CN103374405B - A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil - Google Patents
A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil Download PDFInfo
- Publication number
- CN103374405B CN103374405B CN201210130673.XA CN201210130673A CN103374405B CN 103374405 B CN103374405 B CN 103374405B CN 201210130673 A CN201210130673 A CN 201210130673A CN 103374405 B CN103374405 B CN 103374405B
- Authority
- CN
- China
- Prior art keywords
- oil
- reaction zone
- hydrogenation
- reaction
- 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
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of combined hydrogenation method producing high-grade low-freezing point diesel oil.First under the condition of hydrogenation, bio-oil mixes with recycle hydrogen by hydrotreatment reaction zone, diesel raw material oil mixes by hydrofining reaction district with recycle hydrogen, the hydro-upgrading reaction zone at least comprising hydroisomerizing performance catalyzer is entered after the liquid mixing that hydrotreatment resultant flow point obtains from the raw product separation of the liquid obtained and hydrofining, hydro-upgrading resultant flow point continues fractionation from the liquid obtained and obtains petroleum naphtha and high-grade low-freezing point diesel product, under response behaviour, the hydrogenation active component of the hydrogenation catalyst that hydrotreatment reaction zone uses is the W of sulphided state, Mo, one or more in Ni and Co.Compared with prior art, the inventive method not only effectively can improve bio-oil as storage stability during oil fuel, can also direct production high-grade low-freezing point clean diesel.
Description
Technical field
The invention belongs to the working method of renewable energy source, relate to a kind of method of hydrotreating, particularly a kind of with bio-oil and diesel oil distillate for stock oil, the combined hydrogenation method of direct production high-grade low-freezing point diesel oil.
Background technology
The energy in current global range is mainly derived from fossil energy, comprise coal and oil, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, and not only resource is day by day exhausted, and heaviness and in poor quality degree aggravation.Along with sustained economic development, the environmental regulation increasingly stringent in the world, various countries are very vigorous to the demand of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, and produce satisfactory product with minimum cost, the especially development and utilization of renewable resources.
Bio-oil derives from plant, animal or microorganism etc., and be renewable resources, its comprehensive utilization obtains worldwide extensive attention, and each research unit and energy company are all being devoted to take it as the research of raw material production cleaning product.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, but because in this kind of biofuel, oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, all oil engines can not be applicable to.If bio oil, fat are produced automotive fuel by the method for deep hydrogenation, all remove by oxygen or most of product removing production and meet automotive fuel standard, this method directly can meet the requirement of existing market.
Existing bio-oil hydrogenation method produces the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose vegetables oil hydroconversion process, adopt coker naphtha, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), petroleum hydrocarbon cut and the bio oil such as wax oil cut, fat is directly mixed into hydroconversion reaction zone, beds is passed through under the effect of hydrogen, produce the raw material etc. of diesel product or preparing ethylene by steam cracking.US5705722 discloses the diesel oil blending component producing diesel oil distillate scope containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation.
EP1741767 and EP1741768 discloses a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil first through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydroprocessing processes, cause very adverse influence to isomerization catalyst, device can not long-period stable operation.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes pressure drop rise that running period is shortened, and needs more catalyst changeout of often stopping work.Particularly independent with bio oil, fat for raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact.Carry out conventional raw material weighted BMO spaces (as the hydrotreated lube base oil of routine or either shallow hydrofining etc.) according to this area general knowledge, although extend (generally can reach 500 hours) running period to some extent, but still long period steady running problem can not be solved.Containing multiple different organo-functional group in bio-oil, the reaction of these organo-functional groups in hydrogenation process is comparatively complicated, influence each other between different reactions, the major cause affecting bio-oil raw material hydrogenation process stability is still indefinite, and therefore improving run stability is the major issue that this area needs to solve.Simultaneously when producing low freezing point diesel fuel cut also because catalyst activity is affected the shortcomings such as the running period that causes is short.
