CN1041430C - Hydro-treated catalyst and preparation method thereof - Google Patents
Hydro-treated catalyst and preparation method thereof Download PDFInfo
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- CN1041430C CN1041430C CN95105207A CN95105207A CN1041430C CN 1041430 C CN1041430 C CN 1041430C CN 95105207 A CN95105207 A CN 95105207A CN 95105207 A CN95105207 A CN 95105207A CN 1041430 C CN1041430 C CN 1041430C
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Abstract
The present invention provides a catalyst suitable for the hydrotreatment of heavy distillate oil, which comprises 65 to 80 wt% of gamma-Al2O3, 3 to 6 wt% of NiO, 15 to 25 wt% of MoO3 and 2 to 5 wt% of P. An alumina carrier used in the catalyst is prepared with a PH swing method, the specific surface area of the alumina carrier is larger than 280 to 380 m<2>/g, the pore volume is larger than 0.66 cc/g, and the volume of pores with the pore diameter of 40 to 50A accounts for more than 70% of the total pore volume. The gamma-Al2O3 after being impregnated in Mo-Ni-P co-impregnation liquid in a spraying mode is loaded on the surface of the carrier to obtain the high-activity hydrotreating catalyst. The method of the present invention has the advantages of simple technology, wide raw material sources and low price. The denitrification rate of the catalyst for the hydrodenitrogenation of heavy oil is higher than 99.5% when the nitrogen content of the heavy oil is higher than 2000 ppm.
Description
The invention belongs to catalyzer, particularly a kind of with γ-Al
2O
3Be hydrodenitrogenation catalyst of carrier and preparation method thereof.
Hydrotreating catalyst generally adopts γ-Al
2O
3Make carrier, then on carrier load Mo or W, Ni or Co, P to improve activity of such catalysts.Its carrier γ-Al
2O
3Because preparation method's difference causes activity of such catalysts also to differ widely.United States Patent (USP) 4,562,059 disclosed Al
2O
3The preparation method is: with a kind of aluminum salt solution and another kind of adjustment solution that does not contain aluminium salt of containing, make the aluminum oxide that pore volume is concentrated through the PH swing method, what its effect was best is the sodium aluminate and the nitric acid precipitator method, explanation aluminum oxide useful as catalysts carrier in the literary composition, but do not have the yet specific surface data of unlisted aluminum oxide of concrete use-case.United States Patent (USP) 4,721,696 and 4,758,330 provide and prepare Si modified aluminas and make the method for hydrotreating catalyst for carrier with it, the PH swing method is adopted in the preparation of its alumina supporter, use three kinds of solution, a kind of is aluminium salt (mainly being aluminum nitrate), and another kind of is composite alkali aluminum salt (mainly being sodium metaaluminate), after above-mentioned two kinds of solution swing becomes glue more than 5 times, add the third solution-alkalimetal silicate (mainly being sodium metasilicate), thereby be prepared into Si modification γ-Al
2O
3The Si modified aluminas that this method is prepared, the aperture is big, and the hole of 200-1000A accounts for 50-60%, and its active component content of Mo-Ni-P catalyzer of making is low, and pore volume is big, can not be used for the heavy-oil hydrogenation denitrogenation, generally only is used for desulfurization, the demetalization of residual oil.
The object of the present invention is to provide a kind of technology simply with γ-Al
2O
3Be the Catalysts and its preparation method of carrier, this catalyzer is applicable to heavy fraction of oil hydrodenitrification or desulfurization.
Its composition of hydrotreating catalyst of the present invention and scope (weight percent) are:
γ-Al
2O
3?60-80 NiO 3-8
MoO
3 15-27 P
2O
5 4.5-11.2
This catalyzer is owing to used the γ-Al with premium properties
2O
3Make carrier, thus in load after the Mo-Ni-P active ingredient, its physical parameter is:
Specific surface (m
2.g) 160-200
Pore volume (cc/g) 0.3-0.4
The aperture is concentrated hole (%) 75-90 of 40-100A
Described γ-Al
2O
3Physical parameter be:
Specific surface (m
2/ g) 250-350m
2/ g pore volume (cc/g) 0.6-0.75cc/g
The hole of aperture 40-100A accounts for the 75-90% of total pore volume.
