CN103102921B - Two-stage hydrogenation method for producing high quality low freezing point motor fuel - Google Patents
Two-stage hydrogenation method for producing high quality low freezing point motor fuel Download PDFInfo
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- CN103102921B CN103102921B CN201110353772.XA CN201110353772A CN103102921B CN 103102921 B CN103102921 B CN 103102921B CN 201110353772 A CN201110353772 A CN 201110353772A CN 103102921 B CN103102921 B CN 103102921B
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- 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 invention relates to a two-stage hydrogenation method for producing a high quality low freezing point motor fuel. The method is characterized in that a biological oil raw material and hydrogen pass through a first stage hydrogenation reaction zone containing at least two hydrogenation reactors, wherein the mixture passes through a low temperature operation reactor, and then passes through a high temperature operation reactor; the hydrogen-rich gas is recycled at the first stage; the liquid enters a second stage hydrogenation modification reaction zone; the sub-hydrogen gas after hydrogenation modification is recycled at the second stage; the liquid product is subjected to fractionation to obtain naphtha and a low freezing point diesel oil; and under a reaction state, active 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, and active components of the hydrogenation catalyst used at the second stage are reduction state Pt and/or Pd. Compared to the method in the prior art, the method of the present invention has the following advantages that: a low freezing point motor fuel can be produced, activity stability of the catalyst can be ensured, and stable and long period device operation can be ensured.
Description
Technical field
The present invention relates to a kind of method of hydrotreating, particularly a kind of is stock oil with bio-oil, the two-stage method method of hydrotreating of direct production high-grade low-freezing point automotive fuel.
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 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.
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.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is the less stable of catalyzer, and running period shortens, and needs 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, cannot meet the requirement of industrial application.
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.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first paragraph hydrofining (operational condition of optimization and the sulphided state hydrogenation catalyst of composition grating), second segment hydro-upgrading (use noble metal catalyst), it can be directly raw material production high-grade low-freezing point automotive fuel with bio-oil, 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.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating producing high-grade low-freezing point automotive fuel, take bio-oil as stock oil, under the condition of hydrogenation, first by using sulfide type catalyst first paragraph reaction zone, then by using the second segment reaction zone of noble metal hydrogenation modifying catalyst, the method of the low condensation point automotive fuel of direct production, can the high-quality diesel oil blending product of direct production, the situation that diesel product can not be occurred biofuel that conventional animal-plant oil obtains is gone mouldy, can ensure that hydrogenation catalyst has longer running period simultaneously, be suitable for industrial application.
The two-stage method method of hydrotreating that the present invention produces high-grade low-freezing point automotive fuel comprises following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and Co of sulphided state;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle in first paragraph reaction zone after gas-phase dehydration process, the second segment reaction zone using catalyst for hydro-upgrading is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of catalyst for hydro-upgrading is Pt and/or Pd of reduction-state;
D gas phase that the reaction effluent gas-liquid separation of () second segment reaction zone obtains recycles in second segment reaction zone, and liquid phase fractionation in separation column that the reaction effluent gas-liquid separation of second segment reaction zone obtains obtains petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
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.
In the inventive method step (b), the Hydroprocessing conditions of the hydrotreating reactor of cold operation is generally reaction pressure 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h
-1~ 6.0h
-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Process furnace or interchanger are set between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, to adjust the temperature of reaction of the hydrotreating reactor of high-temperature operation.
In the inventive method step (b), reaction mass first by the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use with the weight content of oxide basis for 3% ~ 20%.Reaction mass continues through the hydrogenator of high-temperature operation, and the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation counts 15% ~ 40% with oxide weight.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than catalyzer in cold operation hydrogenator 3 ~ 25 percentage points.Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also can load multiple catalysts.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.Hydrogenation active component is the catalyzer of oxidation state, carries out conventional sulfidizing before the use, makes hydrogenation active component be converted into sulphided state.Business hydrogenation catalyst 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), first paragraph reaction zone hydrogenation active component is the catalyzer of oxidation state, carries out conventional sulfidizing before the use, makes hydrogenation active component be converted into sulphided state, or use the catalyzer that ex situ presulfiding is good.
