CN102641739B - Hydrogenation catalyst of a kind of alkalinous metal and the equal distribution gradient of active metal component concentration and preparation method thereof - Google Patents
Hydrogenation catalyst of a kind of alkalinous metal and the equal distribution gradient of active metal component concentration and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to the preparation method of the hydrogenation catalyst of a kind of active metal and alkalinous metal concentration in gradient increase distribution, by the rarer active metal solution of preparation and alkalinous metal solution or deionized water, in spray-stain process, progressively add denseer active metal solution and the saturated spray-stain carrier of alkalinous metal solution; Or pass through active metal solution and the alkalinous metal solution of preparation variable concentrations, be immersed in from low to high on carrier by active metal maceration extract and alkalinous metal solution concentration; Or with the lower solution of alkali concentration or deionized water dipping, progressively add the higher solution of alkalinous metal concentration in dipping process in maceration extract; Drying and roasting; Again with the lower solution of active metal concentrations or deionized water dipping, progressively add the higher solution of active metal concentrations in dipping process in maceration extract; Or alkalinous metal be immersed in active metal dipping after; Catalyst has higher desulfurization, denitrogenation and metal removal activity and stability, and preparation process is simple.
Description
Technical field
The present invention relates to hydrogenation catalyst of a kind of alkalinous metal and the equal distribution gradient of active metal component concentration and preparation method thereof.
Background technology
Along with crude oil heaviness, in poor quality aggravation in world wide, the increasingly stringent of environmental regulation, the demand of market to light-end products but increases year by year simultaneously, hydrogen addition technology is faced with great challenge as the manufacturing process mainly producing clean fuel, in the urgent need to developing better hydrogenation technique and activity, hydrogenation catalyst that stability is more excellent.
Hydrotreatment and the reforming catalyst of modern petroleum refining industry almost all adopt alumina support.Due to the irregular condensation of surface hydroxyl, alumina support all has certain acidity, and these acid centres easily cause hydrocarbon condensation and form carbon deposit, cause catalysqt deactivation.Especially some is very easily caused to the hydroprocessing processes of carbon deposit, the power of catalyst support surface acidity directly determines that catalyst can the length of stable operation cycle.At present, hydrotreating catalyst all with aluminium oxide or containing one or more other elements if the aluminium oxide of Si, Ti, P, B, F etc. is for carrier.In catalyst preparation process, above-mentioned element can be introduced in different phase in system, its objective is basically identical, be i.e. the acidity of regulating catalyst and/or the interaction that improves between active component and carrier.
At present, the hydrogenation catalyst containing IA and IIA race metal promoter is widely used.In gasoline hydrogenation field, US Patent No. P 5459118 discloses a kind of containing the alkali-metal gasoline hydrogenation catalyst of IA race, effectively can suppress olefin saturated.CN 1252222C discloses a kind of preparation method of selective hydrogenation catalyst for gasoline, and feature take aluminium oxide as carrier, with molybdenum and cobalt for active component, simultaneously containing auxiliary agent potassium and phosphorus.CN 1123309A discloses a kind of Hydrodemetalation catalyst and preparation method. and its carrier take aluminium oxide as precursor, alkali metal (potassium) and phosphorus and active component is introduced by different impregnation method, reduce the edge active of catalyst, improve the appearance metal ability of catalyst.
The common feature of above patented technology is that the CONCENTRATION DISTRIBUTION of alkalinous metal in catalyst carrier is comparatively even.At present, the report about the preparation method of the hydrogenation catalyst of alkalinous metal uneven concentration distribution is less.
Summary of the invention
The object of this invention is to provide hydrogenation catalyst of a kind of alkalinous metal and the equal distribution gradient of active metal component concentration and preparation method thereof.Hydrogenation catalyst containing alkalinous metal is used for mink cell focus field of hydrogenation, is particularly useful for deasphalted oil, decompressed wax oil, wax tailings, the hydro-upgrading of reduced crude and decompression residuum and conversion.The advantage of the inventive method is: catalyst granules increases to outer alkalinous metal and active metal component concentration in gradient distribution gradually from interior, and catalyst preparation process of the present invention is simple, low cost of manufacture.
