CN103102961B - Residue oil hydrogenation method for diesel oil by-production - Google Patents
Residue oil hydrogenation method for diesel oil by-production Download PDFInfo
- Publication number
- CN103102961B CN103102961B CN201110353701.XA CN201110353701A CN103102961B CN 103102961 B CN103102961 B CN 103102961B CN 201110353701 A CN201110353701 A CN 201110353701A CN 103102961 B CN103102961 B CN 103102961B
- Authority
- CN
- China
- Prior art keywords
- oil
- hydrogenation
- reaction zone
- paragraph
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
The present invention relates to a residue oil hydrogenation method for diesel oil by-production. According to the method, under a hydrogenation condition, a biological oil and circulation hydrogen are mixed, and pass through a first stage hydrogenation reaction zone, the stream generated from hydrogenation is separated to obtain hydrogen-rich gas, the hydrogen-rich gas is recycled, the separated liquid and the residue oil are mixed and enter a second stage residue oil hydrogenation reaction zone, the sub-hydrogen gas separated from the oil generated through second stage hydrogenation is recycled, and the separated liquid product is subjected to fractionation to obtain naphtha, diesel oil and hydrogenation wax oil, wherein hydrogenation activity components of the hydrogenation catalyst used at the first stage are one or a plurality of materials selected from sulfurization state W, Mo, Ni and Co under a reaction state. Compared to the method in the prior art, the residue oil hydrogenation method of the present invention has the following characteristics that: the high quality diesel oil can be by-produced on the residue oil hydrotreating device, activity stability of the catalyst is good, and the device can stably operate for a long period.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly a kind of can the residual hydrogenation method of by-product diesel oil.
Background technology
The energy in current global range is mainly derived from fossil energy, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality trend aggravation, and world economy sustainable development, environmental regulation increasingly stringent need to produce a large amount of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, produce satisfactory product with minimum cost.Conversion for residual oil mainly contains residual hydrogenation and coking two kinds of approach, and wherein residual hydrogenation is the important technology producing clean fuel, and hydrogenated residue provides high-quality charging for catalytic cracking, can reduce SO in catalytic cracking unit operating process flue gas
xand NO
xdischarge, and the sulphur content increasing light oil yield and effectively reduce in catalytic gasoline.
Bio-oil, as renewable resources, obtains the extensive attention in the world, and each research unit and enterprise are all making great efforts to carry out its research as clean energy.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, but because fatty acid methyl ester oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, and are not suitable for all oil engines.Bio-oil produces automotive fuel by the method for hydrogenation, and all remove by oxygen or partly remove the product produced and meet automotive fuel standard, this method directly can meet the requirement of existing market.
Existing animal-plant 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), the petroleum hydrocarbon cuts such as wax oil cut and bio-oil are mixed into hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.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.
For residual hydrogenation technology, mainly for the feature of residual oil, select the catalyst loading technology of grating and the operational condition of optimization, for catalytic cracking unit provides the raw material after hydrogenation.CN200810246649.6 discloses a kind of method of hydrotreating of residual oil, CN200610007532.3 discloses a kind of method of hydrotreating producing catalytically cracked material, CN02133138.3 discloses a kind of heavy hydrocarbon hydroprocessing method, CN01114166.2 discloses a kind of process for hydrogenating residual oil, US20050311134 discloses a kind of hydrogenating conversion process of heavy resid, EP19930201257 discloses a kind of hydroprocessing process, the i.e. hydroprocessing process of residue oil fraction, the density 0845 ~ 0.870g/cm of the diesel product of these method by-products
3, cetane value 40 ~ 48, sulphur content 100 ~ 600 μ g/g, can not meet the requirement of the Europe IV standard or higher standard.In addition, the method that diesel oil for residual hydrogenation by-product carries out upgrading is mainly CN01123761.9 and discloses a kind of method reducing aromatic content of diesel oil in residual hydrogenation equipment, the method is only carry out hydrogenation aromatics-removing to the diesel oil of by-product, there is no the introducing of renewable raw materials, add process cost.
