CN104437578A - Hydrodesulfurization catalyst, preparation method and applications thereof - Google Patents
Hydrodesulfurization catalyst, preparation method and applications thereof Download PDFInfo
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- CN104437578A CN104437578A CN201310422138.6A CN201310422138A CN104437578A CN 104437578 A CN104437578 A CN 104437578A CN 201310422138 A CN201310422138 A CN 201310422138A CN 104437578 A CN104437578 A CN 104437578A
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Abstract
The present invention provides a hydrodesulfurization catalyst, which comprises a modified titania-alumina composite carrier and nickel phosphide loaded on the carrier, wherein the modified titania-alumina composite carrier comprises an alkaline earth metal component and a group VIB metal component. The catalyst of the present invention has low temperature hydrogenation activity and good stability when the catalyst is used for the C5-C9 distillate oil hydrodesulfurization process. The present invention further provides a preparation method of the catalyst and a C5-C9 distillate oil hydrodesulfurization method.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst, the Hydrobon catalyst that the composite carrier load nickel phosphide being specifically related to a kind of modification obtains, its preparation method and application thereof.
Background technology
Containing sulphur, nitrogen, oxygen and metal impurities in petroleum distillate, the existence of these impurity not only can affect the character of oil product, and can discharge the pernicious gas of contaminated environment in the process used, and reduces activity and the life-span of catalyst.In the hydroprocessing processes taking petroleum hydrocarbon as raw material, raw material reacts with hydrogen under high-temperature and high-pressure conditions, to deviate from the harmful substance in raw material, and such as organic sulfur compound, organic nitrogen compound and organo-metallic compound etc.
At present, catalytic desulfurhydrogenation (HDS) technology reduces the main path of petrol and diesel oil sulfur content.Adopt two-stage method process for pyrolysis gasoline hydrotreatment, detailed process is: one section adopts the non-noble metal Al such as noble metal or Ni such as load P d
2o
3as selective hydrogenation catalyst, with the diene in hydrogenation and removing raw material; The Al of two sections of metals such as industrial general employing load C o, Mo, Ni
2o
3deng Hydrobon catalyst, to remove monoene and sulfide.Abroad in pyrolysis gasoline hydrogenation catalyst, French IFP secondary hydrogenation adopts the catalyst of LD and HR two profiles number, and LD-145 is Mo-Ni type catalyst, and HR-304B is Mo-Co type catalyst.The G-35B of the Girdler catalyst company exploitation of Japan and the S-12 catalyst of Uop Inc.'s exploitation are all Co-Mo/Al
2o
3catalyst.At home in pyrolysis gasoline hydrogenation catalyst, the industrialization of Yanshan Mountain branch of domestic Beijing Chemical Research Institute uses the TiO of load C o-Mo or Co-Mo-Ni
2-A1
2o
3for the BY-5 catalyst of carrier.
Transition metal phosphide is the class new catalytic material being subject to extensive concern after nitride and carbide, because it not only has very high hydrodesulfurization and the activity of hydrodenitrogeneration, and is having H
2under S existent condition, phosphide than nitride or carbide more stable, and there is better anti-sulfur poisonous performance.In addition, phosphide also shows better hydrogenation selectivity, and hydrogen-consuming volume is few, and by reducing hydrogen consumption, more effectively can utilize Hydrogen Energy, phosphide has become depth H DS catalyst of new generation, wherein crystalline state Ni
2the catalytic performance of P is best.But non-loading type Ni
2the specific area of P catalyst is very little (is less than 1m
2/ g), in order to improve its active surface area, need by Ni
2p load is on the carrier of high specific surface area.
