CN103374400B - Hydrogenation method produces the combined method of high-quality burning oil - Google Patents
Hydrogenation method produces the combined method of high-quality burning oil Download PDFInfo
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Abstract
The present invention relates to the combined method that a kind of hydrogenation method produces high-quality burning oil.First under the condition of hydrogenation, bio-oil mixes with recycle hydrogen by hydrotreatment reaction zone, hydrotreatment resultant flow point uses from the gas circulation obtained, being separated the liquid obtained mixes by hydrofining reaction district with kerosene feedstock oil and recycle hydrogen, then the hydro-upgrading reaction zone at least comprising hydroisomerizing performance catalyzer is entered, hydro-upgrading resultant flow point continues fractionation from the liquid obtained and obtains petroleum naphtha and kerosene fuel product, under response behaviour, the hydrogenation active component of the hydrogenation catalyst that hydrotreatment reaction zone uses is Pt and/or Pd of reduction-state.Compared with prior art, the inventive method not only effectively can improve bio-oil as storage stability during oil fuel, can also direct production high-quality burning oil.
Description
Technical field
The invention belongs to the working method of renewable energy source, relate to a kind of method of hydrotreating, particularly a kind of with bio-oil and boat coal cut for stock oil, the combined hydrogenation method of direct production high-quality burning oil.
Background technology
The energy in current global range is mainly derived from fossil energy, mainly comprise coal and oil, and motor for automobile fuel is mainly derived from oil.Fossil energy belongs to Nonrenewable energy resources, and resource is day by day exhausted, and oil more has the trend of heaviness and the aggravation of in poor quality degree.Along with sustained economic development, the environmental regulation increasingly stringent in the world, emission standard is more and more higher, various countries are very vigorous to the demand of light clean fuel, these all require that new oil substitutes is constantly found while improving existing oil Refining Technologies by oil company and R&D institution, and produce satisfactory product with minimum cost, especially can to the development and utilization of renewable resource.
Bio oil, fat are renewable resourcess, and therefore its comprehensive utilization also obtains worldwide extensive attention, and be devoted to take it as the research of raw material production cleaning product with all strength.Proven technique by the first-generation biofuel utilizing the method for transesterify to carry out production biofuel (being generally fatty acid methyl ester).But because in this kind of biofuel, oxygen level is high, although many countries and regions have put into effect the standard of biofuel successively, all oil engines can not be applicable to.If bio oil, fat are produced automotive fuel by the method for deep hydrogenation, all remove by oxygen or most of product removing production and meet automotive fuel standard, this method directly can meet the requirement of existing market.
Existing bio oil, fat hydrogenation method produces the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose vegetables oil hydroconversion process, adopt coker naphtha, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), petroleum hydrocarbon cut and the bio oil such as wax oil cut or residue oil fraction, fat is directly mixed into hydroconversion reaction zone, beds is passed through under the effect of hydrogen, produce the raw material etc. of diesel product or preparing ethylene by steam cracking.US5705722 discloses the diesel oil blending component producing diesel oil distillate scope containing the vegetables oil such as unsaturated fatty acids, fat and animal oil mixing back end hydrogenation.
EP1741767 and EP1741768 discloses a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil first through hydrotreatment, then by isomerization catalyst bed layer, obtain low freezing point diesel fuel component, but owing to generating water in hydroprocessing processes, cause very adverse influence to isomerization catalyst, device can not long-period stable operation.
Comprise in the bio-oil hydrogenation process of aforesaid method, one of subject matter run into is that bed carbon distribution causes pressure drop rise that running period is shortened, and needs more catalyst changeout of often stopping work.Particularly independent with bio oil, fat for raw material or bio-oil blending ratio higher time, the running period of hydrogenation catalyst is more subject to obvious impact.Carry out conventional raw material weighted BMO spaces (as the hydrotreated lube base oil of routine or either shallow hydrofining etc.) according to this area general knowledge, although extend (generally can reach 500 hours) running period to some extent, but still long period steady running problem can not be solved.Containing multiple different organo-functional group in bio-oil, the reaction of these organo-functional groups in hydrogenation process is comparatively complicated, influence each other between different reactions, the major cause affecting bio-oil raw material hydrogenation process stability is still indefinite, and therefore improving run stability is the major issue that this area needs to solve.And also because catalyst activity is affected the shortcomings such as the running period that causes is short when producing light ends.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of method of hydrotreating producing high-quality burning oil, with bio-oil and kerosene(oil)fraction for stock oil, direct production high-quality burning oil product under the condition of hydrogenation, has hydrogenation process and stablizes, the features such as running period is long.
