CN1352229A - Heavy oil hydrogenating treatment catalyst and its preparing method - Google Patents
Heavy oil hydrogenating treatment catalyst and its preparing method Download PDFInfo
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- CN1352229A CN1352229A CN 00123223 CN00123223A CN1352229A CN 1352229 A CN1352229 A CN 1352229A CN 00123223 CN00123223 CN 00123223 CN 00123223 A CN00123223 A CN 00123223A CN 1352229 A CN1352229 A CN 1352229A
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Abstract
The present invention is a kind of hydrogenizing treatment catalyst and its preparation. The catalyst has alumina as carrier and VIII and/or VIB metal as active component. During its preparation, two kinds of different pseudo-thin diasphore are mixed and kneaded with composite pore expanding agent to form moldable matter, which is extruded in strip extruder and high temperature roasted to obtain the carrier; and the active component is then loaded onto the carrier through soaking. The catalyst is suitable for suitable for hydrodenitrification and/or hydrodesulfurization process of heavy oil, especially residual oil.
Description
The present invention relates to a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof, particularly residuum hydrogenating and metal-eliminating or Hydrobon catalyst and preparation method thereof.
At present, industrial hydrotreating catalyst is carrier with the aluminum oxide normally, is active ingredient with group VIII and group vib metallic element.As everyone knows, the pore structure of catalyzer is to the catalytic perfomance important influence of catalyzer.For catalyst for hydroprocessing of heavy oil, especially residual hydrocracking catalyst system therefor, generally need have bigger aperture and pore volume, be beneficial to the internal diffusion of macromolecular reaction thing in the mink cell focus, avoid or slow down because the reaction deposition of the metallic impurity that generate and blocking catalyst duct, thereby cause catalyst activity to descend fast.
The catalyzer of being introduced among the JP57-123820 adopts physics expanding agent carbon black to carry out reaming, and the carbon black usage quantity is big, causes prepared catalyzer aperture distribution disperse, bad mechanical strength, and the catalyzer aperture is also less.The prepared catalyzer of JP57-123820 can several apertures be 14nm, and the pore volume of aperture between 10-20nm accounts for 50% of total pore volume, and physical strength is 4.9N/mm.
USP4,454,026 catalyzer of being introduced have bigger aperture, but its tap density is lower, is 0.40g/ml, and pore size distribution also relatively disperses, and the pore volume of aperture between 10-20nm accounts for percentage＜60% of total pore volume.
CN1 in 160,602, adopts physics and chemical enlargement agent simultaneously, and prepared carrier and above-mentioned patent relatively have bigger aperture and pore volume, and pore distribution and physical strength also improve significantly, and tap density is moderate.But add expanding agent during owing to moulding, weakened the cohesiveness between the aluminum hydroxide particles to a certain extent, therefore, the physical strength of this carrier is still lower, and the pore distribution concentration degree is also not ideal enough.By the prepared catalyzer physical strength of this carrier is 8.6N/mm, and the aperture accounts for total pore volume about 60% at the pore volume between the 10-20nm.
The objective of the invention is: provide a kind of heavy oil hydrogenating treatment catalyst and preparation method thereof at problems of the prior art.Make the catalyzer pore distribution concentration, the physical strength that make good, have good hydrodemetallation (HDM) and desulphurizing activated and activity stability.
Preparation of catalysts process of the present invention and principal character thereof are:
(1) two kinds of aluminum oxide of different nature and compound expanding agent (physics expanding agent, chemical enlargement agent), extrusion aid, peptizing agent, water are mixed and pinch, until becoming plastic; Extruded moulding; Roasting obtains carrier of the present invention.Said roasting is at 600-1100 ℃ of following roasting 1-5 hour.
(2) with containing the solution impregnation carrier of the present invention of active metal component, drying (about 100 ℃ or seasoning) and roasting then, catalyzer of the present invention.
In step (1), adopted compound expanding agent, i.e. physics expanding agent and chemical enlargement agent.Among the present invention, use physics and chemically composited expanding agent, the two synergy can reach tangible reaming effect, also can reduce its consumption separately.Described physics expanding agent is a carbon black, and its consumption is 1-15m%, is preferably 3-10m%; The chemical enlargement agent is a boric acid, phosphoric acid or borate, phosphoric acid salt, and add-on is 0.05-5.0m%, is preferably 0.1-1.5m%.Described extrusion aid is sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, is preferably the sesbania powder, and add-on is 2.0-8.Om%.Described peptizing agent can be organic acid such as formic acid, acetate etc., or mineral acid such as nitric acid etc., and add-on is 0.5-10.0m%, is preferably 1.0-3.0m%.
