CN102728372B - Preparation method of hydrofining catalyst - Google Patents
Preparation method of hydrofining catalyst Download PDFInfo
- Publication number
- CN102728372B CN102728372B CN201110093564.0A CN201110093564A CN102728372B CN 102728372 B CN102728372 B CN 102728372B CN 201110093564 A CN201110093564 A CN 201110093564A CN 102728372 B CN102728372 B CN 102728372B
- Authority
- CN
- China
- Prior art keywords
- accordance
- alumina precursor
- grams
- boron
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a preparation method of a hydrofining catalyst, comprising the following steps of: mixing a complex impregnation liquid containing Group VIB and Group VIII metal, humic acid urea and boron compound with an alumina precursor, moulding, drying, and roasting to obtain the hydrofining catalyst. By the adoption of the method, loading and dispersity of active metal and a boron aid on the surface of alumina can be raised, and performance of the catalyst is further improved.
Description
Technical field
The preparation method who the present invention relates to a kind of Hydrobon catalyst, belongs to field of inorganic material preparing technology.
Background technology
Hydrofinishing is to remove the organic important means such as sulphur in oil product, nitrogen, oxygen by catalytic hydrogenation.At present, an importance in Hydrobon catalyst research is to take the alumina support that several different methods Kaolinite Preparation of Catalyst is used to carry out modification to obtain well behaved catalysis material.
Aluminium oxide, as catalytic carrier material, has a very wide range of applications in field of hydrogenation.But, due to aluminium oxide when the catalyst carrier acidity a little less than, and easily and active metal component generation strong interaction and form the species of non-activity, therefore, easily there is the sintering of active metal component or carrier with aluminium oxide as catalyst carrier merely and affect the Activity and stabill of catalyst.So, in the time that aluminium oxide is used as catalyst carrier, conventionally add one or more other elements, with the acid of regulating catalyst and/or improve the interaction between active component and carrier.The comparatively common practice is in carrier or catalyst preparation process, the elements such as boron, silicon, phosphorus, titanium to be introduced wherein.
CN 1052501A adopts boric acid ammonia spirit oxide impregnation alumina supporter, obtains the alumina support that boron content is higher.But owing to being combined and thering is precipitation with ammoniacal liquor at dipping process mesoboric acid, make the larger containing boron particles of generation, during therefore for catalyst carrier, be unfavorable for the raising of catalytic performance; Meanwhile, owing to using ammoniacal liquor in dipping process, ammonia and nitrogen pollution is serious.
CN 1070418A introduces boron by boric acid and the dry glue of aluminium in kneading mode, although adopt this kind of method can adjust arbitrarily the amount of added boron, the decentralization of the boron adding in kneading mode on carrier is poor.
CN 1082387C discloses a kind of mesoporous alumina gel and preparation method thereof.In this alumina gel, dispersed one or more are selected from the oxide of boron oxide, silica, phosphorous oxide, and the oxide of described boron, silicon and phosphorus joins in carrier by coprecipitation, preparation method's complexity.Because being adopts coprecipitation that boron, silicon and P elements are added in aluminium oxide, a large amount of boron, silicon and P elements be dispersed in alumina body mutually in, thereby auxiliary agent can not be given full play to its effect.
The disclosed Hydrobon catalyst of CN 1083475C is the maceration extract that contains VI B family and VIII family metal, organic carboxyl acid, polyalcohol and boron additive to be sprayed on alumina support simultaneously, after drying, roasting, obtains Hydrobon catalyst.In the maceration extract that the method adopts, complexing agent adopts organic carboxyl acid and polyalcohol, after boron reacts with polyhydric alcohol complex, can make the acidity of solution increase, and under organic carboxyl acid exists, the acidity of maceration extract strengthen, in the time of oxide impregnation alumina supporter, intensity and the pore structure that can damage carrier, also can affect the decentralization of active metal and boron simultaneously, and then affect the performance of catalyst.In addition, due to boron and polyhydric alcohol complex, active metallic ion can with organic acid complexing, also can with polyhydric alcohol complex, so boron and active metallic ion exist the problem of competition coordination, so also can affect the decentralization of active metal and boron.
Summary of the invention
For overcoming weak point of the prior art, the invention provides a kind of preparation method of Hydrobon catalyst.The method can improve boron and active metal load capacity and the degree of scatter at carrier surface, and then has improved the performance of catalyst.