Above-mentioned Preparation of catalysts method is carried out as follows:
(1) preparation γ-Al
2O
3
A. in colloid generating kettle, add end water and be heated to 50-80 ℃, add aluminate solution or acid earlier, transfer PH to 2-3, stirred 5-10 minute,
B. add alkaline solution or alkali metal aluminate solution, till making PH to 8-10 under continuous the stirring, stirred 5-10 minute,
C. above-mentioned a, the repetitive operation of b process 2-5 time, and make it fully to react 40-80 minute after-filtration,
D. filter cake gets aluminum hydroxide solid elastomer with dilute ammonia solution washing 4-6 time after the 100-140 ℃ of drying,
E. be extruded into three leaves or Herba Galii Bungei shape bar after 200 mesh sieves being crossed in the aluminum hydroxide solid elastomer fragmentation,, get γ-Al at 450 ℃ of-600 ℃ of following roasting 2-12 hours
2O
3,
(2) preparation Mo-Ni-P co-impregnated solution, its component concentration ranges (g/100ml co-impregnated solution) is:
MoO
3 30-50 NiO 5-10
P 2-8
(3) co-impregnated solution is sprayed in the γ-Al for preparing
2O
3On the bar,
(4) material after spraying is in airtight container the vexed 1-2 of soaking hour, and low temperature dries in the shade then, 100-140 ℃ of oven dry down, is the Mo-Ni-P hydrotreating catalyst after the 450-550 ℃ of roasting again.
Distillate in the refining of petroleum, particularly the nitrogenate molecule is big in the heavy oil fraction, and is difficult to remove, and requires support of the catalyst to have high surface, big and concentrated hole is so that the absorption and the diffusion of high-load metal component of uniform loading (30-40%) and reactant molecule.Can satisfy above-mentioned requirements by alumina catalyst support catalyzer provided by the present invention.
γ-the Al of alumina supporter that hydrotreating catalyst of the present invention is used for adopting the PH swing method to prepare
2O
3, described PH swing method is promptly used two kinds of solution, its pH value is replaced under the situation about changing to acid by alkali by acid to alkaline again become glue.These two kinds of solution can be aluminate solution and alkaline solution, or acid solution and alkali metal aluminate solution; Described aluminate solution can be the solution of aluminum nitrate, aluminum chloride or Tai-Ace S 150; Described alkaline solution can be ammoniacal liquor, sodium hydroxide solution.Described alkali metal aluminate solution is a sodium aluminate solution; Described acid solution can be nitric acid, hydrochloric acid, sulphuric acid soln.Two kinds of solution alternately being added pH value is changed between soda acid, also is that aluminum hydroxide sol is among the variation of resolution of precipitate partly.Adopt the γ-Al of this method preparation
2O
3Specific surface can reach 250-350m
2/ g, pore volume 0.55-0.75cc/g, the aperture is the 75-90% that the concentrated hole of 40-100A accounts for total pore volume.It is a kind of support of the catalyst with premium properties.
The used aluminate of preparation alumina catalyst support mainly is a Tai-Ace S 150, particularly derives from the cheap bauxitic clay alum liquor that deferrization makes after the sulfuric acid stripping, and its concentration is 3-10g Al
2O
3/ 100ml, but the alkaline solution working concentration is 5-20g NH
3The ammoniacal liquor of/100ml or the NaOH of 2-6N.
Change repetitive operation through 2-5 soda acid, 40-80 minute after-filtration of last fully reaction, filter cake washs 4-8 time with dilute ammonia solution.If the SO when making precipitation agent in the control wash filtrate with ammoniacal liquor
4 2-Content＜0.5% is (to Al
2O
3), if check then that with NaOH Na content＜0.05% in the filter cake is (to Al
2O
3).Filter cake gets aluminum hydroxide solid elastomer after 100-140 ℃ of drying, the X-ray test is typical pseudo-boehmite, differential thermal analysis three water-contents＜1%.