In prior art, bio-oil hydrogenation produces the method for automotive fuel, the petroleum fractions hybrid process of general needs and larger proportion, otherwise can not running period be ensured, or directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity, can not long-term operation.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first reaction zone hydrotreatment (hydrogenation catalyst of grating and suitable processing condition etc.), second reaction zone diesel oil hydrofining, 3rd reaction zone hydro-upgrading pour point depression, can directly with bio-oil and diesel oil for raw material production high-grade low-freezing point diesel product, solving bio-oil hydrogenation unit can not the problem of long period steady running, significantly can reduce the condensation point of diesel oil distillate simultaneously.And the weighted BMO spaces of routine does not still reach required stability, conventional weighted BMO spaces generally can realize the running period of 500 hours, the use properties of catalyzer obviously declines, and uses reacting system pressure during fixed bed to fall obvious rising, needs more catalyst changeout.And the present invention program, in steady running after 1000 hours, the Pressure Drop of catalyst performance and reactive system does not all have considerable change, and according to this trend, estimating completely can steady running 1 ~ 3 year.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of combined hydrogenation method producing high-grade low-freezing point diesel oil, with bio-oil and diesel oil distillate for stock oil, the diesel product of direct production high-quality super low sulfur, low condensation point under the condition of combined hydrogenation, there is hydrogenation process stablize, the features such as running period is long.
The combined hydrogenation method that the present invention produces high-grade low-freezing point diesel oil comprises following content:
A one or more in () bio-oil are the first stock oil, one or more of straight-run diesel oil or secondary processing diesel oil cut are the second stock oil;
B () is under hydroprocessing operations condition, the first stock oil under hydroconversion condition by comprising the first reaction zone of the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first stock oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is one or more in W, Mo, Ni and Co of sulphided state, first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration process Posterior circle uses;
C (), under hydrofining operational condition, the second stock oil is by the second reaction zone of filling Hydrobon catalyst under hydroconversion condition, and second reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas phase recycles;
(d) first reaction zone hydrogenation effluent be separated the liquid phase obtained and be separated with second reaction zone hydrogenation effluent after the liquid-phase mixing obtained under hydroisomerizing condition by least comprising the 3rd reaction zone of hydroisomerizing performance catalyzer;
(e) the 3rd the gas phase of reaction zone reaction effluent recycle, the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and is obtained petroleum naphtha and high-quality super low sulfur, low freezing point diesel fuel product cut;
F () supplements S-contained substance in the first reaction zone, to maintain hydrogen sulfide content in circulation gas.
In the inventive method step (a), the bio-oil used can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, one or more during animal grease comprises butter, lard, sheep oil, fish oil and roasts grease that other animals obtain etc.
In the inventive method step (a), straight-run diesel oil is generally the diesel oil distillate that Atmospheric vacuum fractionation obtains, the straight-run diesel oil of preferred intermediate base crude oil and naphthenic base crude.Secondary processing diesel oil is generally secondary petroleum refining process, as the technological processs such as catalytic cracking, hydrotreatment, coking, thermally splitting, viscosity breaking, ethene obtain diesel oil distillate, coal tar diesel oil distillate.
In the inventive method step (a), the ratio of the first stock oil and the second stock oil is 1:99 ~ 99:1, preferred 5:95 ~ 95:5, best 10:90 ~ 90:10.
In the inventive method step (b), the Hydroprocessing conditions of the first reaction zone is generally reaction pressure 2.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 3.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.2h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (b), first reaction zone beds generally can arrange 2 ~ 5, in the beds that first reaction mass passes through, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of all hydrogenation catalyst volumes in first paragraph reaction zone, preferably 20% ~ 70%, best 30% ~ 60%.The hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer, preferably increases by 5 ~ 20 percentage points.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.The business hydrogenation catalyst that first reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, the hydrogenation catalysts such as ICR179, Uop Inc. is newly developed HC-P, HC-KUF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.
In the inventive method step (c), the Hydroprocessing conditions of second reaction zone is generally reaction pressure 2.0MPa ~ 20.0MPa, can be identical with the first reaction zone, also can not be identical, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (c), the Hydrobon catalyst that second catalyzer of answering district to use is routine, business hydrogenation catalyst mainly contains, as the FH-5 that Fushun Petrochemical Research Institute (FRIPP) develops, FH-5A, FH-98, FH-DS, FH-UDS series waits hydrogenation catalyst, the HR-416 of Inst Francais Du Petrole, HR-448, HR-548, the hydrogenation catalysts such as HR-568, the ICR174 of CLG company, ICR178, ICR179, the hydrogenation catalysts such as ICR417, the HC-P of Uop Inc.'s exploitation, HC-K, the catalyzer such as UF-210, the TK-525 of Topsor company, TK-559, TK-574, TK-576, TK-607, TK-907, the hydrogenation catalysts such as TK-911, the KF-756 of AKZO company, KF-757, KF-840, the hydrogenation catalysts such as KF-848, the DN2531 of Criterion company, the hydrogenation catalysts such as DN3330 and DN2318.