The concrete preparation process of the hydrogenation catalyst of alkalinous metal and the equal distribution gradient of active metal concentrations is:
The preparation of hydrogenation catalyst: select Al
2o
3or containing SiO
2, TiO
2, ZrO
2al
2o
3as carrier, alkalinous metal and active metal are made into maceration extract, adopt the saturated method that sprays to prepare hydrogenation catalyst.
Active metal component of the present invention is selected from VIB and/or group VIIIB metallic compound, preferred molybdenum and/or tungsten and/or nickel and/or cobalt compound.
Alkalinous metal of the present invention from least one component in IA group and IIA race, preferred Li, Mg, K, Ca, alkaline metal salt from least one in the water-soluble metal salt of IA and IIA race, preferred LiNO
3, K
2hPO
4, KNO
3, Mg (NO
3)
2, Ca (NO
3)
2.Alkaline metal oxide at the weight content of catalyst between 0.1 ~ 5%.
Spraying can be spray altogether also can spray step by step.The method that sprays altogether is by rarer metal (active metal and the alkalinous metal) solution of preparation or deionized water, is spraying in process, progressively adds the saturated sprayed carrier of method removing denseer metal (active metal and alkalinous metal) solution; Or by preparing metal (active metal and the alkalinous metal) solution of variable concentrations, the method sprayed from low to high on carrier by metal impregnation concentration.Both spray method altogether and can use simultaneously, also can separately use.Spray for substep, the solution lower by alkalinous metal concentration or deionized water spray, and spray in process and progressively add the higher solution of alkalinous metal concentration in maceration extract; At 80 ~ 150 DEG C dry 1 ~ 8 hour again, then at 300 ~ 650 DEG C, preferably roasting 2 ~ 6 hours in the air of 400 ~ 550 DEG C; Spray with the lower solution of active metal component concentration or deionized water again, spray in process and progressively add the higher solution of active metal concentrations in maceration extract.It should be noted that, alkalinous metal sprays step also can carry out before active metal sprays after metal sprays.Active metal and alkali metal component are distributed to center in the gradient reduced gradually by surface at catalyst granules.At 80 ~ 150 DEG C dry 1 ~ 8 hour again, then at 300 ~ 650 DEG C, preferably roasting 2 ~ 6 hours in the air of 400 ~ 550 DEG C.
By a kind of hydrogenation catalyst prepared by the inventive method, it is characterized in that:
1) Al is selected
2o
3or containing SiO
2, TiO
2, ZrO
2al
2o
3as carrier;
2) pore volume is 0.2 ~ 3.0ml/g, is preferably 0.45 ~ 1.3ml/g;
3) specific surface is 20 ~ 400m
2/ g, is preferably 100 ~ 240m
2/ g;
4) catalyst granules neutral and alkali metal component concentration in gradient distribution, on the catalyst particles Zi reducing gradually to interior outward.Catalyst granules center is 0.05 ~ 0.70 with the ratio of the alkalinous metal concentration on surface, be preferably 0.15 ~ 0.45, (center is initial point to 0.33R, R is catalyst granules radius) place is 0.22 ~ 0.85 with the ratio of the alkalinous metal concentration on surface, be preferably 0.28 ~ 0.65,0.66R (R is catalyst granules radius) place is 0.41 ~ 0.93 with the ratio of the alkalinous metal levels on surface, is preferably 0.50 ~ 0.85.Catalyst granules center is 0.05 ~ 0.70 with the ratio of outer surface tenor, be preferably 0.15 ~ 0.45, (center is initial point to 0.33R, R is catalyst granules radius) place is 0.2 ~ 0.8 with the ratio of outer surface tenor, be preferably 0.3 ~ 0.6,0.66R (R is catalyst granules radius) place is 0.4 ~ 0.9 with the ratio of outer surface tenor, is preferably 0.5 ~ 0.8.
The carrier used in method for preparing catalyst of the present invention can be drip a ball forming, spin granulation, extruded, compression molding etc., with drip ball forming and extruded be best.Catalyst shape can be spherical, bar shaped (comprising cylindrical, trilobal, quatrefoil etc.), sheet shape.Be best with spherical and bar shaped.