The preparation method of Hydrobon catalyst of the present invention is as follows:
(1) by the maceration extract that is mixed with of group VIB metallic compound, group VIII metal compound, humic acid urea and boron-containing compound;
(2) maceration extract of step (1) gained is joined in alumina precursor, and constantly stir kneading, make it to become plastic, moulding, then drying and roasting, obtain oxidation state Hydrobon catalyst.
Alumina precursor described in step (2) is before adding the maceration extract of step (1) gained, with low-carbon alcohol solution, alumina precursor is wetting in advance.Described low-carbon alcohols is carbon four and the alcohol of carbon below four, comprises one or more in methyl alcohol, ethanol, propyl alcohol, butanols.Above-mentioned low-carbon alcohols is preferably methyl alcohol and/or ethanol, more preferably ethanol.The concentration of described low-carbon alcohol solution is 50v% ~ 100v%, is preferably 70v% ~ 90v%.Take the volume of alumina precursor saturated extent of adsorption as benchmark, the consumption of described low-carbon alcohol solution is saturated extent of adsorption 10% ~ 100%, is preferably 50% ~ 80%.
The described alumina precursor of step (2) is boehmite rubber powder or can be converted into γ-Al after roasting
2o
3aluminum oxide.In described alumina precursor, can contain conventional modifier, such as one or more in silicon, phosphorus, zirconium, titanium etc.
In step (2), can also add as required other raw material that is conducive to moulding, as materials such as the sesbania powder as extrusion aid, and mix with alumina precursor in advance.
Group VIB element described in step (1) is cobalt and/or nickel, and described VIII family element is molybdenum and/or tungsten.Described boron-containing compound is one or more in boric acid, ammonium borate, tetraboric acid ammonium, ammonium metaborate, ammonium hydrogen borate, is preferably boric acid.Take the weight of final catalyst as benchmark, B
2o
3content is 0.5wt% ~ 15.0wt%, is preferably 2.0wt% ~ 7.0wt%, and group VIB metal oxide content is 10wt% ~ 35wt%, and group VIII metal oxide content is 2wt% ~ 15wt%.
In maceration extract described in step (1), the weight concentration of group VIB element is 3.5wt ~ 14.0wt%, the weight concentration of VIII family element is 5.0wt% ~ 15.0wt%, the weight concentration of described boron is 2.0wt ~ 5.5wt%, and the weight concentration of described humic acid urea is 3.0wt ~ 10.0wt%.
The described dry run of step (2) generally at room temperature ~ 120 ℃ dry 1 hour ~ 24 hours, preferably at room temperature dries in the shade 10 hours ~ 24 hours, is then warming up to 100 ℃ ~ 120 ℃, dry 1 hour ~ 4 hours.Described roasting condition is: roasting 2 hours ~ 10 hours at 500 ℃ ~ 650 ℃.
Method of the present invention has the following advantages:
(1) humic acid urea adopting is owing to containing amino and carboxyl, can form stable complex compound with boron-containing compound and active metallic ion complexing respectively, and there is not the problem of competition coordination, can improve like this boron and active metal load capacity and the decentralization at carrier surface.Because amino in boron-containing compound and humic acid urea forms complex compound, acid suitable, can not damage intensity and the specific area of carrier, can also play the effect of the peptizing agent that aluminium oxide moulding uses.
(2) the present invention merges to a step by the load of aluminium oxide peptization, boron modification and active metal and completes, and has simplified catalyst preparation procedure.
(3) the present invention preferably adopts low-carbon alcohols first that alumina precursor is wetting in advance, can avoid directly maceration extract being joined to the partial over saturation adsorption phenomena that alumina precursor causes, this partial over saturation absorption makes boron and active metal be difficult to mix at follow-up kneading process.After alumina precursor soaks in advance, maceration extract can excessively not be adsorbed onto the inner duct of precursor, simultaneously due to the raising along with temperature in kneading process, the volatilization of low-carbon alcohols, and lower capillary effect, contribute to boron and active metal to evenly spread on alumina support.
(4) the present invention, by the modification of auxiliary agent boron to aluminium oxide, has improved the physico-chemical property of catalyst.Humic acid urea is conducive to improve the metal active centric quantity of catalyst to the complexing of active metal simultaneously, therefore the Hydrobon catalyst that uses method of the present invention to prepare have advantages of active metal loading and decentralization high, thereby make it have higher hydrodesulfurization, denitrification activity.
