-22 | 1996-05-29 | 中国石油化工总公司抚顺石油化工研究院 | Hydrodemetalation catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1181409A (en) | 1998-05-13 |
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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. |
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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. |
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