A kind of hydrogenation method of the present invention produces the combined method of high-quality burning oil, it is characterized in that comprising following content:
A one or more in () bio-oil are the first stock oil, one or more of virgin kerosene or secondary processing kerosene(oil)fraction are the second stock oil;
B () is under hydroprocessing operations condition, the first stock oil is by the first paragraph reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, bio-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 Pt and/or Pd of sulphided state, first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration process Posterior circle uses;
C () is under hydrofining operational condition, step (b) is separated and obtains the second reaction zone that liquid and the second stock oil pass through to load Hydrobon catalyst under hydroconversion condition, under hydroconversion condition, then continue to enter the 3rd reaction zone at least comprising catalyst for hydro-upgrading;
(d) the 3rd the gas phase of reaction zone reaction effluent recycle, the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and is obtained petroleum naphtha and high-quality burning oil cut.
In the inventive method step (a), the bio oil used, fat 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, curcas oil, sunflower seed oil and rice bran wet goods, one or more during animal grease comprises butter, lard, sheep oil, fish oil and roasts grease that other animals obtain etc.Being preferably carbon chain lengths is C
12~ C
16bio-oil, as cocounut oil etc.
In the inventive method step (a), virgin kerosene is generally the kerosene(oil)fraction that Atmospheric vacuum fractionation obtains, the virgin kerosene of preferred intermediate base crude oil and naphthenic base crude.Secondary processing kerosene is generally secondary petroleum refining process, as the kerosene(oil)fraction that the technological processs such as hydrocracking, catalytic cracking, hydrotreatment, coking, thermally splitting, viscosity breaking, ethene obtain, and the kerosene(oil)fraction of coal tar.
In the inventive method step (a), the volume ratio of the first stock oil and the second stock oil is 1:99 ~ 99:1, preferred 5:95 ~ 95:5, best 10:90 ~ 90:10.
In the inventive method step (b), in the first reaction zone, be prohibited from entering the material of sulfur-bearing, nitrogenous impurity.
In the inventive method step (b), the Hydroprocessing conditions of the hydrogenator of cold operation is generally reaction pressure 3.0MPa ~ 20.0MPa, and be preferably 4.0MPa ~ 18.0MPa, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 6.0h
-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrogenator of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, is preferably 4.0MPa ~ 18.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.5h
-1~ 6.0h
-1, average reaction temperature is higher than the hydrogenator of cold operation 50 DEG C ~ 300 DEG C, preferably high 80 DEG C ~ 220 DEG C.Process furnace or interchanger are set between the hydrogenator of cold operation and the hydrogenator of high-temperature operation, to adjust the temperature of reaction of the hydrogenator of high-temperature operation.
Bio-oil is first by the hydrogenator of cold operation, and the active ingredient of the hydrogenation catalyst of use is in the element quality of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%.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 is in the element of precious metals pt and/or Pd, and the content of noble metal hydrogenation active ingredient is 0.10% ~ 3.50%.In the hydrogenator of preferred high-temperature operation, the active component content of catalyzer is higher than the catalyzer in cold operation hydrogenator, preferably high 0.1 ~ 3 percentage point (in element quality).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.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develops HDO-18 catalyzer, also can by described method preparations such as CN00123141.3.The catalyzer of the first reaction zone carries out conventional reduction treatment before use, and the catalyzer of other reaction zone carries out conventional sulfidizing before use.Reduction treatment condition is generally in pressure 2 ~ 15MPa and temperature 200 ~ 400 DEG C, with hydrogen to catalyst reduction 1 ~ 15 hour.
In the inventive method step (c), the Hydroprocessing conditions of second reaction zone is generally reaction pressure 1.0MPa ~ 20.0MPa, can be identical with the first reaction zone, also can not be identical, and hydrogen to oil volume ratio is 150:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, average reaction temperature 130 DEG C ~ 420 DEG C; Preferred operational condition is hydrogen to oil volume ratio 200:1 ~ 2000:1, volume space velocity 0.4h
-1~ 8.0h
-1, average reaction temperature 150 DEG C ~ 400 DEG C.