The specific embodiment
Embodiment 1
115 grams of boehmite dry glue powders, take ethanol as wetting agent, its saturated adsorption value is 270 grams after measured.Get 115 grams of dry glue powders, 3 grams, sesbania powder, after mixing, then adds 135 grams of ethanol gradually, constantly stirs until evenly.Preparation maceration extract is composed as follows: 6.92 grams of boric acid, 10 grams of humic acid ureas, 15.56 grams of ammonium tetramolybdates, 13.98 grams of cobalt nitrates, 160 grams, water.Then maceration extract is joined gradually in above-mentioned wetting alumina precursor, first basic stir agglomerating after, then move in banded extruder after abundant kneading is plastic, be extruded into stripe shape.Under extrudate room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make described Hydrobon catalyst, be numbered Cat1, its physico-chemical property is in table 1.
Embodiment 2
115 grams of boehmite dry glue powders, 3 grams, sesbania powder, after mixing, then adds the ethanolic solution of 130 grams of 60v% under dry state gradually, constantly stirs until evenly.Preparation maceration extract is composed as follows: 6.92 grams of boric acid, 13 grams of humic acid ureas, 15.56 grams of ammonium tetramolybdates, 26.79 grams of cobalt nitrates, 163 grams, water.Then maceration extract is joined gradually in above-mentioned wetting alumina precursor, first basic stir agglomerating after, then move in banded extruder after abundant kneading is plastic, be extruded into stripe shape.Under extrudate room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 600 ℃, and at this temperature constant temperature calcining 4 hours, drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make described Hydrobon catalyst, be numbered Cat2, its physico-chemical property is in table 1.
Embodiment 3
115 grams of boehmite dry glue powders, 3 grams, sesbania powder, after mixing, then adds the ethanolic solution of 150 grams of 60v% under dry state gradually, constantly stirs until evenly.Preparation maceration extract is composed as follows: 6.22 grams of boric acid, 10 grams of humic acid ureas, 19.10 grams of ammonium metatungstates, 15.18 grams of nickel nitrates, 160 grams, water.Then maceration extract is joined gradually in above-mentioned wetting alumina precursor, first basic stir agglomerating after, then move in banded extruder after abundant kneading is plastic, be extruded into stripe shape.Under extrudate room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 600 ℃, and at this temperature constant temperature calcining 4 hours, drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make described Hydrobon catalyst, be numbered Cat3, its physico-chemical property is in table 1.
Embodiment 4
115 grams of boehmite dry glue powders, 3 grams, sesbania powder, after mixing, then adds the ethanolic solution of 150 grams of 60v% under dry state gradually, constantly stirs until evenly.Preparation maceration extract is composed as follows: 8.17 grams of boric acid, 16 grams of humic acid ureas, 25.47 grams of ammonium metatungstates, 9.34 grams of nickel nitrates, 154 grams, water.Then maceration extract is joined gradually in above-mentioned wetting alumina precursor, first basic stir agglomerating after, then move in banded extruder after abundant kneading is plastic, be extruded into stripe shape.Under extrudate room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 650 ℃, and at this temperature constant temperature calcining 3 hours, drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make described Hydrobon catalyst, be numbered Cat4, its physico-chemical property is in table 1.
Embodiment 5
115 grams of boehmite dry glue powders, 3 grams, sesbania powder, after mixing, then adds the ethanolic solution of 150 grams of 60v% under dry state gradually, constantly stirs until evenly.Preparation maceration extract is composed as follows: 11.9 grams of boric acid, 16 grams of humic acid ureas, 10.95 grams of ammonium molybdates, 34.6 grams of nickel nitrates, 160 grams, water.Then maceration extract is joined gradually in above-mentioned wetting alumina precursor, first basic stir agglomerating after, then move in banded extruder after abundant kneading is plastic, be extruded into stripe shape.Under extrudate room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 650 ℃, and at this temperature constant temperature calcining 3 hours, drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make described Hydrobon catalyst, be numbered Cat5, its physico-chemical property is in table 1.
Embodiment 6
According to the method Kaolinite Preparation of Catalyst of embodiment 1, difference is not add alcohol to soak.115 grams of boehmite dry glue powders, 3 grams, sesbania powder, after mixing, then adds 135 grams of ethanol gradually, constantly stirs until evenly.Preparation maceration extract is composed as follows: 6.92 grams of boric acid, 10 grams of humic acid ureas, 15.56 grams of ammonium tetramolybdates, 13.98 grams of cobalt nitrates, 160 grams, water.Then maceration extract is joined gradually in above-mentioned wetting alumina precursor, first basic stir agglomerating after, then move in banded extruder after abundant kneading is plastic, be extruded into stripe shape.Under extrudate room temperature, after dried overnight, at 110 ℃, dry 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make described Hydrobon catalyst, be numbered Cat6, its physico-chemical property is in table 1.
