CN103059983B - Hydrofining catalyst combined filling method - Google Patents
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- CN103059983B CN103059983B CN201110321355.7A CN201110321355A CN103059983B CN 103059983 B CN103059983 B CN 103059983B CN 201110321355 A CN201110321355 A CN 201110321355A CN 103059983 B CN103059983 B CN 103059983B
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Abstract
The invention discloses a hydrofining catalyst combined filling method. According to the method, after the raw material diesel oil and hydrogen are mixed, the mixture passes through four hydrogenation reaction zones in order, and different reaction zones are respectively filled with hydrofining catalysts having different metal content and acid amounts. The reaction effluent is subjected to separation and fractionation so as to obtain a diesel oil product. The invention adopts a grading filling method for different catalysts, can give full play to the respective advantages of different types of catalysts, thus endowing the catalyst grading filling system with higher reaction activity, stability and lower reaction hydrogen consumption on the whole. The method provided in the invention is especially suitable for the hydrofining process of coking diesel oil or catalytic cracking diesel oil.
Description
Technical field
The present invention relates to a kind of Hydrobon catalyst combination loading method, particularly a kind of diesel oil deepness hydrogenation catalyst for refining combination loading method.
Background technology
Along with the raising of people's environmental consciousness and the increasingly stringent of environmental regulation, produce and use fuel for cleaning vehicle more and more to become a kind of development trend.And cleaning for diesel oil, desulfurization and Porous deproteinized bone are the keys that it cleans.
At present, take off in fragrant technology in the desulfurization of diesel oil, hydrotreating techniques remains main, be also the most effective technique means.In hydrogenator, from top to bottom different zones reaction conditions is different, reaction environment chemical reaction type that is different, that carry out is not identical yet, and catalyzer single is in this case difficult to the reaction needed simultaneously meeting differential responses region in reactor usually.Be used alone these catalyzer and often can not meet requirement in actual production completely.For this reason, need to be used by the grading loading of different catalysts, meet the requirement of differential responses in same reactor differential responses region.The performance of catalyst activity is often closely related with many factors, except form with catalyst metal and metal content relevant, the factor such as composition, pore size, Acidity of support of the catalyst affects the performance of catalyst activity too, therefore, the grating of catalyzer should go to consider from multiple angle, finally reaches the preferably performance of catalyst activity, stability.
CN 101092573A discloses a kind of method of hydrotreating producing low-sulfur diesel-oil; the method enters hydrogenator after adopting stock oil to mix with hydrogen; contact with optional Hydrobon catalyst III with hydrogenation protecting agent, Hydrobon catalyst I, Hydrobon catalyst II successively and react; wherein Hydrobon catalyst I with molybdenum and cobalt for active metal component; Hydrobon catalyst II is with tungsten, molybdenum and nickel for active metal component, and Hydrobon catalyst III is the optional active high catalyzer of direct desulfurization.Reaction is produced in the middle of thing and is not separated, and reaction effluent obtains the low-sulfur diesel-oil that sulphur content meets Eu III standard and the Europe IV standard after refrigerated separation.
US 6251262B1 discloses a kind of diesel oil hydrodesulphurizatiomethod method, and the method adopts raw material successively by three reaction zones: the active metal component of the first reaction zone catalyzer is molybdenum and cobalt, take porous alumina as carrier; The catalyzer of second reaction zone is that the metal of load is molybdenum and nickel with porous alumina and small part zeolite for carrier; The active metal component of the catalyzer of the 3rd reaction zone is molybdenum and nickel or molybdenum and cobalt, take porous alumina as carrier.The method temperature 320 DEG C ~ 370 DEG C, pressure 3.0MPa ~ 15.0MPa, liquid hourly space velocity 0.5 h
-1~ 3h
-1, under hydrogen to oil volume ratio 180 ~ 900 condition, be met the diesel oil of the Europe IV standard.
Summary of the invention
There is the difference of chemical reaction type for differential responses region in hydrofining reactor, the invention provides a kind of Hydrobon catalyst combination loading method, better to play the effect of catalyzer.
Reactor is divided into four regions by catalyst combination loading method of the present invention: 1, mechanical impurity, solid particulate interception and olefin saturated region; 2, simple sulfide and nitride reaction remove region; 3, the saturated and isomerizing zone of complicated sulfide, nitride and aromatic hydrogenation; 4, deep hydrodesulfurizationof conversion zone.
