CN103102921A - 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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- CN103102921A CN103102921A CN201110353772XA CN201110353772A CN103102921A CN 103102921 A CN103102921 A CN 103102921A CN 201110353772X A CN201110353772X A CN 201110353772XA CN 201110353772 A CN201110353772 A CN 201110353772A CN 103102921 A CN103102921 A CN 103102921A
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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
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- 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 take bio-oil as stock oil, the two-stage method method of hydrotreating of direct production high-grade low-freezing point automotive fuel.
Background technology
The energy in global range is mainly derived from fossil energy at present, 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 be produced a large amount of light clean fuels, increase new oil substitutes when these all require existing oil Refining Technologies is improved, produce satisfactory product with minimum cost.
Bio-oil obtains the extensive attention in the world as renewable resources, and each research unit and enterprise are all making great efforts to carry out it as the research of clean energy.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because the fatty acid methyl ester oxygen level is high, although many countries and regions have been put into effect the standard of biofuel successively, and be not suitable for all oil engines.Bio-oil is produced automotive fuel by the method for hydrogenation, and soon oxygen is all removed or partly removed and produce the product that meets the automotive fuel standard, and this method can directly satisfy the requirement of existing market.
existing animal-plant oil hydrogenation method is produced 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 the vegetables oil hydroconversion process, adopt the coker gasoline cut, 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 the hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.
EP1741767 and EP1741768 disclose a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil and at first pass through hydrotreatment, then by the isomerization catalyst bed layer, obtain the low freezing point diesel fuel component, but owing to generating water in the hydrotreatment process, isomerization catalyst is caused very adverse influence, and device can not long-period stable operation.
Comprise that in the bio-oil hydrogenation process of aforesaid method, one of subject matter that runs into is the less stable of catalyzer, shorten running period, the more catalyst changeout of need to often stopping work.Particularly separately take bio-oil as raw material or bio-oil blending ratio when higher, more be subject to obvious impact the running period of hydrogenation catalyst, can't satisfy the requirement of industrial application.
Summary of the invention
for the deficiencies in the prior art, the invention provides a kind of two-stage method method of hydrotreating of producing high-grade low-freezing point automotive fuel, take bio-oil as stock oil, under the condition of hydrogenation, at 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 direct production high-quality diesel oil is in harmonious proportion product, make diesel product that the situation that biofuel that conventional animal-plant oil makes is gone mouldy can not occur, can guarantee simultaneously that hydrogenation catalyst has long running period, 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) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, stock oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles at the first paragraph reaction zone after processing, liquid phase with enter the second segment reaction zone that uses catalyst for hydro-upgrading after circulation gas mixes, under response behaviour, the active metal component of catalyst for hydro-upgrading is Pt and/or the Pd of reduction-state;
(d) gas phase that obtains of second segment reaction zone reaction effluent gas-liquid separation recycles at the second segment reaction zone, and liquid phase fractionation in separation column that the gas-liquid separation of second segment reaction zone reaction effluent obtains obtains petroleum naphtha and low freezing point diesel fuel;
(e) replenish S-contained substance in the first paragraph reaction mass, to keep hydrogen sulfide content in first paragraph reaction zone circulation gas.
In the inventive method step (a), the bio-oil that uses 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 condition 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, 120 ℃ ~ 280 ℃ of average reaction temperature; 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 than the hydrotreating reactor of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ~ 220 ℃.Between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, process furnace or interchanger are set, with the temperature of reaction of the hydrotreating reactor of adjusting high-temperature operation.
In the inventive method step (b), reaction mass is at first by in the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is take the weight content of oxide compound as 3%～20%.Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses 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 3～25 percentage points of catalyzer in the cold operation hydrogenator.Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also multiple catalysts can be loaded.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent simultaneously, as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.The hydrogenation activity component is the catalyzer of oxidation state, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state.the business hydrogenation catalyst mainly contains, as 3926 of Fushun Petrochemical Research Institute (FRIPP) development, 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 activity component is the catalyzer of oxidation state, carries out conventional sulfidizing before using, and makes the hydrogenation activity component be converted into sulphided state, perhaps uses the outer good catalyzer of prevulcanized of device.