CN200910187930.1 discloses a kind of method of mixing refining bio-oil improvement residual hydrogenation, mainly bio-oil is directly mixed refining to residual hydrogenation equipment, the working method of the character that then improved by fractionation.But the H generated in production process
2o has adverse influence to residual oil hydrocatalyst, and reaction generates CO and CO
2have an impact to catalyst performance, and methanation reaction can occur, the methane of generation is difficult to discharge system, thus greatly reduces the hydrogen dividing potential drop of reactive system, or discharges methane by the method for discharge, has increased considerably the hydrogen consumption of device like this.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes shorten running period, need more catalyst changeout of often stopping work, particularly independent with bio-oil be raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact.And for mixing the hydrogenation unit of refining bio-oil, the H that reaction process generates
2o, CO and CO
2and CH
4very adverse influence can be produced Deng to existing hydrogenation catalyst system.
In prior art, bio-oil hydrogenation produces the method for automotive fuel, petroleum fractions (gasoline, diesel oil, wax oil or the residual oil) hybrid process of general needs and larger proportion, or directly by hydrofining-catalyst for hydro-upgrading bed, the H that reaction process generates
2o, CO and CO
2and CH
4very adverse influence can be produced Deng to existing hydrogenation catalyst system, affect the life-span of plant running cycle or catalyzer.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first paragraph hydrofining (the bio-oil raw material DNA vaccine that the hydrogenation catalyst of grating and control are suitable for), second segment first paragraph hydrogenated oil and the process of residual oil mixed hydrogenation, can directly with by-product fine-quality diesel oil while production hydrogenated residue, have residual oil hydrocatalyst impact little, the advantages such as the plant running cycle is long.Control the DNA vaccine be suitable in bio-oil hydrogenation process, be conducive to the stability of bio-oil hydrogenation process and the stability of residual hydrocracking process simultaneously.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of hydrotreating being stock oil by-product diesel oil with bio-oil and residual oil, first bio-oil and recycle hydrogen are by loading hydrogenation catalyst first paragraph reaction zone, then liquid and residual oil are mixed into the second segment reaction zone of loading residual hydrogenation catalyst series, can direct production fine-quality diesel oil and hydrogenated residue, have hydrogenation process to stablize, running period is long, affects the features such as little to residual hydrogenation reaction zone.
The residual hydrogenation method of a kind of by-product of the present invention diesel oil comprises following content:
A () take residual oil as stock oil, with one or more in bio-oil for auxiliary material;
B () is under Hydroprocessing conditions, bio-oil and recycle hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first bio-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;
C () first paragraph reaction zone hydrogenation effluent is separated the gas circulation obtained and uses, liquid phase generates oily entering with residual oil raw material and uses the second segment reaction zone of catalyst for hydrotreatment of residual oil to carry out hydrotreatment reaction;
D the gas phase of () second segment reaction zone resultant stream gas-liquid separation recycles, liquid phase fractionation in separation column of second segment reaction zone resultant stream gas-liquid separation obtains petroleum naphtha, diesel oil and hydrogenated residue.
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, and animal grease comprises one or more in butter, lard, sheep oil and fish oil etc.Residual oil can be long residuum or vacuum residuum, also can mix other cuts of other cut close range.In the inventive method, first paragraph reaction zone liquid phase generates oil and accounts for 5% ~ 40% of second segment reaction zone liquid phase feeding weight, is preferably 10% ~ 30%.
In the inventive method step (b), the Hydroprocessing conditions of first paragraph reaction zone is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 8.0h
-1, average reaction temperature 180 DEG C ~ 425 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 1.0h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 400 DEG C.The DNA vaccine of first paragraph reaction zone bio-oil raw material controls to be 40% ~ 95%, is preferably 60% ~ 90%.