In the inventive method step (d), the Hydroprocessing conditions of the 3rd reaction zone is generally reaction pressure 2.0MPa ~ 20.0MPa, can be identical with the first reaction zone, can be identical with second reaction zone, also can not be identical with first, second reaction zone, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (d), the hydroisomerization catalyst (or claiming modifying catalyst) of the 3rd reaction zone is containing beta-molecular sieve, the components such as SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve, described molecular sieve weight content is in the catalyst generally 3% ~ 30%, is preferably 5% ~ 20%.The hydrogenation active metals component of modifying catalyst (in W, Mo, Ni and Co one or more) is generally 10% ~ 40% with the weight content of oxide basis.The commercial catalysts that second segment reaction zone uses mainly contains, as FC-14, FC-16, FC-20 etc. that Fushun Petrochemical Research Institute (FRIPP) develops.
In the inventive method step (e), the sulfur-containing medium supplemented in the first reaction zone material (optimum is dosed in stock oil) can be the compound of sulfur-bearing, as DMDS, CS
2deng.If with second reaction zone or the 3rd reaction zone common recycle hydrogen, then do not need to mend sulphur in addition, but need to ensure that the hydrogen sulfide content in circulation gas is not less than 0.005v%, preferred 0.01v% ~ 2.0v%.Three reaction zones can use independent recycle hydrogen system, also can common recycle hydrogen system, also can any two reaction zone common recycle hydrogen systems.
In the inventive method, Hydrobon catalyst can be supplemented in right amount, by material hydrogenation such as issuable a small amount of alkene in hydro-upgrading process finally arranging of the 3rd reaction zone catalyst for hydro-upgrading bed.
Accompanying drawing explanation
Fig. 1 is the combined hydrogenation method principle flow chart that the present invention produces high-grade low-freezing point diesel oil.
Fig. 2 is another principle flow chart of combined hydrogenation method that the present invention produces high-grade low-freezing point diesel oil.Be that the first reaction zone uses the recycle hydrogen of second, third reaction zone as new hydrogen with the difference of Fig. 1, and the injection of corresponding cancellation vulcanizing agent.
Fig. 3 is another principle flow chart of combined hydrogenation method that the present invention produces high-grade low-freezing point diesel oil.Be that second reaction zone and the 3rd reaction zone use independently recycle hydrogen system separately with the difference of Fig. 1.
Embodiment
Method of the present invention is specific as follows: with the mixing oil of one or more in bio-oil for stock oil, under Hydroprocessing conditions, stock oil and hydrogen are by comprising the first reaction zone of at least two kinds of hydrogenation catalysts, the hydrotreatment obtained generates logistics and is separated the gas circulation use obtained in high-pressure separator, also system can be gone out, the liquid distillate obtained; Diesel raw material and hydrogen are mixed into and comprise hydrorefined second reaction zone, and the hydrofining obtained generates logistics and is separated the gas circulation use obtained in high-pressure separator, also can go out system, the liquid distillate obtained; The liquid distillate of the first reaction zone mix with the liquid distillate of second reaction zone after and hydrogen by comprising the 3rd reaction zone with isomery performance catalyst for hydro-upgrading, the hydro-upgrading obtained generates logistics in high-pressure separator, is separated the gas circulation use obtained, also can go out system, liquid fractionation obtains following products: one or more in gas, petroleum naphtha, low freezing point diesel fuel.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.
Particular case of the present invention is further illustrated below by embodiment.