Comparative example 1
According to the method Kaolinite Preparation of Catalyst described in CN 1083475C.Adopt the boehmite dry glue powder identical with embodiment 1 ~ 5, through conventional extruded moulding, then 550 ℃ of dry used carriers that obtain of roasting.Maceration extract is composed as follows: 14.6 grams of sorbierites, and 2.51 grams of boric acid, 21.12 grams of citric acids, 12.85 grams of ammonium tetramolybdates, 10.13 grams of cobalt nitrates, 140 grams, water, is then impregnated on alumina support, and sintering temperature is 550 ℃, and roasting time is 6 hours.Drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make Hydrobon catalyst, be numbered Dcat1, its physico-chemical property is in table 1.
Comparative example 2
According to the method Kaolinite Preparation of Catalyst described in CN 1083475C.Adopt carrier with comparative example 1.Maceration extract is composed as follows: 40 grams of xylitols, and 2.25 grams of boric acid, 13.82 grams of citric acids, 15.97 grams of ammonium metatungstates, 10.14 grams of nickel nitrates, 140 grams, water, is then impregnated on alumina support, and sintering temperature is 600 ℃, and roasting time is 4 hours.Drying sample is placed in to high temperature furnace, is warming up to 550 ℃, and at this temperature constant temperature calcining 6 hours, make Hydrobon catalyst, be numbered Dcat2, its physico-chemical property is in table 1.
The physico-chemical property of table 1 embodiment and comparative example gained catalyst
| Catalyst numbering | MoO 3，wt% | WO 3，wt% | NiO，wt% | CoO，wt% | B 2O 3，wt% | Specific area, m 2/g | Pore volume, ml/g |
| Cat1 | 13.5 | - | - | 3.6 | 3.9 | 248 | 0.76 |
| Cat2 | 13.5 | - | - | 6.9 | 3.9 | 236 | 0.69 |
| Cat3 | - | 15.6 | 3.9 | - | 3.5 | 224 | 0.64 |
| Cat4 | 9.1 | 20.8 | 2.4 | - | 4.6 | 219 | 0.80 |
| Cat5 | 9.5 | 17.8 | 8.9 | - | 6.7 | 249 | 0.75 |
| Cat6 | 13.5 | - | - | 3.6 | 3.9 | 214 | 0.74 |
| Dcat1 | 13.5 | - | - | 3.6 | 3.9 | 201 | 0.70 |
| Dcat2 | - | 15.6 | 3.9 | - | 3.5 | 198 | 0.72 |
Embodiment 7
Catalyst hydrogenation activity is evaluated, and using before catalyst of the present invention, need change oxidized catalyst into sulphided state through conventional sulfuration program.Described conditions of vulcanization is conventional in the industry vulcanization, and catalyst can be presulfurization outside device, can be also sulfuration in device.
Evaluate raw material cracked diesel oil used, character is as follows: density is 0.891g/cm
3, sulfur content 5800 μ g/g, nitrogen content is 953 μ g/g.
By 5 grams of catalyst, be loaded in miniature hydrogenation reactor, then reactor is warming up to 120 ℃, constant temperature makes catalyst dehydration for 2 hours.Dehydration finishes rear injection sulfurized oil: sulfurized oil is the boat coal that has added 3wt% carbon disulfide, and charging rate is 100ml/h.The temperature of reactor is risen to 200 ℃, 240 ℃, 280 ℃, 320 ℃ again, and each temperature spot constant temperature 1 hour; Finally be warming up to 340 ℃, keep 12 hours, start to pump into above-mentioned raw materials oil after completing sulfuration.
The present embodiment process conditions used are: 350 ℃ of temperature, pressure 5MPa, liquid air speed 1.0h
-1, hydrogen-oil ratio is 500.
Table 2 feedstock oil hydrogenation activity evaluation table
| ? | Feedstock oil | Cat1 | Cat2 | Cat3 | Cat6 | Dcat1 | Dact2 |
| Density, g/cm 3 | 0.891 | 0.862 | 0.859 | 0.860 | 0.864 | 0.869 | 0.866 |
| S，μg/g | 5800 | 90.1 | 92.4 | 91.2 | 93.1 | 96.1 | 97.9 |
| N，μg/g | 953 | 58.0 | 57.2 | 56.0 | 59.6 | 70.2 | 68.8 |
There is good physico-chemical property from the visible the inventive method of table 1 institute controlling catalyst, and can illustrate by evaluation result (in table 2), when the high-sulfur of Hydrobon catalyst processing of the present invention, the feedstock oil of nitrogen content, its sulphur, nitrogen content obviously reduce, oil property be improved significantly, therefore Hydrobon catalyst of the present invention is the comparatively good Hydrobon catalyst of a kind of performance.