The effect of invention.
The inventive method has hydrogenation catalyst mainly for the preparation of one.The advantage of the inventive method is: alkalinous metal concentration in gradient distributes, and preparation process is simple, low cost of manufacture.
Accompanying drawing explanation
The active metal of the catalyst granules center to face that Fig. 1 the present invention obtains and alkalinous metal CONCENTRATION DISTRIBUTION.
The active metal of the catalyst granules center to face that Fig. 2 the present invention obtains and alkalinous metal CONCENTRATION DISTRIBUTION.
Detailed description of the invention
Can find out in catalyst granules with reference to the accompanying drawings, alkali metal component concentration can exist with the distribution form of Fig. 1, also can exist with the distribution form of Fig. 2.Fig. 2 can find: from catalyst particle surface to center, and three platforms have appearred in active metal and alkalinous metal CONCENTRATION DISTRIBUTION, two steps.Here it should be noted that, active metal component and the distribution on the catalyst particles of alkali metal component concentration can exist with one or more stepped form.But total trend is: self-catalysis agent particle surface is to center, and active metal and alkali metal component concentration in gradient decline.
Embodiment 1
The present embodiment is with Al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method that sprays is adopted to prepare the catalyst that active metal component is Mo, Ni.
Take 150g carrier, spray 82.5ml ammonia spirit, spray in process at the uniform velocity instill 82.5ml containing 29.8g ammonium molybdate (containing MoO
382m%), 27.0g nickel nitrate (containing NiO 25.2m%), 5g KNO
3ammonia spirit stir in dipping solution, instillation limit, limit sprays, within 5 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 60 DEG C dry 2 hours, then at 120 DEG C dry 5 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst, is numbered C-1.
Embodiment 2
The present embodiment is to contain 1.5%m SiO
2al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method sprayed is adopted to prepare the catalyst that active metal component is Mo, Co.
Take 150g carrier, spray 105ml containing 10g ammonium molybdate (containing MoO
382m%), 8g cobalt nitrate (containing CoO 25.2m%) and 2g LiNO
3ammonia spirit, spray in process at the uniform velocity instill 60ml containing 19.8g ammonium metatungstate (containing MoO
382m%), 19.0g cobalt nitrate (containing CoO 25.2m%) and 8g LiNO
3ammonia spirit stir in dipping solution, instillation limit, limit sprays, within 15 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 120 DEG C dry 4 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst, is numbered C-2.
Embodiment 3
The present embodiment is to contain 1.0%m SiO
2, 1.5m% TiO
2al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method sprayed is adopted to prepare the catalyst that active metal component is W, Ni.
Take 150g carrier, spray 50ml containing 3g ammonium molybdate (containing MoO
382m%), 3g nickel nitrate (containing NiO25.2m%), 2g Mg (NO
3)
2with 2g 85% phosphorus aqueous acid, after having sprayed, then spray 50ml containing 7g ammonium metatungstate (containing MoO
382m%), 5g nickel nitrate (containing NiO 25.2m%), 3g Mg (NO
3)
2with 2g 85% phosphorus aqueous acid, after having sprayed, then spray 65ml containing 19.8g ammonium metatungstate (containing WO
382m%), 19.0g nickel nitrate (containing NiO 25.2m%), 5g Mg (NO
3)
2stir in dipping solution with 5g 85% phosphorus aqueous acid, instillation limit, limit sprays, within 15 minutes, sprayed.To spray in equipment homogenizing after 20 minutes, at 60 DEG C dry 2 hours, after taking-up at 120 DEG C dry 5 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst, is numbered C-3.
Embodiment 4
The present embodiment is to contain 2.0m% ZrO
2al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method that sprays is adopted to prepare the catalyst that active metal component is Mo, Ni.