Said two kinds of aluminum oxide of different nature can be that aluminium hydroxide is pseudo-boehmite, γ-Al in the step (1)
2O
3, δ-Al
2O
3, η-Al
2O
3The ratio of the two is 1: 25-25: 1 (weight).
Two kinds of aluminum oxide have dual dispersed texture, can adjust the pore structure of catalyzer neatly.Baked aluminum oxide, because nodulizing, the crystal grain gathering is grown up, macropore is more, helps improving the macropore ratio of catalyzer; Simultaneously, because crystal grain is assembled, associativity strengthens, and the catalyzer physical strength also increases.Among the present invention, can directly carry out roasting without drying after the carrier moulding, reduce operation steps, shorten the production cycle, help reducing the catalyzer manufacturing cost.In addition, shaping carrier is moist, and its contained moisture is evaporated in high-temperature calcination process in a large number, can produce the high-temperature water vapor treatment effect.The existence of water vapor reduces aperture, in, macropore increases, and remedies loss such as the macropore that operation caused that mixes the pinching bar, it is concentrated to help making the effective pore radius to distribute.
Active ingredient is selected from periodic table of elements group vib and VIII family metal in dipping solution of the present invention.Formulations prepared from solutions process of the present invention adds certain density ammoniacal liquor, simultaneously, also introduces a kind of organic acid such as oxysuccinic acid or citric acid.This stability of solution is good, helps improving metal and carrier interactions, makes metal more even in the inner dispersion of carrier granule, thereby improves the hydrogenating desulfurization and the metal removal activity of catalyzer.
The catalyzer that the inventive method is prepared, the catalyzer pore volume is 0.5-1.2ml/g, is preferably 0.6-0.9ml/g, specific surface area is 100-200m
2/ g, preferably 120-180m
2/ g can several apertures be 15-23, is preferably 16-20nm, and the aperture accounts for more than 70% of total pore volume at the pore volume between the 10-20nm.The pore volume of aperture＞16nm accounts for the 40-75% of total pore volume.
Catalyzer contains the group vib metal oxide (as MoO
3) 1.0-14.0w%, be preferably 3.0-12.0w%, contain group VIII metal oxide (as NiO or CoO) 0.1-8.0w%, 0.5-5.0w% preferably, remainder is an aluminum oxide.Physical strength 〉=10.0N/m m, tap density 〉=0.50g/ml is preferably 0.52-0.60g/ml.
The catalyzer of the inventive method preparation has bigger aperture and pore volume, moderate specific surface area, suitable good, the pore distribution concentration of tap density, physical strength, is applicable to especially residual hydrocracking process of mink cell focus.
Further set forth feature of the present invention below by embodiment.
Embodiment 1
The 500g pseudo-boehmite (is produced by Chemical Fertilizer Factory No.1, Qilu Petrochemical Co., water content 30%) and 33g aluminum oxide powder and 26.3g carbon black, 3.36g phosphoric acid, 7.8g acetate, 15.6g sesbania powder, 211g water purification mix and pinch, become plastic, on banded extruder, be extruded into 1.2mm Herba Galii Bungei bar then, 650 ℃ of following roastings 4 hours, get carrier S 1.
Get that ammonium molybdate 60.83g is dissolved in 40ml, concentration is in the ammoniacal liquor of 14m%, stir make the ammonium molybdate dissolving after, add 77.83g Xiao Suangu and 25g citric acid, continue to stir, treat complete molten after, with ammoniacal liquor liquor capacity is diluted to 500ml.
With prepared solution impregnating carrier S1, then 110 ℃ of dryings 6 hours, 550 ℃ of roastings 4 hours, catalyzer C
1
Embodiment 2
500g pseudo-boehmite dry glue powder (with embodiment 1) and 61g aluminum oxide powder and 22g carbon black, 3.95g phosphoric acid, 8.6g acetate, 16.5g sesbania powder, 470g water purification are mixed and pinch, become plastic, on banded extruder, be extruded into 1.2mm Herba Galii Bungei bar then, 750 ℃ of following roastings 3 hours, get carrier S 2.
