CN103102922B - Two-stage hydrogenation method for producing solvent oil - Google Patents
Two-stage hydrogenation method for producing solvent oil Download PDFInfo
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- CN103102922B CN103102922B CN201110353774.9A CN201110353774A CN103102922B CN 103102922 B CN103102922 B CN 103102922B CN 201110353774 A CN201110353774 A CN 201110353774A CN 103102922 B CN103102922 B CN 103102922B
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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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Abstract
The present invention relates to a two-stage hydrogenation method for producing a solvent oil. 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 hydrocracking reaction zone; the sub-hydrogen gas after hydrocracking 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 one or a plurality of materials selected from reduction state W, Mo, Ni and Co. Compared to the method in the prior art, the method of the present invention has the following advantages that: low aromatic hydrocarbon solvent oil production methods are increased, 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 taking bio-oil as stock oil, the two-stage method method of hydrotreating of direct production solvent oil.
Background technology
World economy sustainable development, at present in global range, the main source of Chemicals is fossil energy, wherein most importantly oil and coal.These two kinds of fossil energies all belong to Nonrenewable energy resources, not only resource is day by day exhausted, and heaviness and in poor quality aggravation, difficulty of processing and tooling cost increase gradually, except being improved, existing oil Refining Technologies finds new oil substitutes, produce satisfactory product with minimum cost, especially the development and utilization of renewable resources obtains paying attention to more and more widely.
Bio-oil is as renewable resources, and chief component is carbon, hydrogen and oxygen, and very similar to the composition of alkane, alcohol, ether etc., each research unit and enterprise are all making great efforts to carry out its research as clean energy.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because 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, all removes or partly remove and produce the product that meets automotive fuel standard by oxygen, and this method can directly meet 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 vegetables oil hydroconversion process, adopt 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 hydrogenation catalyst bed, produce diesel product or preparing ethylene by steam cracking raw material etc.US5705722 discloses containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation and has produced the diesel oil blending component of diesel oil distillate scope.EP1741767 and EP1741768 disclose a kind of method of producing low freezing point diesel fuel cut with animal-plant oil.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter running into is that bed carbon distribution causes shortening running period, the more catalyst changeout of need to often stopping work, and also the main purpose product of these technology is automotive fuel.
Solvent oil is important petroleum products, and its added value is higher than fuel product, and particularly the added value of high-grade low aromatic solvent naphtha is higher.High-grade low aromatic solvent naphtha raw materials for production are limited at present (generally only limits to gasoline fraction or the kerosene(oil)fraction of paraffinic crude, or reforming raffinate oil etc.), owing to requiring aromaticity content lower (some solvent oil index request aromaticity content is lower than 0.1%), therefore need to adopt complicated processing route, condition harshness, production cost is high, has limited the production of high-grade low aromatic solvent naphtha.
In prior art, bio-oil is conventionally by method independent or that produce automotive fuel with the method for other petroleum products mixing back end hydrogenations.The present invention uses grating technology and the operational condition of reduction-state hydrogenation catalyst by optimization, first paragraph hydrotreatment (sulfurized hydrogenation catalyst of grating), second segment hydrocracking (reduced form hydrocracking catalyst), can be directly taking bio-oil as raw material production low aromatic solvent naphtha.The present invention has expanded the raw material sources of high added value low aromatic solvent naphtha, and production cost is low, can further improve added value of product.
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 solvent oil, separately taking bio-oil as stock oil, first paragraph uses the sulphided state hydrogenation catalyst of grating, second segment uses reduction-state hydrocracking catalyst, the features such as direct production solvent oil under the condition of hydrogenation, has hydrogenation process stable, and running period is long.
The two-stage method method of hydrotreating that the present invention produces solvent oil comprises following content:
(a) one or more in bio-oil are stock oil;
(b) under hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, in hydrogenator, load hydrogenation catalyst, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, in W, Mo, Ni and Co that the active ingredient of first paragraph reaction zone hydrogenation catalyst is sulphided state one or more;
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles in first paragraph reaction zone after processing, liquid phase enters the second segment reaction zone that uses hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, in W, Mo, Ni and Co that the active metal component of hydrocracking catalyst is reduction-state one or more;
(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 all kinds of SOLVENTS oil distillate;
(e) in first paragraph reaction mass, supplement S-contained substance, to maintain hydrogen sulfide content in the circulation gas of first paragraph reaction zone.
In the inventive method step (a), the bio-oil using 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 DEG C ~ 280 DEG C 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 DEG C ~ 300 DEG C, preferably high 80 ~ 220 DEG C.Between the hydrotreating reactor of cold operation and the hydrotreating reactor of high-temperature operation, process furnace or interchanger are set, to adjust the temperature of reaction of hydrotreating reactor of high-temperature operation.
In the inventive method step (b), reaction mass is first by the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is taking the weight content of oxide compound as 3%～20%.Reaction mass continues by the hydrogenator of high-temperature operation, and the active ingredient of the hydrogenation catalyst using 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 cold operation hydrogenator.Reactor generally can arrange 2 ~ 5, is preferably 2.In each hydrogenator, can load a kind of catalyzer, 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 adopt commercial catalyst, also can be by the existing method preparation in this area.Hydrogenation activity component is the catalyzer of oxidation state, before using, carries out conventional sulfidizing, makes hydrogenation activity component be converted into sulphided state.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.First paragraph reaction zone hydrogenation effluent separates can comprise fractionating system, also can not comprise fractionating system (only comprising Separate System of Water-jet).While comprising fractionating system, the middle runnings (being diesel oil distillate) that fractionating system fractionation is obtained enters second segment reaction zone.
In the inventive method step (b), the catalyzer that first paragraph reaction zone hydrogenation activity component is oxidation state carried out conventional sulfidizing before using, and made hydrogenation activity component be converted into sulphided state, or used 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 DEG C ~ 465 DEG C 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 DEG C ~ 445 DEG C of average reaction temperature.The working pressure of second segment reaction zone can be identical with first paragraph reaction zone, also can be different.The liquid phase that enters 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 intermediate oil that fractionation obtains through separation column after the gas-liquid separation of first paragraph reaction zone.
In the inventive method step (c), the hydrocracking catalyst of second segment reaction zone has cracking function, as contains the component such as Y zeolite and/or ZSM-5 molecular sieve.The hydrogenation active metals component of hydrocracking catalyst is generally 5%～40% in the weight content of oxide compound.The weight content of molecular sieve component in hydrocracking catalyst is generally 5%～60%.In hydrocracking catalyst, can contain other refractory inorganic oxides simultaneously.The commercial catalysts that second segment reaction zone is used mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3971,3976, FC-12, FC-18, FC-24, FC-26, FC-32, FC-46, FC-50, FDW-1 etc.
In the inventive method step (c), catalyzer uses hydrogen 200 DEG C～500 DEG C temperature before use, under preferably 220 DEG C～450 DEG C conditions, reduces.Whenever forbid to inject sulfur-bearing, nitrogenous medium in second segment system, avoid poisoning of catalyst.
In the inventive method step (d), the low aromatic solvent naphtha obtaining is mixed solvent oil distillate, can continue according to the actual requirements fractionation and obtain vegetable oil extraction solvent, No. 90 solvent oils, No. 120 solvent oils, No. 200 solvent oils, D30, D40 etc. trade mark low aromatic solvent naphtha.Specifically can specifically determine according to the boiling range of mixed solvent oil.If there is unconverted oil, unconverted oil can go out system, also capable of circulation time reactive system.
In the inventive method step (e), in first paragraph reaction mass (optimum is dosed in the liquid phase feeding of first paragraph reaction zone), supplementary sulfur-containing medium 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 supplementing of sulphur, can ensure that the hydrogen sulfide content in the circulation gas of first paragraph reaction zone is not less than 0.005v%, preferably 0.01v%～2.0v%.
Brief description of the drawings
Fig. 1 is the two-stage method method of hydrotreating principle flow chart that the present invention produces solvent oil.
Fig. 2 is the another one principle flow chart that the present invention produces the two-stage method method of hydrotreating of solvent oil.
Embodiment
Method of the present invention is specific as follows: taking one or more the mixing oil in bio-oil as stock oil, under hydroprocessing condition, stock oil and hydrogen are by low temperature and the high temperature hydrogenation reactor of filling sulphided state catalyzer, the hydrogenated oil obtaining separates in high-pressure separator (abbreviation high score) gas obtaining and recycles in first paragraph reaction zone after processed, the liquid distillate obtaining and hydrogen are mixed into and comprise the second segment reaction zone with cracking performance Nobel metal hydrogen cracking catalyst, obtaining hydrocracking logistics separates in high-pressure separator (abbreviation high score) gas obtaining and recycles at second segment, the liquid fractionation obtaining obtains all kinds of SOLVENTS oil production, also consider, at first paragraph, a part of middle runnings and unconverted oil are looped back to first paragraph reaction zone.The bio-oil that embodiment uses is 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 | Cracking catalyst |
| Catalyzer composition | ? | ? | ? | ? |
| MoO 3，wt% | 6.2 | 13.0 | 22.5 | 20.6 |
| NiO，wt% | 1.8 | ? | 4.1 | 3.5 |
| CoO，wt% | ? | 2.3 | ? | ? |
| Y molecular sieve, wt% | ? | ? | ? | 13.5 |
| 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 | >0.30 | >0.30 | >0.34 |
Table 2 embodiment processing condition and test-results.
| Processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Soybean oil | Rapeseed oil | Viscotrol C | Sesame oil+10% 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 | 15:85 | 45:55 | 100 |
| Reaction pressure, MPa | 16.0 | 8.0 | 6.0 | 4.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1500:1 | 500:1 |
| Volume space velocity, h -1 | 1.5 | 0.5 | 2.5 | 1.2 |
| 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 | 16.0 | 8.0 | 6.0 | 4.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 800:1 | 2000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.8 | 1.0 | 0.5 | 3.0 |
| Average reaction temperature, DEG C | 320 | 380 | 320 | 350 |
| Sulfur-containing medium | DMDS | DMDS | CS 2 | CS 2 |
| Hydrogen sulfide content in circulation gas, μ L/L | 1000 | 9000 | 500 | 2000 |
| Second segment reaction zone operational condition | ? | ? | ? | ? |
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 15.0 | 16.0 | 6.0 | 4.0 |
| Entrance hydrogen to oil volume ratio | 1000 | 500 | 800 | 2000 |
| Volume space velocity, h -1 | 2.0 | 1.0 | 3.0 | 4.0 |
| Average reaction temperature, DEG C | 300 | 280 | 340 | 350 |
| Solvent oil cut | ? | ? | ? | ? |
| Yield, quality % | 85 | 82 | 78 | 86 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～175 | 61～165 | 65～120 | 65～150 |
Table 3 embodiment processing condition and test-results.
| Processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen | Oleum Gossypii semen |
| Cold operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 1 | ? | ? | ? |
| Reaction pressure, MPa | 153.0 | ? | ? | ? |
| Entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 3.0 | ? | ? | ? |
| Average reaction temperature, DEG C | 230 | ? | ? | ? |
| High-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 1.5 | 1.0 | 1.0 | 1.0 |
| Average reaction temperature, DEG C | 320 | 320 | 320 | 320 |
| Sulfur-containing medium | DMDS | DMDS | DMDS | DMDS |
| Hydrogen sulfide content in circulation gas, μ L/L | 800 | 800 | 800 | 800 |
| Two step process condition | ? | ? | ? | ? |
| Catalyzer | Cracking catalyst | Cracking catalyst | Cracking catalyst | Cracking catalyst |
| Reaction pressure, MPa | 15.0 | 15.0 | 15.0 | 15.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Cumulative volume air speed, h -1 | 2.0 | 2.0 | 2.0 | 2.0 |
| Average reaction temperature, DEG C | 300 | 300 | 300 | 300 |
| Runtime, h | 1000 | 200 | 500 | 1000 |
| Solvent oil cut | ? | ? | ? | ? |
| Yield, quality % | 86 | 86 | 55 | 38 |
| Aromaticity content | Do not detect | Do not detect | Do not detect | Do not detect |
| Sulphur content, μ g/g | Do not detect | Do not detect | Do not detect | Do not detect |
| Boiling range scope, DEG C | 61～180 | 61～180 | 61～180 | 61～180 |
Yield is taking second segment reaction zone feeds as benchmark.
Can be found out by embodiment, the method for hydrotreating of bio-oil by this technology can the various high-quality low aromatic solvent of direct production oil production, by selecting different bio-oils, can production high-quality low aromatic solvent naphtha, and running is stable.
Claims (9)
1. a two-stage method method of hydrotreating of producing solvent oil, is characterized in that comprising following content:
(a) one or more in bio-oil are stock oil;
(b) under hydroprocessing condition, stock oil and hydrogen are by the first paragraph reaction zone of at least two hydrogenators, in hydrogenator, load hydrogenation catalyst, stock oil and hydrogen are first by the hydrogenator of cold operation, then by the hydrogenator of high-temperature operation, under response behaviour, the W that the active ingredient of first paragraph reaction zone hydrogenation catalyst is sulphided state, Mo, in Ni and Co one or more, reaction mass is first by the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst using is taking the weight content of oxide compound as 3%～20%, reaction mass continues by the hydrogenator of high-temperature operation, the active ingredient of the hydrogenation catalyst using 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 3～25 percentage points of the catalyzer in cold operation hydrogenator,
(c) first paragraph reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration recycles in first paragraph reaction zone after processing, liquid phase enters the second segment reaction zone that uses hydrocracking catalyst after mixing with second segment reaction zone circulation gas, under response behaviour, in W, Mo, Ni and Co that the active metal component of hydrocracking catalyst is reduction-state one or more;
(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 solvent oil cut;
(e) in first paragraph reaction mass, supplement S-contained substance, 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, volume space velocity is 0.3h
-1～6.0h
-1, 120 DEG C～280 DEG C 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 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 80～220 DEG C than the hydrotreating reactor of cold operation.
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, 180 DEG C～465 DEG C of average reaction temperature.
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 hydrocracking catalyst of second segment reaction zone has cracking function, hydrocracking catalyst contains Y zeolite and/or ZSM-5 molecular sieve component; The hydrogenation active metals component of hydrocracking catalyst is taking the weight content of oxide compound as 5%～40%, and the weight content of molecular sieve component in hydrocracking catalyst is 5%～60%.
9. in accordance with the method for claim 1, it is characterized in that: in first paragraph reaction mass, supplementary sulfur-containing medium is the compound of sulfur-bearing, or the oil light-end products of sulfur-bearing, 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 |
|---|---|---|---|---|
| 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 |
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| BRPI0500591A (en) * | 2005-02-18 | 2006-10-03 | Petroleo Brasileiro Sa | process for hydroconversion of vegetable oils |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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