Take 150g carrier, spray 82.5ml containing 14.75g ammonium molybdate (containing MoO
3aqueous solution 82m%), spray in process at the uniform velocity instill 82.5ml containing 14.75g ammonium molybdate (containing MoO
382m%) with 27.0g nickel nitrate (containing NiO 25.2m%), 5g LiNO
3, 5g Mg (NO
3)
2stir in dipping solution with 5g phosphorus aqueous acid, instillation limit, limit sprays, within 10 minutes, sprayed.To spray in equipment homogenizing after 20 minutes, at 60 DEG C dry 2 hours, after taking-up at 120 DEG C dry 6 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst, is numbered C-4.
Embodiment 5
The present embodiment is with Al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method that sprays is adopted to prepare the catalyst that active metal component is Mo, Ni.
Take 150g carrier, spray 15ml deionized water, spray in process at the uniform velocity instill 75ml containing 10g ammonium molybdate (containing MoO
382m%), 8g nickel nitrate (containing NiO 25.2m%), 1g KNO
3, 2g LiNO
3, 2gMg (NO
3)
2stir in dipping solution with 2g 85% phosphorus aqueous acid, instillation limit, limit sprays, and after having sprayed, and then sprays 30ml again containing 5g ammonium molybdate (containing MoO
382m%), 4g nickel nitrate (containing NiO 25.2m%), 0.5g KNO
3, 1gLiNO
3, 1gMg (NO
3)
2with 1g85% phosphate aqueous solution, after spraying 15ml, at the uniform velocity instill 45ml containing 14.8g ammonium molybdate (containing MoO
382m%), 15g nickel nitrate (containing NiO 25.2m%), 2g KNO
3, 2g LiNO
3with 2g Mg (NO
3)
2stir in maceration extract with 4g 85% phosphorus aqueous acid, instillation limit, limit sprays, within 15 minutes, sprayed.To spray in equipment homogenizing after 10 minutes, at 120 DEG C dry 7 hours, then roasting 6 hours in 500 DEG C of air, obtained catalyst, is numbered C-5.
Embodiment 6
The present embodiment is with containing 1.5m% TiO
2with 2.0m% ZrO
2al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method that sprays is adopted to prepare the catalyst that active metal component is Mo, Ni.
Take 150g carrier, spray 75ml containing 9.0g ammonium molybdate (containing MoO
382m%), 8.0g nickel nitrate (containing NiO25.2m%), 3.5g Ca (NO
3)
2with 2g 85% phosphorus aqueous acid, after having sprayed, and then spray 90ml containing 20.8g ammonium molybdate (containing MoO
382m%), 19.0g nickel nitrate (containing NiO 25.2m%), 8.0g Ca (NO
3)
2with 4g phosphorus aqueous acid.Within 10 minutes, spray.To spray in equipment homogenizing after 20 minutes, at 60 DEG C dry 2 hours, after taking-up at 120 DEG C dry 6 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst, is numbered C-6.
Comparative example 1
The present embodiment is with Al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method that sprays is adopted to prepare the catalyst that active metal component is Mo, Ni.
Take 150g carrier, spray 165ml containing 29.8g ammonium molybdate (containing MoO by saturated absorption amount of solution
382m%), 27.0g nickel nitrate (containing NiO 25.2m%) and 5g KNO
3ammonia spirit.To spray in equipment homogenizing after 5 minutes, at 60 DEG C dry 2 hours, after taking-up at 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst.Be numbered C-7.
Comparative example 2
The present embodiment is with Al
2o
3make carrier, water absorption rate is 1.10mL/g.The saturated method that sprays is adopted to prepare the catalyst that active metal component is Mo, Ni.
Take 150g carrier, spray 185ml containing 29.8g ammonium molybdate (containing MoO
382m%), 27.0g nickel nitrate (containing NiO 25.2m%) and 5g KNO
3ammonia spirit.To spray in equipment homogenizing after 20 minutes, at 60 DEG C dry 2 hours, after taking-up at 120 DEG C dry 3 hours, then roasting 3 hours in 500 DEG C of air, obtained catalyst, is numbered C-8.
Embodiment 7
Adopt the characterization methods such as ICP/AES, BET, EDX to characterize catalyst C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, detailed physico-chemical property is in table 1.