In the inventive method step (b), 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.Beds generally can arrange 2 ~ 5.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-K UF-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 (b), reaction system hydrogen sulfide in gas phase concentration controls higher than 0.005v%, preferred 0.01v% ~ 2.0v%, to maintain the sulfided state of catalyst stabilization, keeps catalytic activity.Specifically can be realized by the method for adding S-contained substance in reaction mass, also the circulation gas containing hydrogen sulfide in step (c) can be circulated in step (b) and use.Containing water in the hydrogenation effluent of first paragraph reaction zone, suitable method can be adopted to remove, as cooled rear separation removal.First paragraph reaction zone hydrogenation effluent is separated the gas phase obtained and can uses at first paragraph reaction zone internal recycle, also can as the hydrogen make-up of second segment reaction zone.The gas phase of second segment reaction zone resultant stream gas-liquid separation recycles in second reaction zone, also can be circulated to the first reaction zone on a small quantity.
In the inventive method step (c), the Hydroprocessing conditions of second segment reaction zone is generally reaction pressure 8.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 4.0h
-1, average reaction temperature 280 DEG C ~ 465 DEG C; Preferred operational condition is reaction pressure 10.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 500:1 ~ 2500:1, volume space velocity 0.1h
-1~ 2.0h
-1, average reaction temperature 300 DEG C ~ 460 DEG C.First paragraph reaction zone hydrogenation effluent does not need cooling to carry out gas-liquid separation, and the water that reaction generates enters in gas phase.The working pressure of second segment reaction zone can be identical with first paragraph, also can be different.
In the inventive method step (c), the residual hydrogenation catalyst series of second segment reaction zone can use the hydrogenation catalyst of this area routine, specifically can comprise protective material, Hydrodemetalation catalyst, Hydrobon catalyst and hydrodenitrification (de-carbon residue) catalyzer etc., mainly contain ICR series protective material and the ICR catalyst series of the exploitation of CHEVRON company, the RM series of CRITERION company exploitation and RN catalyst series, the RF series protective material of Uop Inc.'s exploitation, RF catalyst series and RCD catalyst series, the KG series protective material of AKZO company exploitation and KFR catalyst series, the TK series protective material of Haldor Topsoe company exploitation and TK catalyst series, the RG series protective material of RIPP exploitation and RDM, RMS, RSN catalyst series, the FZC series protective material of FRIPP exploitation and FZC catalyst series, as: FZC-100, FZC-101, FZC102, FZC-103, FZC104, FZC-105, FZC106, FZC10, FZC-11, FZC12, FZC13, FZC-14, the protective materials such as FZC15, FZC-201, FZC202, FZC-203, FZC-204, FZC-21, FZC22, FZC-23, the Hydrodemetalation catalysts such as FZC-24, FZC301, FZC-302, FZC-303, FZC31, FZC-32, FZC-33, the Hydrobon catalysts such as FZC-34, FZC-40, FZC-41, the hydrodenitrifications such as FZC-41A (de-carbon residue) catalyzer etc.
In the inventive method, first paragraph and second segment reaction zone hydrogenation active component are the catalyzer of oxidation state, carry out conventional sulfidizing before the use, make hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.
Accompanying drawing explanation
Fig. 1 is the residual hydrogenation methodological principle schema of a kind of by-product diesel oil of the present invention.
Fig. 2 is the another one principle flow chart of the residual hydrogenation method of a kind of by-product diesel oil of the present invention.
Embodiment
Method of the present invention is specific as follows: the mixing oil of one or more in bio-oil and recycle hydrogen under Hydroprocessing conditions by comprising the first paragraph hydroconversion reaction zone of at least two kinds of hydrogenation catalysts, the hydrogenated oil obtained be separated in high-pressure separator (abbreviation high score) gas obtained mix with the gas phase of second segment reaction zone reaction product carry out dewatering and depriving hydrogen sulphide process Posterior circle use, the liquid distillate obtained and residual oil and recycle hydrogen are mixed into the second segment reaction zone comprising serial residual oil hydrocatalyst, obtain hydrotreatment logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle at second segment, the liquid fractionation obtained obtains following products: gas, petroleum naphtha, fine-quality diesel oil and hydrogenated residue.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 first paragraph reaction zone of embodiment 1 and embodiment 3 uses the component loops hydrogen (as Fig. 2 flow process) of second segment reaction zone, and embodiment 2 first paragraph reaction zone uses vulcanizing agent to maintain hydrogen sulfide content (as Fig. 1 flow process).