In the inventive method step (c), the hydroprocessing condition 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, 180 ℃ ~ 465 ℃ of average reaction temperature; 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, 200 ℃ ~ 445 ℃ of average reaction temperature.The working pressure of second segment reaction zone can be identical with the first paragraph reaction zone, also can be different.The liquid phase that enters the second segment reaction zone can be the liquid phase material after the gas-liquid separation of first paragraph reaction zone, can be also the liquid phase material diesel oil distillate that fractionation obtains through separation column after the gas-liquid separation of first paragraph reaction zone.
In the inventive method step (c), the catalyst for hydro-upgrading of second segment reaction zone has the isomery function, as contains the components such as 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 of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01%～1.50%.In catalyst for hydro-upgrading, the massfraction of molecular sieve is generally 5%～40%.Other component in catalyst for hydro-upgrading is generally the porous refractory oxides such as aluminum oxide, silicon oxide, amorphous aluminum silicide.
In the inventive method step (c), catalyzer uses hydrogen 200 ℃～500 ℃ temperature before use, reduces under preferred 220 ℃～450 ℃ conditions.Whenever forbid to inject sulfur-bearing, nitrogenous medium in the second segment system, avoid poisoning of catalyst.
The sulfur-containing medium that replenishes 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, and CS
2Deng, can be also the oil light-end products of sulfur-bearing, as boat coal of sulfur-bearing etc.By replenishing of sulphur, can guarantee that the hydrogen sulfide content in first paragraph reaction zone circulation gas is not less than 0.005v%, preferred 0.01v%～2.0v%.
In prior art, the bio-oil hydrogenation is produced the method for automotive fuel, generally need to the petroleum fractions hybrid process of larger proportion, otherwise can not guarantee running period, perhaps directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity.The present invention uses grating technology and the operational condition of catalyzer by optimization, first paragraph hydrofining (the sulphided state hydrogenation catalyst of the operational condition of optimization and composition grating), second segment hydro-upgrading (use noble metal catalyst), can be directly take bio-oil as raw material production high-grade low-freezing point automotive fuel, solved the problem that the bio-oil hydrogenation unit can not the long period steady running, condensation point that simultaneously can the decrease diesel oil distillate.
Description of drawings
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: the mixing oil of one or more in the bio-oil is as stock oil, under the hydroprocessing condition, stock oil and hydrogen are by low temperature and the high temperature hydrogenation reactor of filling sulphided state catalyzer, the hydrogenated oil that obtains separates in high-pressure separator (abbreviation high score) gas that obtains and recycles at the first paragraph reaction zone after processed, the liquid fractionation that obtains and hydrogen are mixed into and comprise the second segment reaction zone with isomery performance noble metal hydrogenation modifying catalyst, obtaining the hydro-upgrading logistics recycles at the second segment reaction zone at the gas that high-pressure separator (abbreviation high score) separation obtains, the liquid fractionation that obtains obtains following products: gas, petroleum naphtha, one or more in low freezing point diesel fuel, if further improve the character of diesel product or extend the cycle of operation, can consider that also a part of diesel oil and unconverted oil loop back first paragraph reaction zone reactive system.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.
Further illustrate particular case of the present invention below by embodiment.