With broken 200 orders of crossing of the aluminum hydroxide solid elastomer that so makes, use the HNO of 2-6% then
3Or acetic acid peptization extrusion, be shaped as three leaves or the Herba Galii Bungei type of 1.2-1.4mm, long 1-3mm.Get γ-Al after 2-12 hour in activation under 500-600 ℃
2O
3
The preparation of co-impregnated solution: preparation Mo-Ni-P co-impregnated solution, can use MoO
3, basic nickel carbonate and phosphoric acid is raw material or all can with Ammonium Heptamolybdate, nickelous nitrate and phosphoric acid preparation.Strength of solution is decided on the catalyzer composition, and its composition range is: MoO
330-50g/100ml, NiO 5-10g/100ml, P are 2-8g/100ml, all the other are deionized water.Slowly add MoO after water and phosphoric acid can being heated to 30-50 ℃ during a kind of batching before using
3Be warming up to 80-90 ℃ with basic nickel carbonate, be stirred to complete molten till.Can earlier phosphoric acid be added in the Ammoniun Heptamolybdate Solution during with back three kinds of raw materials, it be mixed with nickel nitrate solution again, above-mentioned two kinds of methods all can obtain the solution of stable transparent.
Supporting of active ingredient: the calculating for preparing catalyzer by desire is formed to join and is decided co-impregnated solution, and it is sprayed in the carrier γ-Al for preparing
2O
3On the bar, spray step to guarantee solution just suppressed by vector all absorb and do not have unnecessaryly, does not have not enoughly yet, need to measure the water regain of carrier before therefore spraying, thereby the concentration of decision use solution.Supporting also of active ingredient can be used the method for soaking, and the recyclable continuation of excessive solution is used.Material after spraying needs vexed soaking 1-2 hour in airtight container, reenters baking oven 100-140 ℃ drying then after low temperature dries, and promptly gets the Mo-Ni-P hydrotreating catalyst after the 450-550 ℃ of roasting.
Hydrotreating catalyst of the present invention adopts the γ-Al of PH swing method preparation
2O
3Make carrier, have the advantage active high, that denitrification percent is high, when in the stock oil during nitrogen content 1200～2000PPM, denitrification percent still can＞99.5%.Method for preparing catalyst technology of the present invention is simple, raw material sources are extensive and cheap, prepared catalyzer is suitable for the hydrotreatment of distillate, the particularly hydrodenitrification of mink cell focus fraction, hydrogenating desulfurization, also can be used for the hydrofining of low pressure poor ignition quality fuel hydrofining, especially coker gas oil and residual oil catalytic cracking gained diesel oil.γ-Al that catalyzer of the present invention is prepared
2O
3Carrier also can be used for preparing other hydrotreating catalyst, or is used as the integral part of hydrocracking catalyst.
Embodiment 1
Add end water 5 liters in 20 liter stirring tanks, (concentration is with Al inwardly to add alum liquor after being heated to 70 ℃
2O
3Count 7.2g/100ml), regulate pH value 2.5-3.0, (concentration is with NH to add ammoniacal liquor under fully stirring
3Count 10.25g/100ml), regulating PH to 9.0 stops to feed in raw material, stirred 10 minutes, slowly add alum liquor again and transfer PH, so repeating aforesaid operations, promptly to swing 3 rear slurry pH values be to stop to feed in raw material in 9.0 o'clock, stirred aging 1 hour, removes by filter mother liquor, and, check SO in the filtrate with weak ammonia washing precipitation 5-6 time
4 2-Content＜0.5% is (to Al
2O
3Meter) till, 120 ℃ of dryings of filter cake get aluminum hydroxide solid elastomer 395 grams, with its broken 200 mesh sieves of crossing, use 4%HNO
3Solution sticking and and be extruded into 1.2 3 leaves or Herba Galii Bungei type bar, dry back 540 ℃ of roastings 4 hours are γ-Al
2O
3Carrier A.