Hydrobon catalyst combination loading method of the present invention, comprises following content:
After raw material diesel oil mixes with hydrogen, successively by four hydroconversion reaction zones, with Hydrobon catalyst contact reacts, hydrogenation reaction effluent obtains diesel product through separation and fractionation; The wherein Hydrobon catalyst of the following character of hydroconversion reaction zone grading loading:
Load molybdenum-nickel catalyzator in first reaction zone, metal content is 5 ~ 15 wt% with oxide basis, and the total acid content of catalyzer is 0.2 ~ 0.5mmol/g;
Second reaction zone filling molybdenum-cobalt catalyst, wherein metal content is 10 ~ 15 wt% with oxide basis, and catalyzer total acid content is 0.2 ~ 1.0 mmol/g;
Load molybdenum-nickel catalyzator, tungsten-nickel catalyzator or tungsten-molybdenum-nickel catalyzator in 3rd reaction zone, metal content is 20 ~ 50 wt% with oxide basis, and the total acid content of catalyzer is 1.0 ~ 3.0 mmol/g;
4th reaction zone filling molybdenum-cobalt catalyst, its metal content is 20 ~ 30 wt% with oxide basis, and catalyzer total acid content is 0.2 ~ 1.0 mmol/g.
According to method of the present invention, wherein the first reaction zone is mechanical impurity, solid particulate interception and olefin saturated region.Contain more mechanical impurity and unsaturated hydrocarbons (as alkene, diolefine etc.) with the raw material of the first reaction zone catalyst exposure, the easy polymerization coking on a catalyst of unsaturated hydro carbons is deposited in catalyst surface and duct together with mechanical impurity.Therefore, the present invention holds the strong large pore volume catalyzer of dirty ability in-built being filled with of the first conversion zone, the shape of this region inner catalyst can be that Raschig ring shape, butterfly, porous cheese etc. hold the strong irregular shape catalyst of dirty ability, meanwhile, catalyzer has certain olefin saturated ability to remove alkene and diolefine.
Second reaction zone is that simple sulfide and nitride reaction remove region., condition lower at second reaction zone interior reaction temperature relaxes, and the reaction therefore mainly carried out in this region is the hydrogenation and removing reaction of simple sulfide, nitride.For this reason, the inventive method uses the Mo-Co type Hydrobon catalyst of low-metal content, low acid amount in this conversion zone, so both can meet simple sulfide, the simple needs that remove reaction of nitride in this region, also reduce the possibility of this region inner catalyst coking simultaneously.
3rd reaction zone is the saturated and isomerizing zone of complicated sulfide, nitride and aromatic hydrogenation.The raw material contacted with the 3rd conversion zone removes relative to the easy coking material in the first reaction zone and second reaction zone, lower relative to the 4th reaction zone temperature of reaction, hydrogen dividing potential drop is higher, and reaction environment is better.Therefore, in this region, load the catalyzer with high hydrogenation activity and certain heterogeneous activity carry out aromatic saturation and isomerization reaction, sterically hindered effect is eliminated containing the dibenzothiophene class sulfide of sterically hindered effect by a saturated aromatic ring or alkyl isomerization reaction for 4,6 in this reaction zone.For this reason, can fill Mo-Ni or the W-Ni catalyzer of peracidity, high metal content in this region, also can be body phase method catalyzer.Both be conducive to the carrying out of hydrotreated lube base oil and isomerization reaction like this, meanwhile, the reaction mass of this region clean and the condition of mitigation relatively reduce the carbon distribution coking amount of peracidity catalyzer, are conducive to the stable performance of this type of catalyst activity.
4th reaction zone is deep hydrodesulfurizationof conversion zone.Through the reaction of first three conversion zone, in 4th conversion zone, reactant is mainly residue sulfide and nitride, this part unreacted reactant is after hydrogenation in the 3rd reaction zone and isomerization reaction, sterically hinderedly to eliminate, but this conversion zone is the highest at whole reactor interior reaction temperature, hydrogen dividing potential drop is minimum, obvious by thermodynamical restriction, select in this region for this reason direct desulfurization active stronger, by hydrogen dividing potential drop and the less Mo-Co type catalyzer of thermodynamical restriction.Meanwhile, in order to reduce the coking reaction impact on catalyst activity of this region inner catalyst under high temperature, hydrogen partial pressure severe condition, this region inner catalyst should have lower acidity.So both be beneficial to the carrying out of this region direct desulfurization reaction, be also conducive to improving this region catalyst stability.Therefore, under hydrofining technology condition, bavin oil-hydrogen mixture is by territory, above-mentioned four reaction areas.