The carrier of disclosed support type catalyst of phosphatizing nickel comprises at present: A1
2o
3, SiO
2, MCM-41, HZSM-5, KUSY, SBA-15, active carbon, TiO
2or SiO
2-A1
2o
3deng, but the interaction between different carriers and active component has a great impact the performance of catalyst and structure thereof.Simply introduce the pluses and minuses of above-mentioned various carrier below respectively: due to macropore γ-A1
2o
3there is the excellent properties such as larger specific area, suitable pore structure, stronger mechanical strength and good heat endurance, therefore, can as industrial traditional hydrodesulfurizationcatalyst catalyst for oil product carrier.If catalyst of phosphatizing nickel is with γ-A1
2o
3for carrier, in preparation process, phosphate is easy to and γ-A1
2o
3the A1 of surface four-coordination
3+there is strong interaction and generate AlPO in ion
4, thus cause the loss even destruction of catalyst surface institutional framework of the P elements of active component, make catalyst activity reduction, thus limit macropore γ-A1
2o
3the application of load catalyst of phosphatizing nickel in hydrogenation industry.SiO
2be considered to the good carrier of load nickel phosphide, but SiO
2interaction between carrier and metal component is more weak thus be unfavorable for the dispersion of active component at carrier surface, also can reduce the activity of hydrodesulfurization.The mesopore molecular sieves such as MCM-41 are also used as the carrier of Hydrobon catalyst.This kind of mesopore molecular sieve has high-specific surface area, homogeneous adjustable mesoporous pore size and stable skeleton structure, but its duct easily blocks, and produces negative effect sometimes to the activity of catalyst.SBA-15 has higher hydrothermal stability and wider aperture (5 ~ 30nm) adjustable range, but its production cost constrains its industrial applications.TiO
2not only play the effect of conventional carrier as hydrodesulfurization catalyst support, but also play the effect of electronics promoter.TiO
2the catalyst developed as carrier has the features such as the good and anti-Poisoning of active high and low temperature activity is strong, but TiO
2also there are some weakness, as its specific area is relatively little, generally at 70 ~ 100m as catalyst carrier
2/ g, active Detitanium-ore-type is at high temperature easily converted into the rutile structure of inertia, bad mechanical strength and acidity is more weak, makes it be difficult to industrially be widely used.Common TiO
2-Al
2o
3carrier loaded nickel phosphide, phosphorus loss is serious, Al
2o
3and the strong effect between P can reduce Ni
2phosphorus nickel ratio in P active component, therefore needs higher Ni
2p load capacity, adds cost; Meanwhile, catalytic activity is reduced.
In above-mentioned loaded catalyst, because the content of active component is less, cause the activity of catalyst lower.But along with the appearance of the new standard of low sulfur content, current Hydrobon catalyst cannot meet the new standard of low sulfur content, therefore how developing a kind of highly active Hydrobon catalyst has become urgent problem.
Summary of the invention
For deficiency of the prior art, the invention provides a kind of Hydrobon catalyst obtained based on the composite carrier load nickel phosphide of modification, the low temperature hydrogenation activity of this catalyst is high, and has good stability.Present invention also offers the preparation method of above-mentioned catalyst, this preparation method is simple, easy, and easily controls.
For achieving the above object, the invention provides a kind of Hydrobon catalyst, it comprises titanium dioxide-aluminum oxide composite carrier and the load nickel phosphide thereon of modification, and the titanium dioxide-aluminum oxide composite carrier of described modification comprises alkaline earth metal component and group vib metal component.
By catalyst provided by the invention, by using the TiO of alkaline-earth metal and the modification of group vib metal component
2-Al
2o
3complex carrier (or being called for short carrier), makes Al
2o
3have an effect with alkaline-earth metal and group vib metal component.As the described modification TiO of use
2-Al
2o
3during composite carrier load nickel phosphide, the strong interaction of Al to phosphorus can be greatly reduced, greatly reduce and generate AlPO
4adverse effect; Play TiO simultaneously
2as the effect of the electronics promoter of hydrodesulfurization catalyst support.Based on the TiO of modification
2-Al
2o
3complex carrier carrys out load Ni
2the catalyst that P obtains can have higher hydrogenation activity and hydrodesulfurization performance.Meanwhile, catalyst also has higher stability.
In the present invention, described alkaline-earth metal is as magnesium, calcium, strontium, barium and radium, and the metal of described group vib is as chromium and molybdenum.In a specific embodiment of catalyst of the present invention, in described alkaline-earth metal, the content of described alkaline earth metal component is 1 ~ 5wt% based on total catalyst weight; In group vib metal, the content of group vib metal component is 0.1 ~ 5wt% based on total catalyst weight.In above-mentioned data area, described modification TiO
2-Al
2o
3composite carrier load Ni
2the catalyst that P obtains has higher hydrogenation activity and hydrodesulfurization performance.In a specific embodiment, in group vib metal, the content of group vib metal component is 0.3 ~ 3wt% based on total catalyst weight.In one embodiment, described alkaline-earth metal is calcium; ; The metal of described group vib is molybdenum.When alkaline-earth metal selects calcium, when the metal of group vib selects molybdenum, then the excellent performance of the titanium dioxide-aluminum oxide composite carrier of obtained modification.