The main composition of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Catalyst for refining | Modifying catalyst |
| Catalyzer forms | |||||
| MoO 3，wt% | 8.0 | 5.2 | 24.5 | 20.7 | 18.0 |
| NiO，wt% | 2.8 | 4.5 | 3.6 | 2.5 | |
| CoO，wt% | 1.8 | ||||
| Beta-molecular sieve, wt% | 10.6 | ||||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| The leading indicator of catalyzer | |||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | 0.33 | 0.32 | >0.34 |
The main character of table 2 diesel raw material oil.
| Catalyzer | Catalytic diesel oil | Medium diesel oil |
| Density, g/cm 3 | 0.965 | 0.897 |
| Cut scope, DEG C | 166~375 | 150~365 |
| Sulphur content, wt% | 1.8 | 1.2 |
| Nitrogen content, μ g/g | 1020 | 560 |
| Condensation point, DEG C | 5 | 15 |
| Cetane value | 17 | 35 |
Table 3 embodiment processing condition and test-results.
| First reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Catalyzer | Catalyzer 1/ catalyzer 3 | Catalyzer 2/ catalyzer 3 | Catalyzer 2/ catalyzer 3 | Catalyzer 2/ catalyzer 1/ catalyzer 3 |
| Catalyst volume ratio | 15:85 | 25:75 | 40:60 | 10:20:70 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Rapeseed oil | Plam oil |
| Reaction pressure, MPa | 17.0 | 6.0 | 10.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 2500:1 | 500:1 | 1000:1 | 1500:1 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 0.5 | 1.0 |
| Average reaction temperature, DEG C | 370 | 360 | 350 | 360 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | |
| Hydrogen sulfide content in circulation gas, μ L/L | 1000 | |||
| Second reaction zone processing condition | ||||
| Catalyzer | Catalyst for refining | Catalyst for refining | Catalyst for refining | Catalyst for refining |
| Stock oil | Catalytic diesel oil | Medium diesel oil | Medium diesel oil | Catalytic diesel oil |
| Reaction pressure, MPa | 8.0 | 6.0 | 10.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 800:1 | 400:1 | 600:1 | 1000:1 |
| Volume space velocity, h -1 | 2.0 | 1.8 | 0.5 | 2.5 |
| Average reaction temperature, DEG C | 360 | 345 | 320 | 350 |
| 3rd reaction zone processing condition | ||||
| Stock oil | Two reaction zones liquid product volume ratio 50:50 | Two reaction zones liquid product volume ratio 40:60 | Two reaction zones liquid product volume ratio 60:40 | Two reaction zones liquid product volume ratio 70:30 |
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 8.0 | 6.0 | 10.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 1500:1 | 800:1 | 1000:1 | 700:1 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 4.5 | 3.0 |
| Average reaction temperature, DEG C | 330 | 350 | 365 | 310 |
| Diesel product | ||||
| Density, g/cm 3 | 0.839 | 0.825 | 0.810 | 0.830 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Condensation point, DEG C | -25 | -35 | -50 | -15 |
| Cetane value | 58 | 71 | 75 | 63 |
Table 4 embodiment processing condition and test-results.
| First reaction zone processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Catalyzer | Catalyzer 2/ catalyzer 3 | Catalyzer 2/ catalyst for refining/modifying catalyst | Catalyzer 2/ catalyst for refining/modifying catalyst | Catalyzer 2/ catalyst for refining/modifying catalyst |
| Catalyst volume ratio | 40:60 | 50:30:20 | 50:30:20 | 50:30:20 |
| Stock oil volume ratio | Oleum Gossypii semen | Oleum Gossypii semen/catalytic diesel oil | Oleum Gossypii semen/catalytic diesel oil | Oleum Gossypii semen/catalytic diesel oil |
| Stock oil ratio | 100 | 50:50 | 50:50 | 50:50 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 800:1 | 800:1 | 800:1 | 800:1 |
| Volume space velocity, h -1 | 0.6 | 0.66 | 0.66 | 0.66 |
| Average reaction temperature, DEG C | 330 | 350 | 360 | 380 |
| Second reaction zone processing condition | Embodiment 5 | — | — | — |
| Catalyzer | Catalyst for refining | |||
| Stock oil | Catalytic diesel oil | |||
| Reaction pressure, MPa | 8.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 1.5 | |||
| Average reaction temperature, DEG C | 360 | |||
| 3rd reaction zone processing condition | — | — | — | |
| Catalyzer | Modifying catalyst | |||
| Stock oil | Two reaction zones liquid product volume ratio 50:50 | |||
| Reaction pressure, MPa | 8.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 3.0 | |||
| Average reaction temperature, DEG C | 350 | |||
| Runtime, h | 1000 | 100 | 300 | 500 |
| Sulfur-containing medium | CS 2 | |||
| Hydrogen sulfide content in circulation gas, μ L/L | 300 | 500 | 500 | 500 |
| Total pressure drop, MPa | 0.08 | 0.08 | 0.15 | 0.28 |
| Diesel product | ||||
| Density, g/cm 3 | 0.844 | 0.845 | 0.869 | 0.895 |
| Sulphur content, μ g/g | <5 | <5 | 50 | 450 |
| Condensation point, DEG C | -20 | -20 | -10 | 5 |
| Cetane value | 62 | 62 | 55 | 47 |
As can be seen from embodiment, bio-oil and diesel raw material oil can produce high-grade low-freezing point diesel product by the combined hydrogenation method of this technology, or high-grade low-freezing point diesel oil blending component, and can long-period stable operation be realized, operate after 1000 hours, reactive system pressure drop is not risen substantially, and on catalyzer, carbon deposition quantity only has about 3.6wt%, belong to balance carbon deposition quantity, do not affect catalyzer use properties.