The main composition of table 1 first paragraph hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 |
| Catalyzer forms | |||
| MoO 3，wt% | 6.2 | 10.5 | 20.6 |
| NiO，wt% | 2.0 | 4.7 | |
| CoO，wt% | 3.6 | ||
| Alumina supporter, wt% | Surplus | Surplus | Surplus |
| The main character of catalyzer | |||
| Specific surface, m 2/g | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | >0.30 |
The main composition of table 2 second segment residual hydrogenation catalyst series and character.
| Catalyzer | HB1 | HB2 | HDM1 | HDM2 | HDS | HDC |
| Catalyzer forms | ||||||
| MoO 3，wt% | 3.4 | 7.6 | 10.7 | 16.4 | 20.5 | 24.6 |
| NiO，wt% | 1.0 | 2.6 | 3.0 | 3.4 | 4.5 | 5.0 |
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | ||||||
| Specific surface, m 2/g | >100 | >110 | >130 | >130 | >150 | >160 |
| Pore volume, ml/g | 0.80 | 0.75 | 0.60 | 0.55 | 0.40 | >0.35 |
| Proportioning, volume % | 4 | 6 | 12 | 22 | 26 | 30 |
Note: HB refers to protective material, HDM refers to Hydrodemetalation catalyst, and HDS refers to Hydrobon catalyst, and HDC refers to removal of ccr by hydrotreating catalyzer.
Table 3 stock oil main character.
| Stock oil | Normal slag 1 | Normal slag 2 | Soybean oil | Oleum Gossypii semen |
| S，wt% | 3.9 | 3.0 | <0.001 | <0.001 |
| N，wt% | 0.266 | 0.220 | <0.001 | <0.001 |
| Carbon residue, wt% | 12.9 | 11.0 | — | — |
| Ni+V，μg/g | 100 | 90 | 0 | 0 |
Table 4 embodiment and reference example processing condition and test-results.
| First paragraph reaction zone processing condition | Embodiment 1 | Reference example | Embodiment 2 | Embodiment 3 |
| Catalyzer | Catalyzer 1/ catalyzer 3 | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2/ catalyzer 3 | |
| Catalyst volume ratio | 20:80 | 40:60 | 20:30:50 | |
| Stock oil | Oleum Gossypii semen | Soybean oil | Oleum Gossypii semen | |
| Reaction pressure, MPa | 16.0 | 4.0 | 15.0 | |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1500:1 | 1500:1 | |
| Cumulative volume air speed, h -1 | 2.8 | 0.8 | 1.1 | |
| Average reaction temperature, DEG C | 325 | 330 | 340 | |
| Vulcanizing agent | DMDS | |||
| Hydrogen sulfide content, v% | 0.05 | |||
| First paragraph reaction zone DNA vaccine, % | 80 | 82 | 90 | |
| Second segment reaction zone processing condition | ||||
| Catalyzer | Table 2 proportioning | Table 2 proportioning | Table 2 proportioning | Table 2 proportioning |
| Stock oil, weight | 85% residual oil 1+15% first paragraph generates oil | 85% residual oil 1+15% Oleum Gossypii semen | 90% residual oil 1+10% first paragraph generates oil | 80% residual oil 2+20% first paragraph generates oil |
| Reaction pressure, MPa | 16.0 | 16.0 | 16.0 | 14.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000 | 500:1 | 800:1 |
| Volume space velocity, h -1 | 0.4 | 0.3 | 0.3 | 0.36 |
| Average reaction temperature, DEG C | 395 | 395 | 385 | 380 |
| Operate CO+CO in 200 hours Posterior circle gas 2+CH 4, volume % | 4.6 | 10.5 | 2.1 | 3.4 |
| Hydrogenated diesel oil product | ||||
| Yield, wt% | 26.0 | 25.1 | 22.0 | 28.5 |
| Density, g/cm 3 | 0.829 | 0.831 | 0.839 | 0.828 |
| Sulphur content, μ g/g | 91 | 95 | 149 | 78 |
| Cetane value | 73 | 69 | 61 | 76 |
| Hydrogenated residue product | ||||
| Sulphur content, μ g/g | 3600 | 3650 | 2730 | 2650 |
| Nitrogen content, μ g/g | 1280 | 1310 | 800 | 570 |
| Carbon residue, % | 5.7 | 6.0 | 3.5 | 3.9 |
| Metal (Ni+V), μ g/g | 12.0 | 12.5 | 5.6 | 9.1 |
As can be seen from embodiment, by the residual hydrogenation method of this technology can under the prerequisite of producing hydrogenated residue by-product fine-quality diesel oil product, and can long-period stable operation be realized.
Claims (12)
1. a residual hydrogenation method for by-product diesel oil, is characterized in that comprising following content:
A () take residual oil as stock oil, with one or more in bio-oil for auxiliary material;
B () is under Hydroprocessing conditions, bio-oil and recycle hydrogen are by first paragraph reaction zone, first paragraph reaction zone comprises the hydrogenation catalyst bed that at least two hydrogenation active component content raise successively, first bio-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;
C () first paragraph reaction zone hydrogenation effluent is separated the gas circulation obtained and uses, liquid phase generates oily entering with residual oil raw material and uses the second segment reaction zone of catalyst for hydrotreatment of residual oil to carry out hydrotreatment reaction;
D the gas phase of () second segment reaction zone resultant stream gas-liquid separation recycles, liquid phase fractionation in separation column of second segment reaction zone resultant stream gas-liquid separation obtains petroleum naphtha, diesel oil and hydrogenated residue;
Wherein in step (b), first paragraph 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 all hydrogenation catalyst volumes in first paragraph 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; The carrier of described hydrogenation catalyst is aluminum oxide.
2. method according to claim 1, is characterized in that: in step (a), and the bio-oil of use comprises vegetables oil or animal grease.
3. method according to claim 1, is characterized in that: in step (b), and the reaction pressure of first paragraph reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 8.0h
-1, average reaction temperature 180 DEG C ~ 425 DEG C.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), the hydrogen to oil volume ratio 300:1 ~ 2500:1 of first paragraph reaction zone, volume space velocity 1.0h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 400 DEG C.
5. method according to claim 1, is characterized in that: in step (b) first paragraph reaction zone, and 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.
6. method according to claim 1, is characterized in that: in step (c), and the reaction pressure of second segment reaction zone is 8.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 300:1 ~ 3000:1, and volume space velocity is 0.1h
-1~ 4.0h
-1, average reaction temperature 280 DEG C ~ 465 DEG C.
7. method according to claim 1, is characterized in that: in step (c), and the reaction pressure of second segment reaction zone is 10.0MPa ~ 20.0MPa hydrogen to oil volume ratio is 500:1 ~ 2500:1, and volume space velocity is 0.1h
-1~ 2.0h
-1, average reaction temperature is 300 DEG C ~ 460 DEG C.
8. method according to claim 1, is characterized in that: in step (c), and the residual hydrogenation catalyst series of second segment reaction zone comprises protective material, Hydrodemetalation catalyst, Hydrobon catalyst and removal of ccr by hydrotreating catalyzer.
9. method according to claim 1, is characterized in that: first paragraph reaction zone generates oil and accounts for 5% ~ 40% of second segment reaction zone liquid phase feeding weight.
10. method according to claim 1, is characterized in that: first paragraph reaction zone generates oil and accounts for 10% ~ 30% of second segment reaction zone liquid phase feeding weight.
11. methods according to claim 1, is characterized in that: the DNA vaccine of first paragraph reaction zone bio-oil raw material controls to be 40% ~ 95%.