In a specific embodiment of catalyst of the present invention, the content of described nickel phosphide is 1 ~ 25wt% based on total catalyst weight.Owing to using the modification TiO in the present invention
2-Al
2o
3during composite carrier load nickel phosphide, the strong interaction of Al to phosphorus can be greatly reduced, greatly reduce and generate AlPO
4adverse effect, even if use reduce Ni
2p content, the catalyst obtained still has higher hydrogenation activity and hydrodesulfurization ability.In a specific embodiment, the content of described nickel phosphide is 15 ~ 25wt% based on total catalyst weight.
In a specific embodiment of catalyst of the present invention, catalyst provided by the invention also comprises lanthanide metal component on the titanium dioxide-aluminum oxide composite carrier being carried on described modification and/or group VIII metal component.By introducing lanthanide metal component or group VIII metal component on the titanium dioxide-aluminum oxide composite carrier of described modification, the low temperature hydrogenation that can improve this catalyst is further active.In a specific embodiment, the content of lanthanide metal component is 0.1 ~ 3wt% based on total catalyst weight.In another specific embodiment, the content of group VIII metal component is 1 ~ 10wt% based on total catalyst weight, is preferably 1 ~ 5wt%.Described lanthanide series metal is as lanthanum, cerium, praseodymium, neodymium etc.The metal of described group VIII is as cobalt, rhodium, iridium etc.In a specific embodiment, described lanthanide series metal is cerium, and the metal of described group VIII is cobalt.
At a specific embodiment of the present invention, described Hydrobon catalyst is C
5-C
9catalyst for hydrodesulfurizationfraction fraction oil.
Present invention also offers a kind of preparation method of Hydrobon catalyst, comprising:
Steps A: titanium dioxide-aluminum oxide composite oxides are flooded in the mixed solution of solution comprising the alkaline-earth metal aqueous solution and group vib metal component, then dry and roasting, obtains modified titanium oxide-alumina composite carrier;
Step B: modified titanium oxide-alumina composite carrier is flooded comprising in nickel salt solution and phosphatic maceration extract, obtains described catalyst.
According to method provided by the invention, by adopting alkaline-earth metal and group vib metal component to TiO
2-Al
2o
3composite oxides (or being called for short oxide) carry out modification, have prepared modification TiO
2-Al
2o
3complex carrier, then floods described complex carrier, obtains the catalyst of load nickel phosphide.Due to the TiO of the modification of employing
2-Al
2o
3complex carrier, it is to Ni
2the requirement of P load capacity reduces, and the cost of Kaolinite Preparation of Catalyst is reduced.Meanwhile, the TiO of modification
2-Al
2o
3complex carrier can greatly reduce the strong interaction of Al to phosphorus, greatly reduces and generates AlPO
4adverse effect, be conducive to improving the activity of catalyst; Play TiO simultaneously
2as the effect of the electronics promoter of hydrodesulfurization catalyst support.By the preparation-obtained Hydrobon catalyst of above-mentioned preparation method, there is good stability.
According to method provided by the invention, its technique is simple, easy, easily controls, and cost is low, has broad application prospect.
In one particular embodiment of the present invention, the roasting in described steps A can carry out 4 ~ 6h at 500 ~ 600 DEG C, then obtains described modified titanium oxide-alumina support.
The specific area of unmodified front titanium dioxide-aluminum oxide composite oxides provided by the invention is 80 ~ 180m
2/ g, pore volume is 0.4 ~ 1.3cm
3/ g and most probable pore size are 90 ~ 150 dusts.The catalyst selecting the specific area of suitable size and the titanium dioxide-aluminum oxide composite carrier of pore volume to be conducive to obtaining has better active and stability.In addition, in order to make the advantages such as the catalyst prepared has high-specific surface area, compression strength is high, diffusion velocity is fast, reactor bed pressure drop is low, in example of the present invention, described titanium dioxide-aluminum oxide composite carrier is clover shape.