Embodiment 2
Identical with embodiment 1 working method, difference is end water 10 liters, and alum liquor concentration 8.26g/100ml, alkali lye 4.6N NaOH, 70 ℃ of PH of temperature replace scope 3-10 swing 4 times, must do glue 318g, make γ-Al
2O
3Carrier B.
Embodiment 3
Identical with embodiment 2 working method, difference is end water 5 liters, 65 ℃ of temperature, and post precipitation adding 31.1g water glass (SiO is finished in PH 2.5-9.5 swing 2 times
2Content 24.1%), must do glue 310g, be prepared into γ-Al
2O
3Support C.
Embodiment 4
Identical with embodiment 3 working method, difference is that temperature is 70 ℃, swing 3 times after adding water glass 22.1g must do glue 380g, be prepared into γ-Al
2O
3Carrier D.
Embodiment 5
Identical with embodiment 3 working method, difference is that alkali lye is sodium aluminate solution, salic 24.4g/100ml, and 70 ℃ of PH 3-10 get γ-Al
2O
3Dried glue 160 grams are prepared into carrier E.
Embodiment 6
The present embodiment working method is raw material with embodiment 1 with sodium metaaluminate and sulfuric acid, and concentration is respectively 12.5g Al
2O
3/ 100ml and 15g H
2SO
4/ 100ml, 60 ℃ of temperature, PH 3-10 swings 4 times, gets γ-Al
2O
3Dried glue is prepared into carrier F.
Table 1 has been listed above-mentioned six kinds of γ-Al
2O
3The physical data of liquid nitrogen determining adsorption.
Table 1 γ-Al
2O
3Physical data carrier specific surface pore volume mean pore size pore distribution %
m
2/g cc/g A ＜40A 40-100A ＞100A A 271.7 0.65 62.32 8.85 79.26 11.95 B 273.3 0.66 67.40 7.49 69.59 22.90 C 315.9 0.79 60.92 10.91 79.21 18.23 D 330.5 0.74 62.00 3.59 90.5 5.68 E 322.5 0.62 54.80 14.8 77.30 7.90 F 291.3 0.66 61.12 6.56 91.20 2.26
Embodiment 7
Take by weighing 85% phosphatase 79 1.35g, add the industrial MoO that has weighed when placing 406ml water to be heated with stirring to 50 ℃
3229.6g basic nickel carbonate 82.62g continues to be heated with stirring to solution temperature and reaches 90 ℃, keeps 4-8 hour cold filtration, makes co-impregnated solution.
Get 100ml γ-Al
2O
3Carrier A is dripped thereon with above-mentioned co-impregnated solution 50ml after 1 hour equably in baking under 120 ℃, and constantly upset, shakes up, and back vexed soaking about 1 hour in closed unit gone into 120 ℃ in baking oven after drying, and 450-500 ℃ of activation promptly gets the A-M catalyzer.
Embodiment 8
B, C, four kinds of carriers of D, E are sprayed as the method for embodiment 7 respectively, make B-M, C-M, D-M, E-M catalyzer, the catalyzer physical data is listed in table 2.
Table 2 catalyzer physical data catalyst specific surface pore volume mean pore size pore distribution %
m
2/g cc/g A 40A 40-100A ＞100A A-M 153.6 0.32 61.35 5.84 83.93 10.23 B-M 189.5 0.39 63.2 8.35 77.20 14.42 C-M 187.1 0.43 65.8 4.72 82.90 12.35 D-M 188.4 0.42 63.0 4.72 85.26 10.52 E-M 188.5 0.43 58.6 8.55 81.21 10.23
Embodiment 9
Above-mentioned catalyzer is used for heavy distillate (boiling spread 342-525 ℃) hydrodenitrification.Get the 100ml catalyzer in reaction unit, reaction pressure 16MPa, temperature 370-390 ℃, H
2/ oil ratio 1000-1500, stock oil volume space velocity 1.0h
-1, contain N 1200-2000PPM, denitrification percent＞99.5%.Its study on the stability 2000 hours is suitable with the commercial catalysts comparing result.Catalyst reaction the results are shown in table 3.