The chief component 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 | ? | ? | ? | ? |
| The cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 1 | Catalyzer 1/ catalyzer 2 | Catalyzer 1/ catalyzer 2 | Catalyzer 1 |
| The catalyst volume ratio | 100 | 20:80 | 50:50 | 100 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| The 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, ℃ | 220 | 240 | 300 | 260 |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 2 |
| Reaction pressure, MPa | 15.0 | 8.0 | 4.0 | 12.0 |
| The 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, ℃ | 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 |
| The 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, ℃ | 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, ℃ | -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 |
| The cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 1 | ? | ? | ? |
| Reaction pressure, MPa | 12.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 3.0 | ? | ? | ? |
| Average reaction temperature, ℃ | 220 | ? | ? | ? |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 | Catalyzer 2 |
| Reaction pressure, MPa | 12.0 | 12.0 | 12.0 | 12.0 |
| The 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, ℃ | 320 | 320 | 320 | 330 |
| Sulfur-containing medium | DMDS | DMDS | DMDS | DMDS |
| Hydrogen sulfide content in circulation gas, μ L/L | 500 | 500 | 500 | 500 |
| The two step process condition | ? | ? | ? | ? |
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 12.0 | 12.0 | 12.0 | 12.0 |
| The entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| The cumulative volume air speed, h -1 | 3.0 | 3.0 | 3.0 | 3.0 |
| Average reaction temperature, ℃ | 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, ℃ | -25 | -25 | -5 | 10 |
| Sulphur content, μ g/g | <5 | <5 | <5 | <5 |
| Cetane value | >80 | >80 | 75 | 62 |
Can be found out by embodiment, the two-stage method method of hydrotreating of bio-oil by present technique can direct production high-grade low-freezing point diesel product, perhaps fine-quality diesel oil blending component, and can long-time steady operation.
Claims (10)
1. two-stage method method of hydrotreating of producing high-grade low-freezing point automotive fuel is characterized in that comprising following content:
(a) one or more in bio-oil are stock oil;
(b) under the hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, load hydrogenation catalyst in hydrogenator, stock oil and hydrogen is the hydrogenator by cold operation at first, then the hydrogenator by high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is one or more in W, Mo, Ni and the Co of sulphided state;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles at the first paragraph reaction zone after processing, liquid phase with enter the second segment reaction zone that uses catalyst for hydro-upgrading after circulation gas mixes, under response behaviour, the active metal component of catalyst for hydro-upgrading is Pt and/or the Pd of reduction-state;
(d) gas phase that obtains of second segment reaction zone reaction effluent gas-liquid separation recycles at the second segment reaction zone, and liquid phase fractionation in separation column that the gas-liquid separation of second segment reaction zone reaction effluent obtains obtains petroleum naphtha and low freezing point diesel fuel;
(e) replenish S-contained substance in the first paragraph reaction mass, to keep hydrogen sulfide content in first paragraph reaction zone 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 (b), the reaction pressure 3.0MPa of the hydrotreating reactor of cold operation ~ 20.0MPa, hydrogen to oil volume ratio are 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; 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 than the hydrotreating reactor of cold operation high 50 ℃ ~ 300 ℃.
4. according to the described method of 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 80 ~ 220 ℃ than the hydrotreating reactor of cold operation.
5. according to the described method of claim 1 or 3, it is characterized in that: step (b) reaction mass is at first by in the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is take the weight content of oxide compound as 3%～20%; Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation counts 15%～40% with oxide weight.
6. it is characterized in that in accordance with the method for claim 5: in the hydrogenator of high-temperature operation, the active component content of catalyzer is higher than 3～25 percentage points of the catalyzer in the cold operation hydrogenator.
7. according to the described method of claim 1 or 3, it is characterized in that: the first paragraph reaction zone in step (b) arranges 2～5 reactors.
8. 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, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred reaction pressure 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 ℃ ~ 445 ℃.
9. according to the described method of claim 1 or 8, it is characterized in that: in step (c), the catalyst for hydro-upgrading of second segment reaction zone has the 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%.
10. in accordance with the method for claim 1, it is characterized in that: the sulfur-containing medium that replenishes in the first paragraph reaction mass is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing, and in first paragraph reaction zone circulation gas, hydrogen sulfide content is not less than 0.005v%.
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|---|---|---|---|---|
| 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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| 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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