In the inventive method step (c), the Hydrobon catalyst that second catalyzer of answering district to use is routine, business hydrogenation catalyst mainly contains, as hydrogenation catalysts such as 481-3, FDS-4A, FH-40A, FH-40B, FH-40C that Fushun Petrochemical Research Institute (FRIPP) develops, the hydrogenation catalysts such as TK-527, TK-561, TK-568 of Topsor company, KF-840, KF-842 of AKZO company, HR-416, HR-448 of Inst Francais Du Petrole, HR-416, HR-448 of Inst Francais Du Petrole.
In the inventive method step (c), the Hydroprocessing conditions of the 3rd reaction zone is generally reaction pressure 1.0MPa ~ 20.0MPa, comparatively the low 0MPa ~ 2.0MPa of second reaction zone reaction pressure, and hydrogen to oil volume ratio is 200:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, average reaction temperature 130 DEG C ~ 420 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2000:1, volume space velocity 0.4h
-1~ 8.0h
-1, average reaction temperature 150 DEG C ~ 400 DEG C.
In the inventive method step (c), the catalyst for hydro-upgrading of the 3rd reaction zone has isomery function and cracking function, the components such as beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve can be contained, described molecular sieve weight content is in the catalyst generally 3% ~ 30%, is preferably 5% ~ 20%.The hydrogenation active metals component of catalyst for hydro-upgrading (in W, Mo, Ni and Co one or more) is generally 10% ~ 40% with the weight content of oxide basis.The commercial catalysts that second segment reaction zone uses mainly contains, as FC-14, FC-16, FC-20 etc. that Fushun Petrochemical Research Institute (FRIPP) develops.
In the inventive method, three reaction zones can use independent recycle hydrogen system, also can common recycle hydrogen system, also can any two reaction zone common recycle hydrogen systems.Preferably the first reaction zone uses independent recycle hydrogen system.
In the inventive method, Hydrobon catalyst can be supplemented in right amount, by material hydrogenation such as issuable a small amount of alkene in hydro-upgrading process finally arranging of the 3rd reaction zone catalyst for hydro-upgrading bed.
In the inventive method, the 3rd reaction zone uses suitable catalyzer and operational condition, can obtain high-quality kerosene fuel product.Can by conditions such as the temperature of reaction of adjustment the 3rd reaction zone, the yield of adjustment kerosene(oil)fraction, in general, temperature of reaction raises, and the cracking performance of modifying catalyst improves, and the amount that bio-oil is cracked into kerosene increases.Also the internal circulating load of tail oil can be adjusted as required, further the productive rate of adjustment kerosene.Tail oil circulation can be circulated to arbitrary reaction zone, is preferably looped to the 3rd reaction zone.
In prior art, bio-oil hydrogenation produces the method for automotive fuel, the petroleum fractions hybrid process of general needs and larger proportion, otherwise can not running period be ensured, or directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity, can not long-term operation.The present invention is by optimizing the grating technology and operational condition that use catalyzer, first reaction zone hydrofining (hydrogenation catalyst of grating and suitable processing condition), second reaction zone diesel oil hydrofining, 3rd reaction zone hydro-upgrading pour point depression, can directly with bio-oil and kerosene for raw material production high-quality burning oil product, solving bio-oil hydrogenation unit can not the problem of long period steady running.And the weighted BMO spaces of routine does not still reach required stability, conventional weighted BMO spaces generally can realize the running period of 500 hours, the use properties of catalyzer obviously declines, and uses reacting system pressure during fixed bed to fall obvious rising, needs more catalyst changeout.And the present invention program, in steady running after 1000 hours, the Pressure Drop of catalyst performance and reactive system does not all have considerable change, and according to this trend, estimating completely can steady running 1 ~ 3 year.
Accompanying drawing explanation
Fig. 1 is the combined method principle flow chart that hydrogenation method of the present invention produces high-quality burning oil.
Embodiment
Method of the present invention is specific as follows: with the mixing oil of one or more in bio-oil for stock oil, under Hydroprocessing conditions, stock oil and hydrogen are by comprising the first reaction zone of at least two kinds of hydrogenation catalysts, the hydrotreatment obtained generates logistics and is separated the gas circulation use obtained in high-pressure separator, also system can be gone out, the liquid distillate obtained; The liquid distillate of the first reaction zone, diesel raw material and hydrogen are mixed into and comprise hydrorefined second reaction zone, the hydrofining obtained generates logistics and continues through the 3rd reaction zone comprising and have isomery performance catalyst for hydro-upgrading, the hydro-upgrading obtained generates logistics in high-pressure separator, is separated the gas circulation use obtained, also can go out system, liquid fractionation obtains following products: one or more in gas, petroleum naphtha, kerosene.The bio-oil that embodiment uses is commercially available prod, uses front filtering solid impurity.