Claims (14)
1. produce a combined hydrogenation method for high-grade low-freezing point diesel oil, it is characterized in that comprising following content:
A one or more in () bio-oil are the first stock oil, one or more of straight-run diesel oil or secondary processing diesel oil cut are the second stock oil;
B () is under hydroprocessing operations condition, the first stock oil under hydroconversion condition by comprising the first reaction zone of the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first stock oil and hydrogen pass through the low beds of hydrogenation active component content, then the high beds of hydrogenation active component content is passed through, under response behaviour, hydrogenation active component is one or more in W, Mo, Ni and Co of sulphided state, first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration process Posterior circle uses;
C (), under hydrofining operational condition, the second stock oil is by the second reaction zone of filling Hydrobon catalyst under hydroconversion condition, and second reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas phase recycles;
(d) first reaction zone hydrogenation effluent be separated the liquid phase obtained and be separated with second reaction zone hydrogenation effluent after the liquid-phase mixing obtained under hydroisomerizing condition by least comprising the 3rd reaction zone of hydroisomerization catalyst;
(e) the 3rd the gas phase of reaction zone reaction effluent recycle, the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and is obtained petroleum naphtha and high-quality super low sulfur, low freezing point diesel fuel product cut;
F () supplements S-contained substance in the first reaction zone, to maintain hydrogen sulfide content in circulation gas.
2. in accordance with the method for claim 1, it is characterized in that: in step (a), the bio-oil of use comprises vegetables oil or animal grease.
3. in accordance with the method for claim 1, it is characterized in that: in step (a), the straight-run diesel oil used comprises the diesel oil distillate that atmospheric and vacuum distillation of petroleum obtains, secondary processing diesel oil comprises the diesel oil distillate of catalytic cracking, catalytic cracking weighted BMO spaces, coking, viscosity breaking, thermally splitting, hydrocracking, ethylene process production, and coal tar diesel oil distillate.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure of the first reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C.
5. in accordance with the method for claim 1, it is characterized in that: in step (b), the reaction pressure of the first reaction zone is 4.0MPa ~ 18.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.2h
-1~ 4.0h
-1, average reaction temperature is 200 DEG C ~ 445 DEG C.
6. according to the method described in claim 1,4 or 5, it is characterized in that: in step (b), first reaction zone beds arranges 2 ~ 5, in the beds that first reaction mass passes through, hydrogenation active component is with the weight content of oxide basis for 3% ~ 10%, and the hydrogenation catalyst that first reaction mass passes through accounts for 10% ~ 80% of the first all hydrogenation catalyst volumes in reaction zone; The hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 3 ~ 25 percentage points in oxide weight than adjacent upstream catalyzer.
7. in accordance with the method for claim 6, it is characterized in that: in step (b) first reaction zone, in the beds that first reaction mass passes through, the hydrogenation catalyst that first reaction mass passes through accounts for 20% ~ 70% of all hydrogenation catalyst volumes in first paragraph reaction zone; The hydrogenation active component of the downstream catalyst that reaction mass passes through increases by 5 ~ 20 percentage points in oxide weight than adjacent upstream catalyzer.
8. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is 180 DEG C ~ 465 DEG C.
9. in accordance with the method for claim 8, it is characterized in that: hydrogen to oil volume ratio is 300:1 ~ 2500:1, volume space velocity is 0.4h
-1~ 5.0h
-1, average reaction temperature is 200 DEG C ~ 445 DEG C.