In an embodiment of the inventive method, described alkaline-earth metal is calcium; The metal of described group vib is molybdenum.Titanium dioxide-aluminum oxide composite oxides comprise calcium the aqueous solution and containing molybdenum the aqueous solution in flood, obtain the titanium dioxide-aluminum oxide composite carrier of calcium and molybdenum modification.
In one particular embodiment of the present invention, in described step B, after dipping, also can carry out drying and baking operation, obtain described catalyst.In an instantiation, described in comprise nickel salt solution and phosphatic maceration extract for acid.Described nickel salt solution and the phosphatic maceration extract of comprising must can make load on complex carrier have nickel phosphide, described in comprise nickel salt solution and phosphatic maceration extract as comprised the maceration extract of nickelous hypophosphite.
In an embodiment of the inventive method, in described maceration extract, also comprise the solution of lanthanide metal component and/or the solution of group VIII metal component.By this operation, on the titanium dioxide-aluminum oxide composite carrier of described modification, load has the metal component of lanthanide metal component or group VIII further, and the low temperature hydrogenation that can improve this catalyst is further active.In a specific embodiment, described lanthanide series metal is cerium.In another specific embodiment, the metal of described group VIII is cobalt, and by introducing cerium and/or cobalt in catalyst, the low temperature hydrogenation that can improve this catalyst is further active and desulphurizing activated.
According to a further aspect in the invention, additionally provide a kind of hydrodesulfurizationprocess process, under the existence of the catalyst that its intermediate distillates is prepared at described catalyst or method, carry out hydrodesulfurization.In a specific embodiment, described distillate is C
5-C
9distillate.In another specific embodiment, described distillate is C
6-C
8distillate.
In an embodiment of the inventive method, in hydrodesulfurization, reaction temperature is 210 ~ 300 DEG C, and reaction pressure is 2.0 ~ 5.0MPa, and Feed space velocities is 1.5 ~ 5.0h
-1, hydrogen-oil ratio (volume ratio) is 150:1 ~ 450:1.
C is used for according to method provided by the invention
5-C
9the hydrodesulfurization of distillate, especially C
6-C
8the Secondary hydrodesulfurization of distillate, has the advantage that hydrogenation activity is high and hydrodesulfurization ability is strong; And while hydrodesulfurization, can hydrotreated lube base oil monoolefine to greatest extent, the change of feed sulphur content and the requirement of high-speed can be adapted to.
Can under cryogenic for C according to described catalyst provided by the invention
5-C
9the hydrodesulfurization of distillate, high to double-bond hydrogenation saturation degree, hydrotreated lube base oil monoolefine especially to greatest extent, hydrogenation activity is high, and good stability.
According to the present invention, by using alkaline-earth metal and group vib metal component to TiO
2-Al
2o
3composite oxides carry out modification, obtain the modification TiO comprising alkaline earth metal component and group vib metal component
2-Al
2o
3complex carrier; The complex carrier of described modification floods, and obtains the catalyst (Ni comprising nickel phosphide
2p).Described modification TiO
2-Al
2o
3complex carrier has had both Al
2o
3carrier specific area is large, pore structure is suitable for, the excellent properties of mechanical strength and good thermal stability, has played again TiO
2as the effect of the electronics promoter of hydrodesulfurization catalyst support, reduce because of phosphorus and Al
2o
3the loss of activity that causes of interaction.The TiO of described modification
2-Al
2o
3complex carrier, to Ni
2the requirement of P load capacity reduces, and the cost of Kaolinite Preparation of Catalyst is reduced, and the Hydrobon catalyst prepared has higher hydrogenation activity and hydrodesulfurization performance; Sulphur in drippolene and monoene can be removed; The catalytic activity of the catalyst finally prepared can be improved further.
Detailed description of the invention
The present invention describes the present invention in detail by following examples, can make the present invention of those skilled in the art comprehend, but these embodiments does not form any restriction to scope of the present invention.
Bromine valency: bromine valency is for weighing presence of unsaturates in oil samples, and the grams of the bromine consumed with 100 grams of oil samples represents.Bromine valency is higher, and contained by oil samples, unsaturated hydrocarbons is more.Usual employing small-hole drilling is analyzed oil samples.