Table 3
Temperature of reaction ℃ stagnation pressure MPa raw material air speed h
-1Average denitrification percent % relative activity sampling time hA-M 388 16 1.0 99.7 98.8 8-1640B-M 388 16 1.0 99.67 97.5 8-1024C-M 388 16 1.0 99.76 103.0 8-1056E-M 388 16 1.0 99.84 109.8 8-120HC-K 388 16 1.0 99.22 100 8-1312
HC-K is a commercial catalysts
Specific surface in the above-mentioned data, pore volume, aperture employing ZXF-04 adsorb instrument liquid nitrogen determination of adsorption method automatically.
Claims (10)
1. one kind with γ-Al
2O
3Be the hydrotreating catalyst of carrier, it is characterized in that moiety and scope (weight percent) are:
γ-Al
2O
3 60-80 NiO 3-6
MoO
3 15-27 P
2O
5 4.5-11.2
Its physical parameter is:
Specific surface (m
2/ g) 160-200
Pore volume (cc/g) 0.3-0.4
The aperture is concentrated hole (%) 75-90 of 40-100A.
2. catalyzer as claimed in claim 1 is characterized in that γ-Al
2O
3The carrier physical parameter be:
Specific surface (m
2/ g) 250-350m
2/ g pore volume (cc/g) 0.6-0.75cc/g
The hole of aperture 40-100A accounts for total pore volume 75-90%.
3. one kind with γ-Al
2O
3Be the preparation method of hydrotreatment catalyst of carrier, it is characterized in that carrying out as follows:
(1) preparation carrier γ-Al
2O
3
A. in colloid generating kettle, add end water and be heated to 50-80 ℃, add aluminate solution or acid earlier, transfer pH to 2.5-3.5, stirred 5-10 minute,
B. add alkaline solution or alkali metal aluminate, under constantly stirring, make the pH value till the 8-10, stirred 5-10 minute,
C. behind the above-mentioned a, the repetitive operation of b process 2-5 time, make it fully to react 40-80 minute after-filtration,
D. filter cake gets aluminum hydroxide solid elastomer with dilute ammonia solution washing 4-8 time after the 100-140 ℃ of drying,
E. with extrusion behind the broken mistake of aluminum hydroxide solid elastomer＜200 mesh sieves,, get γ-Al at 450-600 ℃ of following roasting 2-12 hour
2O
3,
(2) preparation Mo-Ni-P co-impregnated solution, its component concentration ranges (g/100ml co-impregnated solution) is:
MoO
3 30-50 NiO 5-10
P 2-8
(3) co-impregnated solution is dipped in the γ-Al for preparing
2O
3On the bar, the material after spraying in airtight container the vexed 1-2 of soaking hour, low temperature dries then, 100-140 ℃ of oven dry down, is the Mo-Ni-P hydrotreating catalyst after the 450-550 ℃ of roasting again.
4. method as claimed in claim 3 is characterized in that described aluminate solution can be the solution of Tai-Ace S 150, aluminum chloride or aluminum nitrate preparation.
5. method as claimed in claim 4 is characterized in that described aluminate solution can also be is starting raw material with the bauxitic clay, the alum liquor that obtains after the acid-soluble material deferrization.
6. method as claimed in claim 3 is characterized in that described alkaline solution can be ammoniacal liquor or sodium hydroxide solution.
7. method as claimed in claim 3 is characterized in that described alkali metal aluminate solution is a sodium aluminate solution.
8. method as claimed in claim 3 is characterized in that described acid solution can be sulfuric acid, nitric acid, hydrochloric acid soln.
9. method as claimed in claim 3, the preparation that it is characterized in that described Mo-Ni-P co-impregnated solution is to use MoO
3, basic nickel carbonate and phosphoric acid boils altogether in 70-90 ℃ and obtains.