Get that 49.55g ammonium molybdate, 38.88g Xiao Suangu and 18g citric acid join 400ml, concentration is in the ammoniacal liquor of 14m%, stir solids is dissolved fully, with ammoniacal liquor liquor capacity is diluted to 500ml then.
With prepared solution impregnating carrier S2, place a night after, under 500 ℃ of temperature, roasting 4 hours catalyzer C
2
Embodiment 3
400g pseudo-boehmite dry glue powder (with embodiment 1) and 120g aluminum oxide powder and 16g carbon black, 3g boric acid, 8g acetate, 18g sesbania powder, 470g water purification are mixed and pinch, become plastic, on banded extruder, be extruded into 1.2mm Herba Galii Bungei bar then,, get carrier S 3 850 ℃ of following roastings 5 hours.
Press embodiment 1 same procedure configuration Mo-Ni solution, make the MoO that contains 10m% and 3m% in the solution respectively
3And NiO, use this solution impregnating carrier S3 then, 500 dryings are 6 hours under 110 ℃ of temperature, getting catalyzer C
3
Embodiment 4
In embodiment 1, it is the cost example that acetate changes nitric acid into, gets carrier S 4.
Press embodiment 3 same procedure impregnated carrier S4, get catalyzer C
4
Embodiment 5
In embodiment 1, it is the cost example that phosphoric acid changes aluminum phosphate into, gets carrier S 5.
Press embodiment 3 same procedure impregnated carrier S4, get catalyzer C
5
Embodiment 6
In embodiment 1, it is the cost example that phosphoric acid changes ammonium borate into, gets carrier S 6.
Press embodiment 3 same procedure impregnated carrier S6, get catalyzer C
6
Comparative example 1
Take by weighing the 500g pseudo-boehmite do than powder (with the present invention with) and 150g carbon black, after mixing, add 22g acetic acid and 780g water, continuing to mix to pinch becomes plastic, presses embodiment 1 same procedure extruded moulding then, drying and roasting get carrier S 7.
Press embodiment 3 same procedure impregnated carrier S7, get catalyzer C
7
Comparative example 2 (CN1,160,602)
Mixed the pinching of 500g pseudo-boehmite dry glue powder (with embodiment 1) and 24g carbon black, 3.15g phosphoric acid, 14g sesbania powder and 450g water become plastic, press embodiment 1 same procedure extruded moulding then, dry 6 hours and roasting get carrier S 8.
Press embodiment 3 same procedure impregnated carrier S8, get catalyzer C
8
Embodiment 7
This example provides the main physico-chemical property of catalyzer in above-mentioned each example, sees Table 1.
The main physico-chemical property of table 1 catalyzer
| Catalyzer | ???C 1 | ???C 2 | ???C 3 | ???C 4 | ??C 5 | ???C 6 | ???C 7 | ???C 8 |
| Tap density g/ml side pressure strength N/mm specific surface area m 2/ g pore volume (mercury penetration method) ml/g can a few aperture nm pore size distribution % 10-20nm MoO 3?m％ CoO??m％ NiO??m％ | ?0.61 ?15.7 ?168 ?0.828 ?17.3 ?78 ?8.90 ?3.25 ?- | ??0.58 ??16.3 ??145 ??0.965 ??17.8 ??81 ??3.68 ??1.01 ??- | ??0.60 ??16.0 ??153 ??0.880 ??18.0 ??79 ??9.12 ??2.96 ??- | ??0.62 ??17.2 ??140 ??0.790 ??16.8 ??79 ??10.03 ??- ??3.02 | ?0.59 ?15.3 ?140 ?0.820 ?17.1 ??77 ??9.07 ??- ??2.32 | ??0.60 ??15.4 ??142 ??0.870 ??18.1 ??78 ??8.98 ??- ??2.65 | ??0.48 ??4.9 ??160 ??0.860 ??14.0 ??48 ??8.85 ??- ??2.61 | ??0.60 ??8.6 ??140 ??0.881 ??17.1 ??60 ??9.03 ??- ??3.02 |
Data show in the table 1, compare catalyzer (C of the present invention with the reference agent
1-C
6) pore distribution concentration, intensity is good, and tap density is suitable.