The physico-chemical property of catalyst C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8 is in table 1.
The physico-chemical property of table 1 catalyst
Note: R is catalyst granules radius, with catalyst granules center for starting point.
As can be seen from Table 1, C-1, C-2, C-3, C-4, C-5, C-6 catalyst granules Zi outward in, active metal and the downward trend of alkalinous metal concentration in gradient.And C-7 and C-8 active metal and alkalinous metal CONCENTRATION DISTRIBUTION comparatively even.
Embodiment 9
The present embodiment is catalyst C-1 stability test, and carry out the active and stability of desulfurization removing nitric with C-7 and contrast, adopt catalyst grade combo dress scheme, load metal remover, desulfurizing agent, denitrifier respectively from the bottom to the top in reactor bed, additional proportion is respectively 40%, 20%, 40%.C-1, C-7 are as desulfurizing agent.
Metal remover is prepared according to CN100363470C embodiment 1.
Denitrifier preparation method is as follows:
Take 300gAl
2o
3(butt 68m%) powder, powdered active carbon 9.1g, the blue or green powder 8g in field, three is mixed, adds the acid solution mixed by 200g water and 15g HAc (acetic acid), kneading 1.5 hours, obtain plastic, banded extruder is extruded into the cloverleaf pattern strip of φ 1.10 ~ 1.35mm, this strip at 120 DEG C dry 4 hours, roasting 4 hours at 750 DEG C.With the impregnated activated metal molybdenum of conventional method and nickel, then at 120 DEG C dry 2 hours, at 550 DEG C, roasting 3 hours, namely made catalyst.Wherein MoO
3content is 15.2m%, NiO mass content is 3.6m%, specific area 220m
2/ g, pore volume is 0.55mL/g.
100mL small fixed hydrogenation plant is evaluated.Evaluating feedstock oil is Saudi Arabian Vacuum slag, and character is as shown in table 2.
Table 2 test raw material oil main character
Appreciation condition is as shown in table 3.
Table 3 process conditions
Active and estimation of stability the results are shown in table 4.Relative desulfurization degree, demetallization per and denitrification percent are 1.00 to compare as benchmark and obtain with the C-1 catalyst runs removal efficiency of 500 hours.As can be seen from Table 4, along with the duration of runs extends, containing the desulfurization degree of the grading composition of C-1 catalyst, demetallization per and denitrification percent apparently higher than comparative example catalyst; The attenuation degree of corresponding desulfurization degree, demetallization per and denitrification percent is less than contrast medium.Can say, the catalyst activity that the inventive method obtains and stability are better than the catalyst that conventional method obtains.
Table 4 catalyst stability contrast experiment
Claims (4)
1. active metal and alkalinous metal concentration in gradient increase a hydrogenation catalyst for distribution, it is characterized in that:
L) with Al
2o
3or containing SiO
2, TiO
2, ZrO
2al
2o
3for carrier;
2) pore volume is 0.2 ~ 3.O ml/g;
3) specific surface is 20 ~ 400m
2/ g;
4) in corresponding metal oxide quality, hydrogenation catalyst contains the MoO of 3.0 ~ 20.0%
3and/or WO
3and/or 2.0 ~ 8.O%CoO and/or NiO;
5) active metal component and the equal distribution gradient of alkalinous metal mass concentration in catalyst granules, increase gradually from granular center to outer surface, catalyst granules center is 0.05 ~ 0.70 with the ratio of the alkalinous metal mass concentration on surface, center is initial point, R is catalyst granules radius, 0.33R place is 0.22 ~ 0.85 with the ratio of the alkalinous metal mass concentration on surface, 0.66R place is 0.41 ~ 0.93 with the ratio of the alkalinous metal mass concentration on surface, catalyst granules center is 0.05 ~ 0.70 with the ratio of outer surface active metal mass concentration, 0.33R place and outer surface active metal mass concentration ratio are 0.2 ~ 0.8, 0.66R place and outer surface active metal mass concentration ratio are 0.4 ~ 0.9.