10. in accordance with the method for claim 1, it is characterized in that: in step (d), the reaction pressure of the 3rd reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is 180 DEG C ~ 465 DEG C.
11. in accordance with the method for claim 10, it is characterized in that: hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 4.0h
-1, average reaction temperature is 200 DEG C ~ 445 DEG C.
12. in accordance with the method for claim 1, it is characterized in that: in step (d), the hydroisomerization catalyst of second segment reaction zone contains beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve, the hydrogenation active metals component of hydroisomerization catalyst with the weight content of oxide basis for 10% ~ 40%.
13. in accordance with the method for claim 1, it is characterized in that: in step (f), the sulfur-containing medium supplemented in reaction mass is the compound of sulfur-bearing, or the sour gas in second reaction zone or the 3rd reaction zone is introduced the first reaction zone mutually, ensures that the hydrogen sulfide content in circulation gas is not less than 0.005v%.
14. in accordance with the method for claim 1, it is characterized in that: in step (a), and the volume ratio of the first stock oil and the second stock oil is 10:90 ~ 90:10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210130673.XA CN103374405B (en) | 2012-04-29 | 2012-04-29 | A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210130673.XA CN103374405B (en) | 2012-04-29 | 2012-04-29 | A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103374405A CN103374405A (en) | 2013-10-30 |
| CN103374405B true CN103374405B (en) | 2015-11-18 |
Family
ID=49460252
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210130673.XA Active CN103374405B (en) | 2012-04-29 | 2012-04-29 | A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103374405B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106479566B (en) * | 2015-08-27 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking producing premium and diesel oil |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693432A1 (en) * | 2005-02-18 | 2006-08-23 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| WO2011112660A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
-
2012
- 2012-04-29 CN CN201210130673.XA patent/CN103374405B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1693432A1 (en) * | 2005-02-18 | 2006-08-23 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| WO2011112660A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103374405A (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374403B (en) | Hydrogenation combination method for producing low-condensation-point diesel oil | |
| CN103374405B (en) | A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil | |
| CN103374399B (en) | Produce the combined hydrogenation method of high-grade low-freezing point diesel oil | |
| CN103374398B (en) | Hydrogenation method for producing high-quality low-condensation-point diesel oil | |
| CN103374396B (en) | Hydrogenation combination method for producing low-condensation-point diesel oil | |
| CN103102897B (en) | Hydrogenation method for production of low-condensation point motor fuel from biolipid | |
| CN103374397B (en) | Hydrogenation combination method for producing low-condensation-point diesel oil | |
| CN103374404B (en) | Hydrogenation combination method for producing high-quality diesel oil | |
| CN103374401B (en) | A kind of method of hydrotreating producing high-quality burning oil | |
| CN103374378B (en) | A kind of method of hydrotreating producing high-grade low-freezing point diesel oil | |
| CN103102916B (en) | Two-stage hydrogenation method for producing low freezing point motor fuel | |
| CN103374407B (en) | A kind of method of hydrotreating producing low freezing point diesel fuel | |
| CN103102910B (en) | Two-stage hydrogenation method for producing low freezing point motor fuel from biological oil | |
| CN103102912B (en) | Two-stage hydrogenation method for producing high quality low freezing point motor fuel | |
| CN103102901B (en) | Hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil | |
| CN103374408B (en) | Produce the method for hydrotreating of low freezing point diesel fuel | |
| CN103374409B (en) | Produce the combined hydrogenation method of high-quality burning oil | |
| CN103102917B (en) | Produce the two-stage method method of hydrotreating of low condensation point automotive fuel | |
| CN103374413B (en) | Hydrogenation combination method for producing high-quality kerosene | |
| CN103374379B (en) | Produce the method for hydrotreating of fine-quality diesel oil | |
| CN103374406B (en) | Hydrogenation method for producing high-quality diesel oil | |
| CN103102924B (en) | Hydrogenation method for producing low freezing point motor fuel from biological oil | |
| CN103374410B (en) | Hydrogenation method for producing high-quality kerosene | |
| CN103102896B (en) | Hydro-upgrading method for production of low-condensation point motor fuel from biolipid | |
| CN103102913B (en) | Wax oil hydrotreating method for diesel oil by-production |
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 |