According to Hydrobon catalyst combination loading method of the present invention, wherein in each reaction zone, the ratio of Hydrobon catalyst specifically can be determined according to the difference of reaction feed and reaction conditions.The volume fraction that each reaction zone catalyzer accounts for whole hydrogenation catalyst is generally as follows: the first reaction zone is 5 ~ 15 v%, second reaction zone 15 ~ 30 v%, the 3rd reaction zone 40 ~ 70 v%, the 4th reaction zone 10 ~ 40 v%.
In the inventive method, described hydrofining technology condition comprises: temperature of reaction is 320 DEG C ~ 400 DEG C, preferably 340 DEG C ~ 380 DEG C; Reaction pressure is 3.0 MPa ~ 10.0 MPa, preferably 4.0 MPa ~ 8.0 MPa; During liquid, volume space velocity is 1.0h
-1~ 6.0h
-1, preferred 1.5h
-1~ 4.0h
-1; Hydrogen to oil volume ratio is 100 ~ 1000, preferably 400 ~ 800.
Catalyst grade of the present invention joins filling method, according to the difference of differential responses regional chemistry reaction type in reactor, as at poor the first reactor of reaction environment and the acid more weak catalyzer of the 4th reaction zone filling, the coking carbon distribution that acidity of catalyst causes can be suppressed like this, thus improve the response characteristic in this region.And react the 3rd maximum reaction zone of difficulty, good 3rd reaction zone of reaction environment at deep desulfuration, high, the acid strong hydrogenation catalyst of filling metal content targetedly, while the desulfurization of guarantee catalyst depth, aromatic saturation, isomerization reaction carry out, reduce the coking carbon distribution of peracidity catalyzer as much as possible.Meanwhile, to join with catalyst cartridge single-stage with traditional single catalyst system and compare, this bright catalyst grade joins filling method, the Mo-Co catalyzer of low-metal content and low acidity has been loaded in either shallow desulfurization reaction zone, while ensure that the reaction of this region is carried out, reduce catalyzer purchase cost, reduce hydrogen consumption, therefore, this catalyst combination loading system has higher reactive behavior, stability and lower reactive hydrogen consumption generally.Therefore, catalyst combination loading method of the present invention is a kind of catalyst system that can be used for Europe IV, the production of Europe V ultra-low-sulphur diesel, and relatively existing catalyst system has better comprehensive use properties.
Embodiment
In the present invention, the catalyzer of employing refers to the non-noble metal hydrogenation catalyst with hydrogenating desulfurization, hydrodenitrification, aromatic saturation function, and the function of catalyzer can stress some aspect.This non-precious metal catalyst is general before use to be existed with oxidation states, needs to carry out prevulcanized, makes non-noble metal oxide be converted into sulfide and just have reactive behavior.Therefore, non-precious metal catalyst in use will keep sulphided state.
In the methods of the invention, the catalyzer that each conversion zone uses can use commercially available prod, also can prepare according to this area Conventional wisdom.
Molybdenum-nickel catalyzator wherein in the first reaction zone, metal content is 5 ~ 15 wt% with oxide basis, and the total acid content of catalyzer is 0.2 ~ 0.5mmol/g.Do not limit the strong acid content of catalyzer, its strong acid content is generally 0.02 ~ 0.06mmol/g.Described molybdenum-nickel catalyzator also should have larger pore volume usually, is generally 0.60 ~ 0.80 mL/g, and specific surface is generally 260 ~ 330 m
2/ g.The carrier of catalyzer is Al
2o
3or silicon-containing alumina, shape is Raschig ring, butterfly or honeycombed.The size of described catalyzer and hydrogenation protecting agent is similar, and diameter is generally 4.9 ~ 5.2mm, long 3 ~ 10 mm.
Molybdenum-the cobalt catalyst of second reaction zone, metal content is 10 ~ 15 wt% with oxide basis, and catalyzer total acid content is 0.2 ~ 1.0 mmol/g.Do not limit the strong acid content of catalyzer, strong acid content can be generally 0.02 ~ 0.08 mmol/g; Catalyst shape is generally cylinder, trifolium, and support of the catalyst is Al
2o
3or silicon-containing alumina.