10. method as claimed in claim 3, the preparation that it is characterized in that described Mo-Ni-P co-impregnated solution can be that ammonium molybdate and phosphoric acid and nickel nitrate solution are mixed with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95105207A CN1041430C (en) | 1995-05-06 | 1995-05-06 | Hydro-treated catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95105207A CN1041430C (en) | 1995-05-06 | 1995-05-06 | Hydro-treated catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135518A CN1135518A (en) | 1996-11-13 |
| CN1041430C true CN1041430C (en) | 1998-12-30 |
Family
ID=5075399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95105207A Expired - Fee Related CN1041430C (en) | 1995-05-06 | 1995-05-06 | Hydro-treated catalyst and preparation method thereof |
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| Country | Link |
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Families Citing this family (10)
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|---|---|---|---|---|
| CN1055955C (en) * | 1997-11-24 | 2000-08-30 | 中国石油化工总公司 | Hydrogenation catalyst and preparation thereof |
| CN1089635C (en) * | 2000-03-02 | 2002-08-28 | 南开大学 | Catalyst using TiO2 as carrier to load metal nitride Mo2N |
| CN100412168C (en) * | 2002-06-07 | 2008-08-20 | 上海博申工程技术有限公司 | Coal tar hydrogenation process and catalyst therefor |
| CN100496738C (en) * | 2004-12-28 | 2009-06-10 | 中国石油化工股份有限公司 | Alumina supporter possessing duplicate orifice, catalyst and preparation method |
| CN100537028C (en) * | 2006-06-16 | 2009-09-09 | 中国石油化工股份有限公司 | Preparation process of hydroprocessing catalyst |
| CN101260318B (en) * | 2007-03-08 | 2013-05-08 | 北京三聚环保新材料股份有限公司 | Lithium-containing hydrorefining catalyst and its preparation method |
| CN102626635B (en) * | 2012-03-16 | 2014-03-05 | 山西盛驰科技有限公司 | Coal tar denitrification catalyst and its preparation method and use |
| CN110642278B (en) * | 2018-06-26 | 2022-02-08 | 中国石油化工股份有限公司 | Method for preparing aluminum hydroxide |
| CN110773185A (en) * | 2019-11-27 | 2020-02-11 | 浙江石油化工有限公司 | Silicon-containing residual oil hydrotreating catalyst and preparation method thereof |
| CN111001424A (en) * | 2019-11-27 | 2020-04-14 | 浙江石油化工有限公司 | Phosphorus-containing residual oil hydrotreating catalyst and preparation method thereof |
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| US4358361A (en) * | 1979-10-09 | 1982-11-09 | Mobil Oil Corporation | Demetalation and desulfurization of oil |
| US4758330A (en) * | 1987-03-11 | 1988-07-19 | Phillips Petroleum Company | Hydrotreating employing silica-modified alumina |
| CN1033285A (en) * | 1987-11-22 | 1989-06-07 | 齐鲁石油化工公司研究院 | Low-voltage hydrogenation denitrification catalyst and uses thereof |
| CN1059551A (en) * | 1990-07-05 | 1992-03-18 | 切夫里昂研究和技术公司 | High activity slurry catalyst process |
| US5118406A (en) * | 1991-04-30 | 1992-06-02 | Union Oil Company Of California | Hydrotreating with silicon removal |
-
1995
- 1995-05-06 CN CN95105207A patent/CN1041430C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4238320A (en) * | 1979-04-19 | 1980-12-09 | Gulf Research & Development Company | Denitrogenation of shale oil |
| US4358361A (en) * | 1979-10-09 | 1982-11-09 | Mobil Oil Corporation | Demetalation and desulfurization of oil |
| US4358631A (en) * | 1980-09-10 | 1982-11-09 | Mitsubishi Denki Kabushiki Kaisha | Heat dissipating electrical bushing |
| US4758330A (en) * | 1987-03-11 | 1988-07-19 | Phillips Petroleum Company | Hydrotreating employing silica-modified alumina |
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| US5118406A (en) * | 1991-04-30 | 1992-06-02 | Union Oil Company Of California | Hydrotreating with silicon removal |
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|---|---|
| CN1135518A (en) | 1996-11-13 |
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