Feed space velocities is inlet amount/catalyst quality per hour, and unit is h
-1.
The detection of specific surface and pore volume: comprise the specific surface of aluminium oxide, complex carrier and catalyst and the detection of pore volume.Specific volume surface area detection method adopts multiple spot BET method, uses F-sorb2400 specific surface area analysis instrument to detect; The detection method of pore volume adopts static capacity method, uses V-sorb2800 pore volume detector to detect.
In following examples, titanium dioxide-aluminum oxide composite carrier selects trifolium-shaped.In the preparation method of catalyst of the present invention, the production firm of aluminium oxide used is not particularly limited.
Embodiment 1
The preparation of modified titanium oxide-alumina composite carrier:
Titanium dioxide-aluminum oxide composite carrier is prepared according to the method in the embodiment 1 of disclosed patent CN1184289C.Getting specific area is 160m
2/ g, pore volume is 0.58ml/g, and most probable pore size is the cloverleaf pattern aluminium oxide 90g of 130 dusts, flood with the 0.557g/ml dilution heat of sulfuric acid of 53 milliliters of titanium sulfates, stir 15 minutes, in 120 DEG C of dryings after 8 hours, in 900 DEG C of calcinings 4 hours, obtained titanium dioxide-aluminum oxide composite oxides A
1, i.e. titanium dioxide-aluminum oxide composite carrier.Gained titanium dioxide-aluminum oxide composite oxides A
1titanium oxide content be 10 % by weight, specific area is 144m
2/ g, pore volume is 0.56ml/g, and most probable pore size is 125 dusts.
Get four water-calcium nitrate 27.7g and four water ammonium molybdate 4.5g are made into mixed solution, add water and be mixed with 140mL solution, prepare in the described solution obtained to four water-calcium nitrate and four water ammonium molybdates and add 100g titanium dioxide-aluminum oxide composite oxides A
1, stir 20 minutes, dry after draining away the water at 120 DEG C, then at 550 DEG C, calcining obtains modified titanium dioxide-aluminum oxide composite oxides A for 4 hours
2, i.e. modified titanium oxide-alumina composite carrier A
2.
The preparation of catalyst:
Preparation 20ml contains the maceration extract solution of the diammonium hydrogen phosphate of 7.1g nickel nitrate and 2.61g, drips nitric acid and makes the pH of maceration extract be 3.0, at ambient temperature, get 10g modified titanium oxide-alumina composite carrier A
2, with impregnation fluid, at 120 DEG C, drying 24 hours, then calcines 4 hours at 550 DEG C, takes out and is cooled to room temperature, obtain catalyst.Catalyst data is in table 1.
Embodiment 2
Step is with embodiment 1, and difference is in described maceration extract solution containing 4.7g nickel nitrate and the diammonium hydrogen phosphate of 1.70g and the cerous nitrate of 1.55g.Catalyst data is in table 1.
Embodiment 3
The preparation of modified titanium oxide-alumina composite carrier:
Step is with embodiment 1, and difference is, in described mixed solution, the addition of four water-calcium nitrate is 15.6g, and the addition of four water ammonium molybdates is 8.7g.
The preparation of catalyst:
Step is with embodiment 1, and difference is that preparation 20ml contains the maceration extract solution of the diammonium hydrogen phosphate of 7.1g nickel nitrate and 2.61g and the cobalt nitrate of 3.70g.Catalyst data is in table 1.
Embodiment 4
The preparation of modified titanium oxide-alumina composite carrier:
Step is with embodiment 1, and difference is, the addition of four water-calcium nitrate is 23.8g, and the addition of four water ammonium molybdates is 0.75g, and calcining heat is 500 DEG C.
The preparation of catalyst:
Step is with embodiment 1, and difference is that preparation 20ml contains the maceration extract solution of the diammonium hydrogen phosphate of 3.97g nickel nitrate and 1.43g and the cobalt nitrate of 0.63g.Catalyst data is in table 1.