Embodiment 8
Under identical appreciation condition, more above-mentioned each routine catalyst hydrogenation desulfurization and hydrodemetallation (HDM) (Ni+V) performance.Estimating stock oil is that isolated island subtracts slag, and its character and evaluation processing condition are as shown in table 2, and evaluation result sees Table 3.
Table 2 stock oil character and processing condition
| The μ g/g of stock oil character S m%/(Ni+V) | ????2.51/44.4 |
| Estimate processing condition temperature of reaction ℃/reaction pressure Mpa hydrogen-oil ratio (v)/air speed h -1 | ????380/14.7 ????850/1.0 |
Table 3 catalyst activity evaluation result
It is active active in following formula calculating with relative taking off (Ni+V) to take off S in the table 3 relatively:
| Catalyzer | ???C 1 | ???C 2 | ???C 3 | ???C 4 | ???C 5 | ???C 6 | ??C 7 | ??C 8 |
| Take off the active % of S relatively and take off (Ni+V) active % relatively | ??114 ??103 | ??108 ??104 | ??112 ??103 | ??111 ??107 | ??109 ??103 | ??112 ??105 | ??97 ??88 | ??100 ??100 |
By table 3 result as can be seen, compare with the reference agent, catalyzer of the present invention has higher hydrogenating desulfurization and hydrodemetallation (HDM) activity.
Claims (15)
1. the preparation method of a heavy oil hydrogenating treatment catalyst may further comprise the steps:
(1) two kinds of aluminum oxide of different nature and compound expanding agent, extrusion aid, peptizing agent, water are mixed pinch, until becoming plastic, extruded moulding, roasting obtains carrier of the present invention;
(2) with the solution impregnation carrier of the present invention that contains active metal component, drying and roasting then gets catalyzer of the present invention.
2. according to the described preparation method of claim 1, it is characterized in that described compound expanding agent is physics expanding agent and chemical enlargement agent.
3. according to the described preparation method of claim 2, it is characterized in that described physics expanding agent is a carbon black, its consumption is 1-15m%; Described chemical enlargement agent is boric acid, phosphoric acid or borate, phosphoric acid salt, and add-on is 0.05-5.0m%.
4. according to the described preparation method of claim 2, it is characterized in that described physics expanding agent is a carbon black, its consumption is 3-10m%; Described chemical enlargement agent is boric acid, phosphoric acid or borate, phosphoric acid salt, and add-on is 0.1-1.5m%.
5. according to the described preparation method of claim 1, it is characterized in that said two kinds of aluminum oxide of different nature are that aluminium hydroxide is pseudo-boehmite, γ-Al
2O
3, δ-Al
2O
3, η-Al
2O
3, the weight ratio of two kinds of different aluminum oxide is 1: 25-25: 1.
6. according to the described preparation method of claim 1, it is characterized in that described extrusion aid is sesbania powder, methylcellulose gum, starch, polyvinyl alcohol, add-on is 2.0-8.0m%.
7. according to the described preparation method of claim 1, it is characterized in that said peptizing agent is organic acid or mineral acid, add-on is 0.5-10.0m%.
8. according to the described preparation method of claim 1, it is characterized in that said organic acid is formic acid, acetate, said mineral acid is a nitric acid, and add-on is 1.0-3.0m%.
9. a heavy oil hydrogenating treatment catalyst is characterized in that the catalyzer pore volume is 0.5-1.2ml/g, and specific surface area is 100-200m
2/ g can several apertures be 15-23nm, and the aperture accounts for more than 70% of total pore volume at the pore volume between the 10-20nm.
10. according to the described catalyzer of claim 9, it is characterized in that the catalyzer pore volume is 0.6-0.9ml/g, specific surface area is 120-180m
2/ g can several apertures be 16-20nm, and the aperture accounts for more than 70% of total pore volume at the pore volume between the 10-20nm.
11., it is characterized in that the pore volume of catalyzer aperture＞16nm accounts for the 40-75% of total pore volume according to claim 9 or 10 described catalyzer.
12., it is characterized in that described catalyzer contains group vib metal oxide 1.0-14.0w% according to the described catalyzer of claim 9, contain group VIII metal oxide 0.1-8.0w%, remainder is an aluminum oxide.