2. active metal according to claim 1 and alkalinous metal concentration in gradient increase a preparation method for the hydrogenation catalyst of distribution, it is characterized in that: with Al
2o
3or containing SiO
2, TiO
2, ZrO
2al
2o
3for carrier, by molybdenum and/or tungsten and/or nickel and/or cobalt compound, with alkaline metal cpds, and deionized water or ammoniacal liquor are mixed and made into active metal maceration extract, adopt the method for saturated spray-stain to prepare hydrogenation catalyst;
Spray employing to spray altogether or spray step by step;
Spray method altogether: by the rarer active metal solution of preparation and alkalinous metal solution, in spray-stain process, progressively add the saturated spray-stain carrier of method of denseer active metal solution and alkalinous metal solution; Or pass through active metal solution and the alkalinous metal solution of preparation variable concentrations, be immersed in from low to high on carrier by active metal solution and alkalinous metal solution concentration;
Or step impregnation: with the solution that alkalinous metal concentration is lower, progressively add the higher solution of alkalinous metal concentration in dipping process in maceration extract; Drying and roasting; Again with the lower solution of active metal concentrations, progressively add the higher solution of active metal concentrations in dipping process in maceration extract; Or alkalinous metal be immersed in active metal dipping after; At 80 ~ 150 DEG C dry 1 ~ 8 hour again, then roasting 2 ~ 6 hours in 300 ~ 650 DEG C of air;
Alkalinous metal is selected from least one component in IA group and IIA race; Alkalinous metal presses the weight content of oxide basis at catalyst between 0.1 ~ 5%.
3. active metal according to claim 2 and alkalinous metal concentration in gradient increase the preparation method of the hydrogenation catalyst of distribution, it is characterized in that: alkalinous metal is selected from Li, Mg, K or Ca in IA group and IIA race.
4. active metal according to claim 2 and alkalinous metal concentration in gradient increase the preparation method of the hydrogenation catalyst of distribution, it is characterized in that: the compound of alkalinous metal is LiNO
3, K
2hPO
4, KNO
3,mg (NO
3)
2or Ca (NO
3)
2.
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| CN103801311B (en) * | 2012-11-08 | 2016-01-06 | 中国石油化工股份有限公司 | A kind of preparation method of hydrotreating catalyst |
| CN105618072B (en) * | 2014-11-03 | 2017-10-27 | 中国石油化工股份有限公司 | The preparation method of Hydrodemetalation catalyst |
| CN105727941B (en) | 2014-12-10 | 2018-09-04 | 中国石油天然气股份有限公司 | A kind of sulfur-tolerant type aromatic saturated hydrogenation catalyst and preparation method thereof |
| CN105728024B (en) | 2014-12-10 | 2018-09-04 | 中国石油天然气股份有限公司 | Preparation method, noble metal hydrogenation catalyst and the application of noble metal hydrogenation catalyst |
| CN104607199B (en) * | 2015-01-30 | 2015-09-30 | 山东益丰生化环保股份有限公司 | A kind of low temperature sulfur tolerant shift Catalysts and its preparation method |
| CN108620118B (en) * | 2017-03-24 | 2020-03-17 | 中国石油化工股份有限公司 | Hydrogenation modification catalyst and preparation method thereof |
| KR102070435B1 (en) * | 2018-07-04 | 2020-01-28 | 전웅 | Method of extracting lithium |
| CN109675605A (en) * | 2019-01-09 | 2019-04-26 | 上海应用技术大学 | A kind of Ni/Co-NCs liberation of hydrogen material, preparation method and applications |
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| CN1458236A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for preparing demetalizing and desulfurizing catalyst of heavy oil hydrogenation |
| CN101927196A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient-decreasing-distributed active metal constituent concentration and preparation method thereof |
| CN101927169A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof |
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| CN1458236A (en) * | 2002-05-15 | 2003-11-26 | 中国石油化工股份有限公司 | Process for preparing demetalizing and desulfurizing catalyst of heavy oil hydrogenation |
| CN101927196A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with gradient-decreasing-distributed active metal constituent concentration and preparation method thereof |
| CN101927169A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst with active metal component concentration in gradient increase and distribution and preparation method thereof |
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