Molybdenum-the nickel of the 3rd reaction zone, tungsten-nickel or tungsten-molybdenum-nickel catalyzator, metal content is 20 ~ 50 wt% with oxide basis, and the total acid content of catalyzer is 1.0 ~ 3.0 mmol/g.Do not limit the strong acid content of catalyzer, strong acid content is generally 0.1 ~ 0.3 mmol/g.General with TiO
2-al
2o
3or silicon-containing alumina or molecular sieve-aluminum oxide are carrier.
Molybdenum-the cobalt catalyst of the 4th reaction zone, its metal content is 20 ~ 30 wt% with oxide basis; Total acid content is 0.2 ~ 1.0mmol/g.Do not limit the strong acid content of catalyzer, strong acid content is generally 0.02 ~ 0.08mmol/g.The pore volume of described molybdenum-cobalt catalyst is 0.40 ~ 0.80 mL/g, and specific surface area is 200 ~ 400 m
2/ g, carrier is generally Al
2o
3or silicon-containing alumina.
Four wherein said hydroconversion reaction zones can be distributed in a reactor, also can be distributed in the hydrogenator of two series connection.
Below by specific embodiment and comparative example, the solution of the present invention and effect are described.
Embodiment 1 ~ 3
According to method of the present invention, different catalyzer is selected to carry out grating, and for the hydrotreatment of diesel raw material.The catalyst grade part system that embodiment 1 ~ 3 is selected is as follows respectively
Table 1 embodiment 1 catalyst grade formula formula
| First reaction zone | Second reaction zone | 3rd reaction | 4th reaction | |
| Metal forms | Mo-Ni | Mo-Co | Mo-Ni | Mo-Co |
| Metal content, wt% | 8 | 14 | 32 | 22 |
| Shape | Raschig ring | Trifolium | Trifolium | Trifolium |
| Carrier | Al 2O 3 | Silicon oxidation aluminium | TiO 2-Al 2O 3 | Al 2O 3 |
| Total acid content, mmol/g | 0.20 | 0.50 | 2.0 | 0.7 |
| Strong acid content, mmol/g | 0.03 | 0.04 | 0.21 | 0.05 |
| Ratio, % | 10 | 20 | 40 | 30 |
Table 2 embodiment 2 catalyst grade formula formula
| First reaction zone | Second reaction zone | 3rd reaction zone | 4th reaction zone | |
| Metal forms | Mo-Ni | Mo-Co | Mo-Ni | Mo-Co |
| Metal content, % | 8 | 14 | 32 | 22 |
| Shape | Raschig ring | Trifolium | Trifolium | Trifolium |
| Carrier | Al 2O 3 | Silicon oxidation aluminium | TiO 2-Al 2O 3 | Al 2O 3 |
| Total acid content, mmol/g | 0.25 | 0.5 | 2.0 | 0.7 |
| Strong acid content, mmol/g | 0.03 | 0.04 | 0.21 | 0.05 |
| Ratio, % | 10 | 10 | 50 | 30 |
Table 3 embodiment 3 catalyst grade formula formula
| First reaction zone | Second reaction zone | 3rd reaction zone | 4th reaction zone | |
| Metal forms | Mo-Ni | Mo-Co | Mo-Ni | Mo-Co |
| Metal content, wt% | 12 | 14 | 28 | 22 |
| Shape | Honeycombed | Trifolium | Trifolium | Trifolium |
| Carrier | Al 2O 3 | Silicon-containing alumina | Al 2O 3-molecular sieve | Al 2O 3 |
| Total acid content, mmol/g | 0.25 | 0.5 | 2.5 | 0.7 |
| Strong acid content, mmol/g | 0.03 | 0.04 | 0.3 | 0.05 |
| Ratio, % | 10 | 15 | 45 | 30 |
Table 4 stock oil character
| Project | Stock oil |
| Density, g/cm 3 | 0.8569 |
| Boiling range, DEG C | 199～379 |
| Sulphur content, μ g/g | 10000 |
| Nitrogen content, μ g/g | 316 |
| Aromaticity content, wt % | 37.5 |
Table 5 embodiment 1 ~ 3 adopt operational condition
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Temperature of reaction, DEG C | 350 | 360 | 370 |
| Reaction pressure, MPa | 6.0 | 8.0 | 6.0 |
| Volume space velocity, h -1 | 1.5 | 2.0 | 2.0 |
| Hydrogen to oil volume ratio | 600 | 600 | 600 |
Table 6 embodiment 1 ~ 3 evaluation result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Start of run | |||
| Sulphur content, μ g/g | 28 | 9.0 | 3.0 |
| Nitrogen content, μ g/g | 12 | 1.0 | 1.0 |
| Aromaticity content, wt% | 20.5 | 13.5 | 12.5 |
| Chemical hydrogen consumption | 0.47 | 0.50 | 0.52 |
| Operate after 6 months | |||
| Sulphur content, μ g/g | 40 | 10.0 | 6.0 |
| Nitrogen content, μ g/g | 12.8 | 13.7 | 14.2 |
| Aromaticity content, wt% | 28 | 14.0 | 16.0 |
| Chemical hydrogen consumption | 0.47 | 0.50 | 0.52 |
Comparative example 1 ~ 3
Comparative example 1 ~ 3 selects the widely used ultra-deep desulfurization catalyzer of current industrial application, and its character is as shown in table 7, the reaction conditions of comparative example 1 ~ 3 and feedstock property identical with embodiment 1 ~ 3, comparative example test-results is as table 8.Embodiment 1 ~ 3 and comparative example 1 ~ 3 adopt flow process of the present invention.