Claims (16)
1. a preparation method for Hydrobon catalyst, comprising:
(1) group VIB metallic compound, group VIII metal compound, boron-containing compound and humic acid urea complexing are mixed with to maceration extract;
(2) maceration extract of step (1) gained is joined in alumina precursor, and constantly stir kneading, make it to become plastic, moulding, then drying and roasting, obtain Hydrobon catalyst.
2. in accordance with the method for claim 1, it is characterized in that the described alumina precursor of step (2) is before adding the maceration extract of step (1) gained, with low-carbon alcohol solution, alumina precursor is wetting in advance.
3. according to the method described in claim 1 or 2, it is characterized in that, take the weight of final catalyst as benchmark, B
2o
3content is 0.5wt%～15.0wt%, and group VIB metal oxide content is 10wt%～35wt%, and group VIII metal oxide content is 2wt%～15wt%.
4. in accordance with the method for claim 2, it is characterized in that described low-carbon alcohols is one or more in methyl alcohol, ethanol, propyl alcohol, butanols.
5. in accordance with the method for claim 2, it is characterized in that described low-carbon alcohols is methyl alcohol and/or ethanol.
6. the concentration that in accordance with the method for claim 2, it is characterized in that described low-carbon alcohol solution is 50v%～100v%.
7. in accordance with the method for claim 2, it is characterized in that, take the volume of alumina precursor saturated extent of adsorption as benchmark, the consumption of described low-carbon alcohol solution is saturated extent of adsorption 10%～100%.
8. in accordance with the method for claim 2, it is characterized in that, take the volume of alumina precursor saturated extent of adsorption as benchmark, the consumption of described low-carbon alcohol solution is saturated extent of adsorption 30%～60%.
9. according to the method described in claim 1 or 2, it is characterized in that the described alumina precursor of step (2) for can be converted into γ-Al after roasting
2o
3aluminum oxide.
10. according to the method described in claim 1 or 2, it is characterized in that the described alumina precursor of step (2) is boehmite rubber powder.
11. according to the method described in claim 1 or 2, it is characterized in that containing in the described alumina precursor of step (2) one or more in silicon, phosphorus, zirconium, titanium.
12. in accordance with the method for claim 1, it is characterized in that the VI B family element described in the maceration extract described in step (1) is molybdenum and/or tungsten, described VIII family element is cobalt and/or nickel, and described boron-containing compound is one or more in boric acid, ammonium borate, tetraboric acid ammonium, ammonium metaborate, ammonium hydrogen borate.
13. in accordance with the method for claim 1, it is characterized in that the boron-containing compound described in step (1) is boric acid.
14. according to the method described in claim 1 or 13, the weight concentration that it is characterized in that group VIB element in the described maceration extract of step (1) is 3.5wt～14.0wt%, the weight concentration of VIII family element is 5.0wt%～15.0wt%, the weight concentration of described boron-containing compound is 2.0wt%～5.5wt%, and the weight concentration of described humic acid urea is 3.0wt～10.0wt%.
15. in accordance with the method for claim 1, it is characterized in that the described roasting condition of step (2) is: roasting 2～10 hours at 500～650 ℃.