Comparative example 1
If step is with embodiment 1, difference is, directly uses 10g titanium dioxide-aluminum oxide composite oxides A
1flood with described maceration extract.Data are in table 1.Comparative example 3
Comparative example 2
Step is with embodiment 2, and difference is, directly uses 10g titanium dioxide-aluminum oxide composite oxides A
1flood with described maceration extract.Data are in table 1.
Comparative example 3
Step is with embodiment 3, and difference is, directly uses 10g titanium dioxide-aluminum oxide composite oxides A
1flood with described maceration extract.Data are in table 1.
The content of table 1 catalyst components
Hydrodesulfurization reaction
The performance evaluation of catalyst in embodiment 1-4 and comparative example 1-3: use catalyst prepared by above-mentioned preparation method to C
6-C
8cut secondary hydrogenation raw material carries out hydrogenation evaluation, and equipment therefor is the small testing device of 200mL trickle bed reactor.Chemical industry seven factory of Sinopec Yanshan Mountain branch company benzene production equipment C taken from by raw material
6~ C
8cut secondary hydrogenation raw material, raw material total sulfur content is 103ppm, and bromine valency is 30.5gBr/100goil.Diene content is 7.0g I/100goil.Before evaluation sulfuration is carried out to catalyst.In the hydrogen gas stream of 100mL/min, with the speed of 10 DEG C/min, reactor is risen to 300 DEG C from room temperature, then be warming up to 550 DEG C with the speed of 1 DEG C/min, and maintain 2h, be down to 300 DEG C with containing the CS of 1%wt
2cyclohexane solution vulcanizing treatment 2h is carried out to it.Appreciation condition and product analyses as shown in table 2, liquid air speed and Feed space velocities in table:
The appreciation condition of table 2. catalyst of the present invention and product analyses
As can be seen from Table 2, although the content of nickel phosphide in comparative example 1 is higher than embodiment 1, when it is for hydrodesulfurization, the hydrodesulfurization effect of the catalyst in embodiment 1 is far superior to comparative example 1.Can learn from table 2, be used for hydrodesulfurization reaction according to catalyst provided by the invention, there is higher hydrodesulfurization activity, greatly can reduce the sulfur content in product, and presence of unsaturates.
Claims (10)
1. a Hydrobon catalyst, it comprises modified titanium oxide-alumina composite carrier and load nickel phosphide thereon, and described modified titanium oxide-alumina composite carrier comprises alkaline earth metal component and group vib metal component.
2. catalyst according to claim 1, is characterized in that, in alkaline-earth metal, the content of described alkaline earth metal component is 1 ~ 5wt% based on total catalyst weight; In group vib metal, the content of group vib metal component is 0.1 ~ 5wt% based on total catalyst weight, is preferably 0.3 ~ 3wt%; The content of nickel phosphide is 1 ~ 25wt% based on total catalyst weight, is preferably 15 ~ 25wt%.
3. catalyst according to claim 1 and 2, it is characterized in that, described catalyst also comprises lanthanide metal component on the titanium dioxide-aluminum oxide composite carrier being carried on described modification and/or group VIII metal component, the content of preferred lanthanide metal component is 0.1 ~ 3wt% based on total catalyst weight, the content of preferred group VIII metal component is 1 ~ 10wt% based on total catalyst weight, is more preferably 1 ~ 5wt%.
4. according to the catalyst in claim 1-3 described in any one, it is characterized in that, described alkaline-earth metal is calcium; The metal of described group vib is molybdenum; Described lanthanide series metal is cerium; The metal of described group VIII is cobalt.
5., as a preparation method for catalyst as described in any one in claim 1-4, comprising:
Steps A: titanium dioxide-aluminum oxide composite oxides are flooded in the mixed solution of solution comprising the alkaline-earth metal aqueous solution and group vib metal component, then dry and roasting, obtains modified titanium oxide-alumina composite carrier;
Step B: modified titanium oxide-alumina composite carrier is flooded comprising in nickel salt solution and phosphatic maceration extract, obtains described catalyst.
6. method according to claim 5, is characterized in that, in described steps A, the specific area of titanium dioxide-aluminum oxide composite oxides is 80 ~ 180m
2/ g, pore volume is 0.4 ~ 1.3cm
3/ g, most probable pore size is 90 ~ 150 dusts.
7. the method according to claim 5 or 6, is characterized in that, also comprises the solution of lanthanide metal component and/or the solution of group VIII metal component in described maceration extract.
8. according to the method in claim 5 ~ 7 described in any one, it is characterized in that, described alkaline-earth metal is calcium; The metal of described group vib is molybdenum; Described lanthanide series metal is cerium; Described group VIII metal is cobalt.
9. a hydrodesulfurizationprocess process, its intermediate distillates in claim 1-4 in catalyst described in any one or claim 5-8 catalyst prepared by any one method existence under carry out hydrodesulfurization, the preferred C of wherein said distillate
5-C
9distillate, more preferably C
6-C
8distillate.
10. method according to claim 9, is characterized in that, in catalytic hydrogenation, reaction temperature is 210 ~ 300 DEG C, and reaction pressure is 2.0 ~ 5.0MPa, and Feed space velocities is 1.5 ~ 5.0h
-1, hydrogen-oil ratio is 150:1 ~ 450:1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498793A (en) * | 2015-11-28 | 2016-04-20 | 南京威安新材料科技有限公司 | Hydrodesulfurization catalyst |
| CN106635135A (en) * | 2016-12-23 | 2017-05-10 | 兰州石化职业技术学院 | Hydrodesulfurization method of catalytic cracking gasoline |
| CN106807417A (en) * | 2017-01-16 | 2017-06-09 | 钦州学院 | A kind of adding hydrogen into resin catalyst and preparation method thereof |
| CN106914259A (en) * | 2017-03-17 | 2017-07-04 | 钦州学院 | A kind of method of hydrotreating of C 5 petroleum resin |
| CN108236965A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | Modified hydrodesulfurization catalyst and preparation method thereof |
| CN111760581A (en) * | 2019-08-30 | 2020-10-13 | 万华化学（宁波）有限公司 | Catalyst for preparing phosgene, preparation method thereof and method for preparing phosgene and comprehensively utilizing energy |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200060A (en) * | 1991-04-26 | 1993-04-06 | Amoco Corporation | Hydrotreating process using carbides and nitrides of group VIB metals |
| CN101612584A (en) * | 2009-07-21 | 2009-12-30 | 西安交通大学 | The preparation method of the catalyst of phosphatizing nickel that a kind of complex carrier supports |
| CN102295955A (en) * | 2010-06-25 | 2011-12-28 | 中国石油天然气股份有限公司 | Hydro-upgrading method for inferior gasoline |
-
2013
- 2013-09-16 CN CN201310422138.6A patent/CN104437578B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5200060A (en) * | 1991-04-26 | 1993-04-06 | Amoco Corporation | Hydrotreating process using carbides and nitrides of group VIB metals |
| CN101612584A (en) * | 2009-07-21 | 2009-12-30 | 西安交通大学 | The preparation method of the catalyst of phosphatizing nickel that a kind of complex carrier supports |
| CN102295955A (en) * | 2010-06-25 | 2011-12-28 | 中国石油天然气股份有限公司 | Hydro-upgrading method for inferior gasoline |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498793A (en) * | 2015-11-28 | 2016-04-20 | 南京威安新材料科技有限公司 | Hydrodesulfurization catalyst |
| CN106635135A (en) * | 2016-12-23 | 2017-05-10 | 兰州石化职业技术学院 | Hydrodesulfurization method of catalytic cracking gasoline |
| CN106635135B (en) * | 2016-12-23 | 2018-08-14 | 兰州石化职业技术学院 | A kind of hydrodesulfurizationprocess process of catalytically cracked gasoline |
| CN108236965A (en) * | 2016-12-27 | 2018-07-03 | 中国石油天然气股份有限公司 | Modified hydrodesulfurization catalyst and preparation method thereof |
| CN106807417A (en) * | 2017-01-16 | 2017-06-09 | 钦州学院 | A kind of adding hydrogen into resin catalyst and preparation method thereof |
| CN106914259A (en) * | 2017-03-17 | 2017-07-04 | 钦州学院 | A kind of method of hydrotreating of C 5 petroleum resin |
| CN111760581A (en) * | 2019-08-30 | 2020-10-13 | 万华化学（宁波）有限公司 | Catalyst for preparing phosgene, preparation method thereof and method for preparing phosgene and comprehensively utilizing energy |
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