Table 7 comparative example 1 ~ 3 catalyzer physico-chemical property
| Project | Catalyzer |
| Chemical constitution, quality % | |
| MoO 3 | 20.2 |
| NiO | 12.3 |
| Carrier | Silicon-containing alumina |
| Physico-chemical property | |
| Pore volume, mL/g | 0.45 |
| Specific surface area, m 2/g | 201 |
| Total acid content, mmol/g | 1.2 |
| Strong acid content, mmol/g | 0.12 |
Table 8 comparative example 1 ~ 3 evaluation result
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| Start of run | |||
| Sulphur content, μ g/g | 55 | 22 | 11.0 |
| Nitrogen content, μ g/g | 8 | 1.0 | 1.0 |
| Aromaticity content, wt% | 23.5 | 15.5 | 13.5 |
| Chemical hydrogen consumption, wt% | 0.52 | 0.53 | 0.56 |
| After 6 months | |||
| Sulphur content, μ g/g | 102 | 45 | 33 |
| Nitrogen content, μ g/g | 28 | 18.5 | 16.0 |
| Chemical hydrogen consumption, wt% | 0.50 | 0.51 | 0.53 |
Found by embodiment 1 ~ 3 and comparative example 1 ~ 3 comparing result, the inventive method grading loading catalyst system processes identical raw material compared to traditional single catalyst system under same process condition, reaction depth is darker, chemical hydrogen consumption is lower, simultaneously, operate after 6 months, this system is active in significantly sacrificing, shows good over-all properties.
Claims (10)
1. a Hydrobon catalyst combination loading method, comprises following content:
After raw material diesel oil mixes with hydrogen, successively by four hydroconversion reaction zones, with Hydrobon catalyst contact reacts, hydrogenation reaction effluent obtains diesel product through separation and fractionation; The Hydrobon catalyst of the wherein different following character of hydroconversion reaction zone grading loading:
Load molybdenum-nickel catalyzator in first reaction zone, metal content is 5 ~ 15 wt% with oxide basis, and the total acid content of catalyzer is 0.2 ~ 0.5mmol/g;
Second reaction zone filling molybdenum-cobalt catalyst, wherein metal content is 10 ~ 15 wt% with oxide basis, and catalyzer total acid content is 0.2 ~ 1.0 mmol/g;
Load molybdenum-nickel catalyzator, tungsten-nickel catalyzator or tungsten-molybdenum-nickel catalyzator in 3rd reaction zone, metal content is 20 ~ 50 wt% with oxide basis, and the total acid content of catalyzer is 1.0 ~ 3.0 mmol/g;
4th reaction zone filling molybdenum-cobalt catalyst, its metal content is 20 ~ 30 wt% with oxide basis, and catalyzer total acid content is 0.2 ~ 1.0 mmol/g.
2. in accordance with the method for claim 1, it is characterized in that, the volume fraction that each reaction zone catalyzer accounts for whole hydrogenation catalyst is as follows: the first reaction zone is 5 ~ 15 v%, second reaction zone 15 ~ 30 v%, 3rd reaction zone 40 ~ 70 v%, the 4th reaction zone 10 ~ 40 v%.