16. in accordance with the method for claim 15, it is characterized in that dry at room temperature the drying in the shade 10～24 hours that step (2) is described, is then warming up to 100～120 ℃, dry 1～4 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110093564.0A CN102728372B (en) | 2011-04-14 | 2011-04-14 | Preparation method of hydrofining catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110093564.0A CN102728372B (en) | 2011-04-14 | 2011-04-14 | Preparation method of hydrofining catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102728372A CN102728372A (en) | 2012-10-17 |
| CN102728372B true CN102728372B (en) | 2014-06-25 |
Family
ID=46985085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110093564.0A Active CN102728372B (en) | 2011-04-14 | 2011-04-14 | Preparation method of hydrofining catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102728372B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114570423B (en) * | 2021-12-27 | 2023-09-15 | 中国科学院山西煤炭化学研究所 | Catalyst for preparing ethanol and propanol from synthesis gas, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0357295B1 (en) * | 1988-08-19 | 1996-07-03 | Sumitomo Metal Mining Company Limited | Catalysts for hydrotreating of hydrocarbons and methods of preparing the same |
| EP0748652A1 (en) * | 1995-06-15 | 1996-12-18 | ENIRICERCHE S.p.A. | Mesoporous alumina gel and process for its preparation |
| CN1362487A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Hydrorefining catalyst and its prepn |
| CN101590417A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Hydrobon Catalyst And Its Preparation Method |
-
2011
- 2011-04-14 CN CN201110093564.0A patent/CN102728372B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0357295B1 (en) * | 1988-08-19 | 1996-07-03 | Sumitomo Metal Mining Company Limited | Catalysts for hydrotreating of hydrocarbons and methods of preparing the same |
| EP0748652A1 (en) * | 1995-06-15 | 1996-12-18 | ENIRICERCHE S.p.A. | Mesoporous alumina gel and process for its preparation |
| CN1362487A (en) * | 2001-01-05 | 2002-08-07 | 中国石油化工股份有限公司 | Hydrorefining catalyst and its prepn |
| CN101590417A (en) * | 2008-05-29 | 2009-12-02 | 北京三聚环保新材料股份有限公司 | Hydrobon Catalyst And Its Preparation Method |
Non-Patent Citations (3)
| Title |
|---|
| Hydrodusulfurization of dibenzothiophenes over molybdenum catalyst support on TiO2-Al2O3;S.Yoshinaka 等;《Catalysis Today》;19981231;第293-298页 * |
| S.Yoshinaka 等.Hydrodusulfurization of dibenzothiophenes over molybdenum catalyst support on TiO2-Al2O3.《Catalysis Today》.1998,第293-298页. |
| 张孔远等.新型混捏法Co-Mo/γ-Al2O3加氢脱硫催化剂.《石油学报（石油化工）》.2005,第21卷(第1期),第6-11页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102728372A (en) | 2012-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103769125B (en) | A kind of preparation method of hydrotreating catalyst | |
| CN101314130B (en) | Boron containing hydrodesulphurization catalyst and preparation method thereof | |
| CN102728335B (en) | Preparation method of boron-modified alumina carrier | |
| CN1854260A (en) | Heavy fractional oil hydrogenation catalyst and production thereof | |
| CN103785401A (en) | Preparation method of hydrodemetalization catalyst for residuum | |
| CN100496738C (en) | Alumina supporter possessing duplicate orifice, catalyst and preparation method | |
| CN101590433A (en) | Modified aluminium oxide supports and the hydrogenation catalyst and the preparation method that make by this carrier | |
| CN105582951A (en) | Preparation method of hydrodemetallization catalyst containing alkaline earth metals | |
| CN104324710B (en) | A kind of hydrogenation protecting catalyst and preparation method and application | |
| CN103769179A (en) | Preparation method of residual oil hydro-treatment catalyst | |
| CN102728372B (en) | Preparation method of hydrofining catalyst | |
| CN102049264A (en) | Hydrodesulphurization catalyst and preparation method thereof | |
| CN100556994C (en) | Phosphorated diesel oil hydrofining catalyst and preparation method thereof | |
| CN111151270B (en) | Distillate oil hydrotreating catalyst and preparation method thereof | |
| CN108452849B (en) | Diesel oil hydrofining catalyst and preparation method and application thereof | |
| CN109794265A (en) | Sulfurized hydrogenation catalyst for refining and preparation method thereof, fraction oil hydrogenation refining method | |
| CN112717965B (en) | Hydrogenation pretreatment catalyst, and preparation method and application thereof | |
| CN105582952B (en) | A kind of preparation method of the Hydrodemetalation catalyst containing rare earth | |
| CN108404897A (en) | A kind of catalyst carrier for hydrgenating heavy oil, preparation method, using its catalyst and catalyst preparation method | |
| CN103933997B (en) | A kind of hydrogenation protecting catalyst and preparation method thereof | |
| CN109772400B (en) | Hydrotreating catalyst and preparation method and application thereof | |
| CN105921160A (en) | Preparation method of catalyst used in bio-oil hydrodeoxygenation | |
| CN103785432B (en) | A kind of catalyst used for hydrogenation of distilled oil fraction and preparation method thereof | |
| CN1163573C (en) | Selectively mercaptan-eliminating catalyst for aviation fuel and its prepn | |
| CN107345158B (en) | A kind of heavy oil hydrogenation treatment method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |