CN104437578B - Hydrodesulfurization catalyst, preparation method and applications thereof - Google Patents
Hydrodesulfurization catalyst, preparation method and applications thereof Download PDFInfo
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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, and in particular to a kind of modified composite carrier load nickel phosphide gained
Hydrobon catalyst, its preparation method and its application arrived.
Background technology
Contain sulphur, nitrogen, oxygen and metal impurities in petroleum distillate, the presence of these impurity can not only affect the property of oil product
Matter, and the pernicious gas of pollution environment can be discharged during use, reduce activity and the life-span of catalyst.With stone
Petroleum hydrocarbon class for raw material hydroprocessing processes in, raw material is reacted under high-temperature and high-pressure conditions with hydrogen, to deviate from raw material in
Harmful substance, such as organic sulfur compound, organic nitrogen compound and organo-metallic compound etc..
At present, catalytic desulfurhydrogenation（HDS）Technology is the main path for reducing petrol and diesel oil sulfur content.It is hydrogenated with using two-stage method
Drippolene is processed, detailed process is：One section using non-noble metal Al such as noble metal or Ni such as load Pd2O3Alternatively
Hydrogenation catalyst, with the diene in hydrogenation and removing raw material；Two sections of industrial general Al using metals such as load C o, Mo, Ni2O3
Deng Hydrobon catalyst, to remove monoene and sulfide.Abroad in pyrolysis gasoline hydrogenation catalyst, bis- sections of French IFP adds
Hydrogen adopts the catalyst of two kinds of models of LD and HR, and LD-145 is Mo-Ni type catalyst, and HR-304B is Mo-Co type catalyst.Day
The G-35B of this Girdler catalyst company exploitation and the S-12 catalyst of Uop Inc.'s exploitation are all Co-Mo/Al2O3Catalyst.
At home in pyrolysis gasoline hydrogenation catalyst, domestic Beijing Chemical Research Institute Yanshan Mountain branch it is useful industrially be load C o-Mo
Or the TiO of Co-Mo-Ni2-A12O3For the BY-5 catalyst of carrier.
Transition metal phosphide is the class new catalytic material received significant attention after nitride and carbide, because
Not only there is the activity of very high hydrodesulfurization and hydrodenitrogeneration for it, and having H2Under conditions of S is present, phosphide compares nitrogen
Compound or carbide are more stable, and with more preferable anti-sulfur poisonous performance.Additionally, phosphide also shows preferably hydrogenation choosing
Selecting property, hydrogen-consuming volume is few, by reducing hydrogen consumption, can more effectively utilize Hydrogen Energy, phosphide to become depth H DS catalysis of new generation
Agent, wherein crystalline state Ni2The catalytic performance of P is optimal.But non-loading type Ni2The specific surface area of P catalyst is very little（Less than 1m2/
G), in order to improve its active surface area, need to be by Ni2P is supported on the carrier of high specific surface area.
The carrier of presently disclosed support type catalyst of phosphatizing nickel includes：A12O3、SiO2、MCM-41、HZSM-5、KUSY、
SBA-15, activated carbon, TiO2Or SiO2-A12O3Deng, but the interaction between different carriers and active component is to catalysis
The performance and its structure of agent has a great impact.The pluses and minuses of above-mentioned various carriers are simply introduced separately below：Due to macropore γ-
A12O3With excellent properties such as larger specific surface area, suitable pore structure, stronger mechanical strength and good heat endurances,
Therefore, it can as industrial traditional hydrodesulfurizationcatalyst catalyst for oil product carrier.If catalyst of phosphatizing nickel is with γ-A12O3To carry
Body, phosphate is easy to and γ-A1 in preparation process2O3The A1 of surface four-coordination3+There is strong interaction and give birth in ion
Into AlPO4, so as to cause the loss even destruction of catalyst surface institutional framework of the P elements of active component, make catalyst live
Property decline, so as to limit macropore γ-A12O3Application of the load catalyst of phosphatizing nickel in hydrogenation industry.SiO2It is considered as negative
The preferable carrier of load nickel phosphide, but SiO2Interaction between carrier and metal component is weaker so as to being unfavorable for that active component exists
The dispersion of carrier surface, can also reduce the activity of hydrodesulfurization.The mesopore molecular sieves such as MCM-41 are used also as hydrodesulfurization catalytic
The carrier of agent.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 to the activity of catalyst sometimes.SBA-15 has higher hydrothermal stability and more
Wide aperture（5～30nm）Adjustable range, but its production cost constrains its industrial applications.TiO2Urge as hydrodesulfurization
Agent carrier not only acts as the effect of conventional carrier, and also acts as the effect of electronics accelerator.TiO2Developed as carrier
Catalyst active high and low temperature activity is good and the features such as strong anti-Poisoning, but TiO2One is there is also as catalyst carrier
A little weakness, such as its specific surface area is relatively small, typically in 70～100m2/ g, the Detitanium-ore-type of activity is easily converted at high temperature
Inert rutile structure, bad mechanical strength and acidity is weaker so as to it is difficult to industrially be widely used.Common
TiO2-Al2O3Carrier loaded nickel phosphide, phosphorus loss is serious, Al2O3Strong effect between P can reduce Ni2In P active components
Phosphorus nickel ratio, it is therefore desirable to higher Ni2P load capacity, increased cost；Meanwhile, reduce catalysis activity.
In above-mentioned loaded catalyst, because the content of active component is less, cause the active relatively low of catalyst.However,
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 to develop a kind of highly active Hydrobon catalyst has become urgent problem.
The content of the invention
For deficiency of the prior art, the present invention is provided and a kind of obtained based on modified composite carrier load nickel phosphide
Hydrobon catalyst, the low temperature hydrogenation activity of the catalyst is high, and with good stability.Present invention also offers above-mentioned
The preparation method of catalyst, the preparation method is simple, easy, and is easily controlled.
For achieving the above object, the invention provides a kind of Hydrobon catalyst, it includes modified titanium oxide-oxidation
Aluminium complex carrier and load nickel phosphide thereon, the modified titanium dioxide-aluminum oxide composite carrier includes alkaline-earth metal group
Divide and vib metals component.
The catalyst provided by the present invention, by using alkaline-earth metal and the TiO of vib metals component modification2-
Al2O3Complex carrier（Or abbreviation carrier）, make Al2O3Have an effect with alkaline-earth metal and vib metals component.When using
State modified TiO2-Al2O3During composite carrier load nickel phosphide, strong interactions of the Al to phosphorus can be greatly reduced, be subtracted significantly
Generation AlPO is lacked4Adverse effect；TiO is played simultaneously2As the effect of the electronics accelerator of hydrodesulfurization catalyst support.
Based on modified TiO2-Al2O3Complex carrier is loading Ni2Catalyst obtained by P can have higher hydrogenation activity and add
Hydrogen desulfurization performance.Meanwhile, catalyst also has higher stability.
In the present invention, the alkaline-earth metal such as magnesium, calcium, strontium, barium and radium, the metal such as chromium and molybdenum of the vib.
In one specific embodiment of catalyst of the present invention, in terms of the alkaline-earth metal, the content of the alkaline earth metal component is based on urges
Agent gross weight is 1～5wt%；In terms of vib metals, the content of vib metals component is based on total catalyst weight
0.1～5wt%.In above-mentioned data area, described modified TiO2-Al2O3Composite carrier load Ni2Catalyst obtained by P
With higher hydrogenation activity and hydrodesulfurization performance.In a specific embodiment, in terms of vib metals, vib
The content of metal component is 0.3～3wt% based on total catalyst weight.In one embodiment, described alkaline-earth metal is calcium；；
The metal of the vib is molybdenum.When alkaline-earth metal selects calcium, and the metal of vib selects molybdenum, then what is obtained is modified
The excellent performance of titanium dioxide-aluminum oxide composite carrier.
In a specific embodiment of catalyst of the present invention, the content of the nickel phosphide is 1 based on total catalyst weight
～25wt%.Due to using the modified TiO in the present invention2-Al2O3During composite carrier load nickel phosphide, Al pair can be greatly reduced
The strong interaction of phosphorus, greatly reduces generation AlPO4Adverse effect, even if using reduce Ni2P content, it is resulting
Catalyst still there is higher hydrogenation activity and hydrodesulfurization ability.In a specific embodiment, the nickel phosphide
Content based on total catalyst weight be 15～25wt%.
In a specific embodiment of catalyst of the present invention, the catalyst that the present invention is provided also includes being carried on described changing
Lanthanide metal component and/or group VIII metal component on the titanium dioxide-aluminum oxide composite carrier of property.By described modified
Titanium dioxide-aluminum oxide composite carrier on introduce lanthanide metal component or group VIII metal component, can further improve this
The low temperature hydrogenation activity of catalyst.In a specific embodiment, the content of lanthanide metal component is based on total catalyst weight
For 0.1～3wt%.In another specific embodiment, the content of group VIII metal component is 1 based on total catalyst weight
～10wt%, preferably 1～5wt%.The lanthanide series metal such as lanthanum, cerium, praseodymium, neodymium etc..The metal of the group VIII for example cobalt, rhodium,
Iridium etc..In a specific embodiment, described lanthanide series metal is cerium, and the metal of the group VIII is cobalt.
In a specific embodiment of the present invention, the Hydrobon catalyst is C5-C9Fraction oil hydrodesulfurizing is catalyzed
Agent.
Present invention also offers a kind of preparation method of Hydrobon catalyst, including：
Step A：By titanium dioxide-aluminum oxide composite oxides comprising the alkaline-earth metal aqueous solution and vib metals component
Solution mixed solution in impregnate, then be dried and roasting, obtain modified titanium oxide-alumina composite carrier；
Step B：Modified titanium oxide-alumina composite carrier is soaked in comprising nickel salt solution and phosphatic maceration extract
Stain, obtains the catalyst.
According to the present invention provide method, by using alkaline-earth metal and group vib metal component to TiO2-Al2O3Composite oxygen
Compound（Or abbreviation oxide）It is modified, has prepared modified TiO2-Al2O3Complex carrier, then to the complex carrier
Impregnated, obtain loading the catalyst of nickel phosphide.Due to the modified TiO for adopting2-Al2O3Complex carrier, it is to Ni2P bears
The requirement of carrying capacity is reduced so that preparing the cost of catalyst reduces.Meanwhile, modified TiO2-Al2O3Complex carrier can be significantly
Strong interactions of the Al to phosphorus is reduced, generation AlPO is greatly reduced4Adverse effect, be conducive to improve catalyst work
Property；TiO is played simultaneously2As the effect of the electronics accelerator of hydrodesulfurization catalyst support.It is made by above-mentioned preparation method
The standby Hydrobon catalyst for obtaining has good stability.
It is its process is simple, easy according to the method that the present invention is provided, it is easily controlled, low cost, it is front with broad application
Scape.
In one particular embodiment of the present invention, the roasting in step A can carry out 4 at 500～600 DEG C～
6h, then obtains described modified titanium oxide-alumina support.
The specific surface area of the unmodified front titanium dioxide-aluminum oxide composite oxides that the present invention is provided is 80～180m2/ g,
Pore volume is 0.4～1.3cm3/ g and most probable pore size are 90～150 angstroms.The oxygen of specific surface area and pore volume from suitable size
Changing titanium-alumina composite carrier is conducive to the catalyst for obtaining to have preferably activity and stability.In addition, in order that preparing
The catalyst of acquisition has that high-specific surface area, compression strength are high, diffusion velocity is fast, the low advantage of reactor bed pressure drop, at this
In one instantiation of invention, described titanium dioxide-aluminum oxide composite carrier is clover shape.
In one embodiment of the inventive method, described alkaline-earth metal is calcium；The metal of described vib is
Molybdenum.Titanium dioxide-aluminum oxide composite oxides impregnate in the aqueous solution in the aqueous solution comprising calcium and containing molybdenum, obtain calcium and molybdenum is modified
Titanium dioxide-aluminum oxide composite carrier.
In one particular embodiment of the present invention, in step B, after dipping, can also be dried and baking operation,
Obtain described catalyst.In an instantiation, described is acidity comprising nickel salt solution and phosphatic maceration extract.It is described
Can must make to be loaded with nickel phosphide on complex carrier comprising nickel salt solution and phosphatic maceration extract, it is described comprising nickel salt solution and
Phosphatic maceration extract such as the maceration extract comprising nickelous hypophosphite.
In one embodiment of the inventive method, in the maceration extract also comprising lanthanide metal component solution and/or
The solution of group VIII metal component.By this operation, further on the modified titanium dioxide-aluminum oxide composite carrier
The metal component of lanthanide metal component or group VIII is loaded with, the low temperature hydrogenation activity of the catalyst can be further improved.
In a specific embodiment, described lanthanide series metal is cerium.In another specific embodiment, the group VIII
Metal is cobalt, and by introducing cerium and/or cobalt in catalyst, the low temperature hydrogenation that can further improve the catalyst is active and de-
Sulphur activity.
According to a further aspect in the invention, a kind of hydrodesulfurizationprocess process is additionally provided, its intermediate distillates is in the catalyst
Or carry out hydrodesulfurization in the presence of the catalyst of method preparation.In a specific embodiment, the distillate is C5-C9
Distillate.In another specific embodiment, the distillate is C6-C8Distillate.
In one embodiment of the inventive method, reaction temperature is 210～300 DEG C in hydrodesulfurization, reaction pressure
Power is 2.0～5.0MPa, and Feed space velocities are 1.5～5.0h-1, hydrogen-oil ratio (volume ratio) is 150:1～450:1.
C is used for according to the method that the present invention is provided5-C9The hydrodesulfurization of distillate, especially C6-C8Two sections of distillate
Hydrodesulfurization, has the advantages that hydrogenation activity is high and hydrodesulfurization ability is strong；And while hydrodesulfurization, being capable of maximum limit
The hydrogenation saturation monoolefine of degree, adapts to the change of feed sulphur content and the requirement of high-speed.
C can be under cryogenic used for according to the catalyst that the present invention is provided5-C9The hydrodesulfurization work of distillate
Skill, it is high to double-bond hydrogenation saturation degree, saturation monoolefine is especially hydrogenated with to greatest extent, hydrogenation activity is high, and good stability.
According to the present invention, by using alkaline-earth metal and vib metals component to TiO2-Al2O3Composite oxides are carried out
It is modified, obtain the modified TiO comprising alkaline earth metal component and vib metals component2-Al2O3Complex carrier；It is described modified
Complex carrier is impregnated, and obtains the catalyst comprising nickel phosphide（Ni2P）.The modified TiO2-Al2O3Complex carrier has both
Al2O3Carrier specific surface area is big, pore structure is suitable, the excellent properties of mechanical strength and good thermal stability, and TiO has been played again2Make
For the effect of the electronics accelerator of hydrodesulfurization catalyst support, reduce because of phosphorus and Al2O3Interaction caused by activity damage
Lose.The modified TiO2-Al2O3Complex carrier, to Ni2The requirement of P load capacity is reduced so that prepare the cost drop of catalyst
It is low, and the Hydrobon catalyst for preparing has higher hydrogenation activity and hydrodesulfurization performance；Can will crack vapour
Sulphur and monoene removing in oil；The catalysis activity of the catalyst for finally preparing can further be improved.
Specific embodiment
The present invention will be more fully described by the following example the present invention, can make those skilled in the art that this is more fully understood
It is bright, but these embodiments do not constitute any restriction to the scope of the present invention.
Bromine valency：Bromine valency is used to weigh presence of unsaturates in oil samples, the grams of the bromine consumed with 100 grams of oil samples
To represent.Bromine valency is higher, and unsaturated hydrocarbons is more contained by oil samples.Generally oil samples are analyzed using small-hole drilling.
Feed space velocities are inlet amount/catalyst qualities per hour, and unit is h-1。
The detection of specific surface and pore volume：The detection of specific surface and pore volume including aluminum oxide, complex carrier and catalyst.Than
Hold surface area detection method and adopt multiple spot BET method, detected using F-sorb2400 specific surface area analysis instrument；The detection side of pore volume
Method adopts static volumetric method, is detected using V-sorb2800 pore volumes detector.
Titanium dioxide-aluminum oxide composite carrier selects trifolium-shaped in following examples.In the preparation side of catalyst of the present invention
In method, the production firm of aluminum 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.Take
Specific surface area is 160m2/ g, pore volume is 0.58ml/g, and most probable pore size is 130 angstroms of cloverleaf pattern aluminum oxide 90g, with 53 millis
The 0.557g/ml dilution heat of sulfuric acid dipping of titanium sulfate is risen, is stirred 15 minutes, after 120 DEG C of dryings 8 hours, in 900 DEG C 4 are calcined
Hour, titanium dioxide-aluminum oxide composite oxides A is obtained1, i.e. titanium dioxide-aluminum oxide composite carrier.Gained titanium dioxide-aluminum oxide
Composite oxides A1Titanium oxide content be 10 weight %, specific surface area is 144m2/ g, pore volume is 0.56ml/g, most probable pore size
For 125 angstroms.
Take four water-calcium nitrate 27.7g and be made into mixed solution with ammonium molybdate tetrahydrate 4.5g, add water and be configured to 140mL solution, to
Four water-calcium nitrate is prepared with ammonium molybdate tetrahydrate and add in the solution for obtaining 100g titanium dioxide-aluminum oxide composite oxides A1,
Stirring 20 minutes, dries after draining away the water at 120 DEG C, then at 550 DEG C calcining obtain within 4 hours modified titanium oxide-
Alumina composite oxide A2, i.e. modified titanium oxide-alumina composite carrier A2。
The preparation of catalyst：
The dipping liquor of the diammonium hydrogen phosphate that 20ml contains 7.1g nickel nitrates and 2.61g is prepared, nitric acid is added dropwise makes dipping
The pH of liquid is 3.0, at ambient temperature, takes 10g modified titanium oxides-alumina composite carrier A2, impregnated with maceration extract, 120
It is dried at DEG C 24 hours, then calcines 4 hours at 550 DEG C, taking-up is cooled to room temperature, obtains final product catalyst.Catalyst data is shown in
Table 1.
Embodiment 2
With embodiment 1, difference is the phosphoric acid containing 4.7g nickel nitrates and 1.70g in the dipping liquor to step
The cerous nitrate of the ammonium of hydrogen two and 1.55g.Catalyst data is shown in Table 1.
Embodiment 3
The preparation of modified titanium oxide-alumina composite carrier：
Step is with embodiment 1, difference, and the addition of four water-calcium nitrate is 15.6g in the mixed solution, four
The addition of water ammonium molybdate is 8.7g.
The preparation of catalyst：
Step with embodiment 1, difference be prepare diammonium hydrogen phosphate that 20ml contains 7.1g nickel nitrates and 2.61g and
The dipping liquor of the cobalt nitrate of 3.70g.Catalyst data is shown in Table 1.
Embodiment 4
The preparation of modified titanium oxide-alumina composite carrier：
Step is with embodiment 1, difference, and the addition of four water-calcium nitrate is 23.8g, the addition of ammonium molybdate tetrahydrate
Measure as 0.75g, calcining heat is 500 DEG C.
The preparation of catalyst：
With embodiment 1, difference is to prepare the diammonium hydrogen phosphate that 20ml contains 3.97g nickel nitrates and 1.43g to step
With the dipping liquor of the cobalt nitrate of 0.63g.Catalyst data is shown in Table 1.
Comparative example 1
If step is with embodiment 1, difference is directly to use 10g titanium dioxide-aluminum oxide composite oxides A1With institute
State maceration extract to be impregnated.Data are shown in Table 1.Comparative example 3
Comparative example 2
Step is directly to use 10g titanium dioxide-aluminum oxide composite oxides A with embodiment 2, difference1With described
Maceration extract is impregnated.Data are shown in Table 1.
Comparative example 3
Step is directly to use 10g titanium dioxide-aluminum oxide composite oxides A with embodiment 3, difference1With described
Maceration extract is impregnated.Data are shown in Table 1.
The content of the catalyst components of table 1
Hydrodesulfurization reaction
The performance evaluation of catalyst in embodiment 1-4 and comparative example 1-3：Using the catalysis prepared by above-mentioned preparation method
Agent is to C6-C8Cut secondary hydrogenation raw material carries out hydrogenation evaluation, and equipment therefor is the small testing device of 200mL trickle bed reactors.It is former
Material takes from the factory benzene production equipment C of Sinopec Yanshan Mountain branch company chemical industry seven6～C8Cut secondary hydrogenation raw material, raw material total sulfur content is
103ppm, bromine valency is 30.5gBr/100goil.Diene content is 7.0g I/100goil.Catalyst is carried out before evaluation
Sulfuration.Reactor is risen to into 300 DEG C from room temperature with the speed of 10 DEG C/min in the hydrogen gas stream of 100mL/min, then with 1 DEG C/
The speed of min is warming up to 550 DEG C, and maintains 2h, is down to 300 DEG C with the CS containing 1%wt2Cyclohexane solution it is vulcanized
Process 2h.As shown in table 2, liquid air speed is Feed space velocities in table for appreciation condition and product analysis result：
The appreciation condition and product analysis result of the catalyst of the present invention of table 2.
From table 2 it can be seen that although the content of the nickel phosphide in comparative example 1 is higher than embodiment 1, it is used for hydrodesulfurization
When, the hydrodesulfurization effect of the catalyst in embodiment 1 is far superior to comparative example 1.It is known that according to the present invention from table 2
The catalyst of offer is used for hydrodesulfurization reaction, and with higher hydrodesulfurization activity, the sulphur that can be substantially reduced in product contains
Amount, and presence of unsaturates.
Claims (15)
1. a kind of Hydrobon catalyst, it includes modified titanium oxide-alumina composite carrier and load nickel phosphide thereon,
Modified titanium oxide-the alumina composite carrier includes alkaline earth metal component and vib metals component, with vib metals
Meter, the content of vib metals component is 0.1～5wt% based on total catalyst weight, in terms of alkaline-earth metal, the alkaline earth gold
The content of category component is 1～5wt% based on total catalyst weight；The content of nickel phosphide based on total catalyst weight be 15～
25wt%.
2. catalyst according to claim 1, it is characterised in that in terms of vib metals, vib metals component
Content is 0.3～3wt% based on total catalyst weight.
3. catalyst according to claim 1 and 2, it is characterised in that the catalyst also includes being carried on described modified
Titanium dioxide-aluminum oxide composite carrier on lanthanide metal component and/or group VIII metal component.
4. catalyst according to claim 3, it is characterised in that the content of lanthanide metal component is based on total catalyst weight
For 0.1～3wt%.
5. catalyst according to claim 3, it is characterised in that the content of group VIII metal component is total based on catalyst
Weight is 1～10wt%.
6. catalyst according to claim 3, it is characterised in that the content of group VIII metal component is total based on catalyst
Weight is 1～5wt%.
7. catalyst according to claim 3, it is characterised in that described alkaline-earth metal is calcium；Described vib
Metal is molybdenum；Described lanthanide series metal is cerium；The metal of the group VIII is cobalt.
8. a kind of preparation method of the catalyst as described in any one in claim 1-7, including：
Step A：By titanium dioxide-aluminum oxide composite oxides molten comprising the alkaline-earth metal aqueous solution and vib metals component
Impregnate in the mixed solution of liquid, be then dried and roasting, obtain modified titanium oxide-alumina composite carrier；
Step B：Modified titanium oxide-alumina composite carrier is impregnated in comprising nickel salt solution and phosphatic maceration extract, is obtained
To the catalyst.
9. method according to claim 8, it is characterised in that titanium dioxide-aluminum oxide composite oxides in step A
Specific surface area is 80～180m2/ g, pore volume is 0.4～1.3cm3/ g, most probable pore size is 90～150 angstroms.
10. method according to claim 8 or claim 9, it is characterised in that also comprising lanthanide metal component in the maceration extract
The solution of solution and/or group VIII metal component.
11. methods according to claim 10, it is characterised in that described alkaline-earth metal is calcium；Described vib
Metal is molybdenum；Described lanthanide series metal is cerium；The group VIII metal is cobalt.
A kind of 12. hydrodesulfurizationprocess process, its intermediate distillates catalyst or claim described in any one in claim 1-7
Hydrodesulfurization is carried out in the presence of the catalyst that in 8-11 prepared by any one method.
13. methods according to claim 12, it is characterised in that the distillate is C5-C9Distillate.
14. methods according to claim 12, it is characterised in that the distillate is C6-C8Distillate.
15. methods according to claim 12, it is characterised in that reaction temperature is 210～300 in catalytic hydrogenation
DEG C, reaction pressure is 2.0～5.0MPa, and Feed space velocities are 1.5～5.0h-1, hydrogen-oil ratio is 150:1～450:1.
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| CN105498793A (en) * | 2015-11-28 | 2016-04-20 | 南京威安新材料科技有限公司 | Hydrodesulfurization catalyst |
| 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 | A kind of Hydrobon catalyst of modification 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 |
| CN111760581B (en) * | 2019-08-30 | 2021-07-23 | 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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