3. in accordance with the method for claim 1, it is characterized in that, the processing condition of described hydrofining reaction are: temperature of reaction is 320 DEG C ~ 400 DEG C, and reaction pressure is 3.0 MPa ~ 10.0 MPa, and during liquid, volume space velocity is 1.0h
-1~ 6.0h
-1, hydrogen to oil volume ratio is 100 ~ 1000.
4. in accordance with the method for claim 1, it is characterized in that, the processing condition of described hydrofining reaction are: temperature of reaction is 340 DEG C ~ 380 DEG C, reaction pressure 4.0 MPa ~ 8.0 MPa, volume space velocity 1.5h during liquid
-1~ 4.0h
-1, hydrogen to oil volume ratio 400 ~ 800.
5. in accordance with the method for claim 1, it is characterized in that, the pore volume of the molybdenum-nickel catalyzator in the first reaction zone is 0.60 ~ 0.80 mL/g, and specific surface is 260 ~ 330 m
2/ g.
6. in accordance with the method for claim 5, it is characterized in that, the carrier of described molybdenum-nickel catalyzator is Al
2o
3or silicon-containing alumina, shape is Raschig ring, butterfly or honeycombed.
7. in accordance with the method for claim 5, it is characterized in that, the diameter of described molybdenum-nickel catalyzator is 4.9 ~ 5.2mm, long 3 ~ 10 mm.
8. in accordance with the method for claim 1, it is characterized in that, the molybdenum-cobalt catalyst shape of described second reaction zone is cylinder, trifolium, and support of the catalyst is Al
2o
3or silicon-containing alumina; Molybdenum-the nickel of the 3rd reaction zone, tungsten-nickel or tungsten-molybdenum-nickel catalyzator, with TiO
2-al
2o
3or silicon-containing alumina or molecular sieve-aluminum oxide are carrier; The pore volume of the molybdenum-cobalt catalyst of the 4th reaction zone is 0.40 ~ 0.80 mL/g, and specific surface area is 200 ~ 400 m
2/ g, carrier is Al
2o
3or silicon-containing alumina.
9. in accordance with the method for claim 1, it is characterized in that, described raw material diesel oil is selected from one or more in coker gas oil, catalytic diesel oil or straight-run diesel oil.
10. in accordance with the method for claim 1, it is characterized in that, the molybdenum-nickel catalyzator in described first reaction zone, strong acid content is 0.02 ~ 0.06mmol/g; The strong acid content of the molybdenum-cobalt catalyst of described second reaction zone is 0.02 ~ 0.08 mmol/g; The strong acid content of the molybdenum-nickel of described 3rd reaction zone, tungsten-nickel or tungsten-molybdenum-nickel catalyzator is 0.1 ~ 0.3 mmol/g; The strong acid content of the molybdenum-cobalt catalyst of described 4th reaction zone is 0.02 ~ 0.08mmol/g.
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|---|---|---|---|---|
| CN104611050B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of catalytic cracking diesel oil method for transformation |
| CN105623726B (en) * | 2014-10-28 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of method of hydrotreating for producing diesel oil |
| CN111073683B (en) * | 2018-10-22 | 2021-08-31 | 中国石油化工股份有限公司 | Method for ultra-deep desulfurization and dearomatization of diesel oil |
| CN111088066B (en) * | 2018-10-23 | 2021-10-08 | 中国石油化工股份有限公司 | Hydrofining process |
| CN113122311B (en) * | 2019-12-31 | 2023-01-10 | 中国石油化工股份有限公司 | Hydrofining catalyst grading method |
Citations (3)
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|---|---|---|---|---|
| US6251262B1 (en) * | 1998-10-05 | 2001-06-26 | Nippon Mitsubishi Oil Corporation | Process for hydrodesulfurization of diesel gas oil |
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN101591566A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of grading method of catalyst of deep hydrodesulfurizationof of diesel oil |
-
2011
- 2011-10-21 CN CN201110321355.7A patent/CN103059983B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6251262B1 (en) * | 1998-10-05 | 2001-06-26 | Nippon Mitsubishi Oil Corporation | Process for hydrodesulfurization of diesel gas oil |
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN101591566A (en) * | 2008-05-29 | 2009-12-02 | 中国石油化工股份有限公司 | A kind of grading method of catalyst of deep hydrodesulfurizationof of diesel oil |
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