13., it is characterized in that described catalyzer contains group vib metal oxide 3.0-12.0w% according to the described catalyzer of claim 12, contain group VIII metal oxide 0.5-5.0w%, remainder is an aluminum oxide.
14., it is characterized in that said catalyzer physical strength 〉=10.0N/mm, tap density 〉=0.50g/ml according to the described catalyzer of claim 9.
15., it is characterized in that said catalyst buildup density is 0.52-0.60g/ml according to the described catalyzer of claim 14.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00123223 CN1123628C (en) | 2000-11-08 | 2000-11-08 | Heavy oil hydrogenating treatment catalyst and its preparing method |
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|---|---|---|---|
| CN 00123223 CN1123628C (en) | 2000-11-08 | 2000-11-08 | Heavy oil hydrogenating treatment catalyst and its preparing method |
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|---|---|
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| CN1123628C CN1123628C (en) | 2003-10-08 |
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| CN1308073C (en) * | 2004-03-16 | 2007-04-04 | 潍坊联信化学有限公司 | Catalyst for improving organic sulfur hydrolysis rate, its carrier and preparation method |
| CN100388980C (en) * | 2003-10-31 | 2008-05-21 | 中国石油化工股份有限公司 | Quasi-thin empholite composition containing organic reaming agent |
| CN101485953B (en) * | 2008-05-27 | 2011-12-14 | 北京三聚环保新材料股份有限公司 | Method for preparing desulfurizing agent |
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| CN103480422A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Catalyst having hydrogenation catalysis function, and preparation method and application thereof, and hydrogenation treatment method |
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| CN109304182A (en) * | 2017-07-28 | 2019-02-05 | 中国科学院宁波材料技术与工程研究所 | Hydrorefining catalyst for treating inferior oil and its preparation method and application |
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2000
- 2000-11-08 CN CN 00123223 patent/CN1123628C/en not_active Expired - Lifetime
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| CN100388980C (en) * | 2003-10-31 | 2008-05-21 | 中国石油化工股份有限公司 | Quasi-thin empholite composition containing organic reaming agent |
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| CN101485953B (en) * | 2008-05-27 | 2011-12-14 | 北京三聚环保新材料股份有限公司 | Method for preparing desulfurizing agent |
| CN102861620A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Method for preparing hydrogenation demetallization catalyst |
| CN102861620B (en) * | 2011-07-07 | 2015-05-13 | 中国石油化工股份有限公司 | Method for preparing hydrogenation demetallization catalyst |
| CN103041871A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Preparation method of alumina supporter |
| CN103041871B (en) * | 2011-10-17 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of preparation method of alumina support |
| CN103055932B (en) * | 2011-10-24 | 2015-02-18 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
| CN103055932A (en) * | 2011-10-24 | 2013-04-24 | 中国石油化工股份有限公司 | Residual oil hydrotreating catalyst and preparation method thereof |
| CN103480422A (en) * | 2012-06-12 | 2014-01-01 | 中国石油化工股份有限公司 | Catalyst having hydrogenation catalysis function, and preparation method and application thereof, and hydrogenation treatment method |
| CN103480422B (en) * | 2012-06-12 | 2016-01-13 | 中国石油化工股份有限公司 | There is the Catalysts and its preparation method of hydrogenation catalyst effect and application and hydrotreating method |
| CN103769118A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN103769118B (en) * | 2012-10-24 | 2017-05-17 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and preparation method thereof |
| CN108236958A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | Preparation method of hydrodesulfurization catalyst |
| CN109304182A (en) * | 2017-07-28 | 2019-02-05 | 中国科学院宁波材料技术与工程研究所 | Hydrorefining catalyst for treating inferior oil and its preparation method and application |
| CN110038542A (en) * | 2018-01-17 | 2019-07-23 | 中国石油化工股份有限公司 | A method of preparing the alpha-alumina supports of alkene epoxidation silver catalyst |
| CN110227481A (en) * | 2019-06-25 | 2019-09-13 | 中化泉州石化有限公司 | A kind of catalyst for hydroprocessing of heavy oil and preparation method thereof |
| CN112675828A (en) * | 2020-12-25 | 2021-04-20 | 中化泉州石化有限公司 | Hydrodesulfurization catalyst and preparation method thereof |
| CN116408115A (en) * | 2021-12-31 | 2023-07-11 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst and preparation method and application thereof |
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