12. methods according to claim 1, is characterized in that: the DNA vaccine of first paragraph reaction zone bio-oil raw material controls to be 60% ~ 90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110353701.XA CN103102961B (en) | 2011-11-10 | 2011-11-10 | Residue oil hydrogenation method for diesel oil by-production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110353701.XA CN103102961B (en) | 2011-11-10 | 2011-11-10 | Residue oil hydrogenation method for diesel oil by-production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103102961A CN103102961A (en) | 2013-05-15 |
| CN103102961B true CN103102961B (en) | 2015-02-18 |
Family
ID=48311167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110353701.XA Active CN103102961B (en) | 2011-11-10 | 2011-11-10 | Residue oil hydrogenation method for diesel oil by-production |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103102961B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348732A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Heavy distillate oil hydrotreating method |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN101768469A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Combined hydrogenation method for mineral oil and animal and vegetable oil |
| CN102041023A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Method for improving residual oil hydrogenation by blending biological grease |
-
2011
- 2011-11-10 CN CN201110353701.XA patent/CN103102961B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| CN101348732A (en) * | 2007-07-18 | 2009-01-21 | 中国石油化工股份有限公司 | Heavy distillate oil hydrotreating method |
| CN101768469A (en) * | 2008-12-31 | 2010-07-07 | 中国石油化工股份有限公司 | Combined hydrogenation method for mineral oil and animal and vegetable oil |
| CN102041023A (en) * | 2009-10-16 | 2011-05-04 | 中国石油化工股份有限公司 | Method for improving residual oil hydrogenation by blending biological grease |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103102961A (en) | 2013-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103102958B (en) | Residual oil hydrogenation method for high quality diesel oil yield increase | |
| CN103102959B (en) | Residual oil hydrogenation method for high quality diesel oil yield increase | |
| CN103102961B (en) | Residue oil hydrogenation method for diesel oil by-production | |
| CN103102960B (en) | Residue oil hydrogenation method for diesel oil by-production | |
| CN103102913B (en) | Wax oil hydrotreating method for diesel oil by-production | |
| CN103102967B (en) | Wax oil hydrotreating method for diesel oil by-production | |
| CN103102964B (en) | Residue oil hydrogenation method for high quality diesel oil by-production | |
| CN103102901B (en) | Hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil | |
| CN103102912B (en) | Two-stage hydrogenation method for producing high quality low freezing point motor fuel | |
| CN103102916B (en) | Two-stage hydrogenation method for producing low freezing point motor fuel | |
| CN103102910B (en) | Two-stage hydrogenation method for producing low freezing point motor fuel from biological oil | |
| CN103102914B (en) | Wax oil hydrotreating method for high quality diesel oil yield increase | |
| CN103374398B (en) | Hydrogenation method for producing high-quality low-condensation-point diesel oil | |
| CN103374401B (en) | A kind of method of hydrotreating producing high-quality burning oil | |
| CN103102963B (en) | Residue oil hydrogenation method for high quality diesel oil by-production | |
| CN103374405B (en) | A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil | |
| CN103102918B (en) | Two-stage hydrogenation method for producing solvent oil | |
| CN103102969B (en) | Wax oil hydrotreating method for high quality diesel oil by-production | |
| CN103102915B (en) | Wax oil hydrotreating method for high quality diesel oil by-production | |
| CN103102968B (en) | Wax oil hydrotreating method for high quality diesel oil yield increase | |
| CN103374413B (en) | Hydrogenation combination method for producing high-quality kerosene | |
| CN103102922B (en) | Two-stage hydrogenation method for producing solvent oil | |
| CN103374407B (en) | A kind of method of hydrotreating producing low freezing point diesel fuel | |
| CN103374378B (en) | A kind of method of hydrotreating producing high-grade low-freezing point diesel oil | |
| CN103102908B (en) | Two-stage hydrogenation method for producing low aromatic hydrocarbon solvent oil from biological oil |
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 |