In the inventive method step (c), the Hydroprocessing conditions of second segment 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 0.3h
-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 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.The working pressure of second segment reaction zone can be identical with first paragraph reaction zone, also can be different.The liquid phase entering second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, also can be the diesel oil distillate that the liquid phase material after the gas-liquid separation of first paragraph reaction zone obtains through separation column fractionation.
In the inventive method step (c), the catalyst for hydro-upgrading of second segment reaction zone has isomery function, as containing components such as beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieves.Catalyst for hydro-upgrading is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.50%.The massfraction of catalyst for hydro-upgrading Middle molecule sieve is generally 5% ~ 40%.Other component in catalyst for hydro-upgrading is generally the porous refractory oxide such as aluminum oxide, silicon oxide, amorphous aluminum silicide.
In the inventive method step (c), catalyzer uses hydrogen 200 DEG C ~ 500 DEG C temperature before use, reduces under preferably 220 DEG C ~ 450 DEG C conditions.Whenever forbid in second segment system, inject sulfur-bearing, nitrogenous medium, avoid poisoning of catalyst.
The sulfur-containing medium supplemented in first paragraph reaction mass (optimum is dosed in the liquid phase feeding of first paragraph reaction zone) in the inventive method step (e) can be the compound of sulfur-bearing, as DMDS, CS
2deng, also can be the oil light-end products of sulfur-bearing, as the boat coal etc. of sulfur-bearing.Supplementing by sulphur, can ensure that the hydrogen sulfide content in the circulation gas of first paragraph reaction zone is not less than 0.005v%, preferred 0.01v% ~ 2.0v%.
Accompanying drawing explanation
Fig. 1 is the two-stage method method of hydrotreating principle flow chart that the present invention produces high-grade low-freezing point automotive fuel.
Fig. 2 is the another one principle flow chart that the present invention produces the two-stage method method of hydrotreating of high-grade low-freezing point automotive fuel.
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 loading low temperature and the high temperature hydrogenation reactor of sulphided state catalyzer, the hydrogenated oil obtained is separated in high-pressure separator (abbreviation high score) gas obtained and recycles in first paragraph reaction zone after processed, the liquid fractionation obtained and hydrogen are mixed into the second segment reaction zone comprising and have isomery performance noble metal hydrogenation modifying catalyst, obtain hydro-upgrading logistics to be separated in high-pressure separator (abbreviation high score) gas obtained and to recycle in second segment reaction zone, the liquid fractionation obtained obtains following products: gas, petroleum naphtha, one or more in low freezing point diesel fuel, if improve the character of diesel product further or extend the cycle of operation, also can consider that a part of diesel oil and unconverted oil loop back first paragraph reaction zone reactive system.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 | Modifying catalyst |
| Catalyzer forms | ||||
| MoO 3，wt% | 7.0 | 15.7 | 24.5 | |
| NiO，wt% | 2.0 | 3.8 | ||
| CoO，wt% | 2.4 | |||
| Pt，wt% | 1.0 | |||
| Pd，wt% | 0.02 | |||
| Beta-molecular sieve, wt% | 10.6 | |||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | ||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | 0.32 | 0.33 | >0.34 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Rapeseed oil | Tung oil+5% turning oil |
| First paragraph reaction zone operational condition | ||||
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 1 | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2 | Catalyzer 1 |
| Catalyst volume ratio | 100 | 20:80 | 50:50 | 100 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 600:1 | 1500:1 | 300:1 |
| Volume space velocity, h -1 | 1.0 | 0.4 | 0.8 | 2.0 |
| Average reaction temperature, DEG C | 220 | 240 | 300 | 260 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 2 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 800:1 | 2000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.5 | 0.4 | 0.8 | 3.0 |
| Average reaction temperature, DEG C | 320 | 300 | 340 | 380 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 10000 | 2000 | 100 | 900 |
| Second segment reaction zone operational condition | ||||
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 15.0 | 16.0 | 4.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 1000 | 500 | 800 | 2000 |
| Volume space velocity, h -1 | 2.0 | 4.5 | 1.5 | 3.5 |
| Average reaction temperature, DEG C | 290 | 270 | 260 | 320 |
| Diesel product | ||||
| Density, g/cm 3 | 0.780 | 0.781 | 0.782 | 0.779 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Condensation point, DEG C | -20 | -15 | -7 | -35 |
| Cetane value | >80 | >80 | >80 | >80 |
Table 3 embodiment processing condition and test-results.
| Processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Soybean oil | Soybean oil | Soybean oil | Soybean oil |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 1 | |||
| Reaction pressure, MPa | 12.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 3.0 | |||
| Average reaction temperature, DEG C | 220 | |||
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 |
| Reaction pressure, MPa | 12.0 | 12.0 | 12.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 0.75 | 0.75 | 0.75 |
| Average reaction temperature, DEG C | 320 | 320 | 320 | 330 |
| Sulfur-containing medium | DMDS | DMDS | DMDS | DMDS |
| Hydrogen sulfide content in circulation gas, μ L/L | 500 | 500 | 500 | 500 |
| Two step process condition | ||||
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 12.0 | 12.0 | 12.0 | 12.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 3.0 | 3.0 | 3.0 | 3.0 |
| Average reaction temperature, DEG C | 300 | 300 | 300 | 300 |
| Runtime, h | 1000 | 200 | 400 | 600 |
| Diesel product | ||||
| Density, g/cm 3 | 0.781 | 0.781 | 0.799 | 0.860 |
| Condensation point, DEG C | -25 | -25 | -5 | 10 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | 75 | 62 |
As can be seen from embodiment, bio-oil can direct production high-grade low-freezing point diesel product by the two-stage method method of hydrotreating of this technology, or fine-quality diesel oil blending component, and can long-time steady operation.
Claims (10)
1. produce a two-stage method method of hydrotreating for high-grade low-freezing point automotive fuel, it is characterized in that comprising following content:
A one or more in () bio-oil are stock oil;
B () is under Hydroprocessing conditions, stock oil and hydrogen pass through the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and Co of sulphided state, reaction mass first by the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use with the weight content of oxide basis for 3% ~ 20%; Reaction mass continues through the hydrogenator of high-temperature operation, the active ingredient of the hydrogenation catalyst used in the hydrogenator of high-temperature operation counts 15% ~ 40% with oxide weight, and in the hydrogenator of high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrogenator 3 ~ 25 percentage points;
C () first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, recycle in first paragraph reaction zone after gas-phase dehydration process, the second segment reaction zone using catalyst for hydro-upgrading is entered after liquid phase mixes with circulation gas, under response behaviour, the active metal component of catalyst for hydro-upgrading is Pt and/or Pd of reduction-state;
D gas phase that the reaction effluent gas-liquid separation of () second segment reaction zone obtains recycles in second segment reaction zone, and liquid phase fractionation in separation column that the reaction effluent gas-liquid separation of second segment reaction zone obtains obtains petroleum naphtha and low freezing point diesel fuel;
E () supplements S-contained substance in first paragraph reaction mass, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
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 (b), the reaction pressure 3.0MPa ~ 20.0MPa of the hydrotreating reactor of cold operation, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrotreating reactor of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.3h
-1~ 6.0h
-1, average reaction temperature is higher than the hydrotreating reactor of cold operation 50 DEG C ~ 300 DEG C.
4. according to the method described in claim 1 or 3, it is characterized in that: in step (b), the average reaction temperature of the hydrotreating reactor of high-temperature operation is higher than the hydrotreating reactor of cold operation 80 ~ 220 DEG C.
5. according to the method described in claim 1 or 3, it is characterized in that: the first paragraph reaction zone in step (b) arranges 2 ~ 5 reactors.
6. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second segment 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 180 DEG C ~ 465 DEG C.
7. in accordance with the method for claim 6, it is characterized in that: in step (c), the reaction pressure of second segment reaction zone is 3.0MPa ~ 18.0MPa, and 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.
8. according to the method described in claim 1 or 6, it is characterized in that: in step (c), the catalyst for hydro-upgrading of second segment reaction zone has isomery function, catalyst for hydro-upgrading contains beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve, catalyst for hydro-upgrading is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 1.50%.
9. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in first paragraph reaction mass is the compound of sulfur-bearing, and in the circulation gas of first paragraph reaction zone, hydrogen sulfide content is not less than 0.005v%.
10. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium supplemented in first paragraph reaction mass is the oil light-end products of sulfur-bearing, and in the circulation gas of first paragraph reaction zone, hydrogen sulfide content is not less than 0.005v%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089135A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Diesel oil fraction upgrading and pour point reducing process |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101089135A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Diesel oil fraction upgrading and pour point reducing process |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
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