Particular case of the present invention is further illustrated below by embodiment.
The main composition of table 1 hydrogenation catalyst and character.
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 3 | Catalyst for refining | Modifying catalyst |
| Catalyzer forms | |||||
| Pt，wt% | 0.4 | 0.05 | 1.2 | ||
| Pd，wt% | 0.1 | 0.1 | |||
| MoO 3，wt% | 15.0 | 20.5 | |||
| NiO，wt% | 3.5 | 3.9 | |||
| Beta-molecular sieve, wt% | 8.0 | ||||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| The main character of catalyzer | |||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | 0.33 | 0.36 | >0.34 |
The main character of table 2 diesel raw material oil.
| Catalyzer | Virgin kerosene | Mixing kerosene |
| Density, g/cm 3 | 0.799 | 0.842 |
| Cut scope, DEG C | 130~230 | 150~270 |
| Sulphur content, μ g/g | 1100 | 900 |
| Nitrogen content, μ g/g | 15 | 120 |
| Smoke point, mm | 24 | 18 |
Table 3 embodiment processing condition and test-results.
| First reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Rapeseed oil | Plam oil |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 2 | Catalyzer 2/ catalyzer 1 | Catalyzer 1 | Catalyzer 2/ catalyzer 1 |
| Catalyst volume ratio | 100 | 30:70 | 100 | 20:80 |
| Reaction pressure, MPa | 10.0 | 8.0 | 15.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 1500:1 | 800:1 | 600:1 | 1000:1 |
| Volume space velocity, h -1 | 3.5 | 2.0 | 0.5 | 1.0 |
| Average reaction temperature, DEG C | 220 | 255 | 180 | 200 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 | Catalyzer 3 |
| Reaction pressure, MPa | 10.0 | 8.0 | 15.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 1500:1 | 800:1 | 600:1 | 1000:1 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 4.0 | 1.5 |
| Average reaction temperature, DEG C | 350 | 350 | 380 | 345 |
| Stock oil | First reaction zone liquid and virgin kerosene volume ratio 60:40 | First reaction zone liquid and virgin kerosene volume ratio 50:50 | First reaction zone liquid and virgin kerosene volume ratio 60:40 | First reaction zone liquid and virgin kerosene volume ratio 30:70 |
| Second reaction zone processing condition | ||||
| Catalyzer | Catalyst for refining | Catalyst for refining | Catalyst for refining | Catalyst for refining |
| Stock oil | Virgin kerosene | Virgin kerosene | Mixing kerosene | Mixing kerosene |
| Reaction pressure, MPa | 3.0 | 12.0 | 8.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 200:1 | 500:1 | 800:1 | 500:1 |
| Volume space velocity, h -1 | 1.0 | 2.0 | 3.5 | 6.0 |
| Average reaction temperature, DEG C | 270 | 310 | 32 | 340 |
| 3rd reaction zone processing condition | ||||
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 3.0 | 12.0 | 8.0 | 6.0 |
| Entrance hydrogen to oil volume ratio | 300:1 | 1000:1 | 1000:1 | 600:1 |
| Volume space velocity, h -1 | 2.0 | 1.0 | 1.5 | 4.0 |
| Average reaction temperature, DEG C | 280 | 300 | 290 | 320 |
| Kerosene fuel product | ||||
| Density, g/cm 3 | 0.791 | 0.793 | 0.822 | 0.813 |
| Sulphur content, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Smoke point, mm | 30 | 29 | 25 | 26 |
Table 4 embodiment processing condition and test-results.
| First reaction zone processing condition | Embodiment 5 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Soybean oil | Soybean oil/mixing kerosene | Soybean oil/mixing kerosene | Soybean oil/mixing kerosene |
| Stock oil ratio | 100 | 50:50 | 50:50 | 50:50 |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 2 | Catalyzer 3/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyst for refining/modifying catalyst |
| Catalyst volume ratio | 100 | 33:33:33 | 33:33:33 | 33:33:33 |
| Reaction pressure, MPa | 8.0 | 8.0 | 8.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 1000:1 | 1000:1 | 1000:1 |
| Volume space velocity, h -1 | 2.0 | 0.68 | 0.68 | 0.68 |
| Average reaction temperature, DEG C | 220 | 350 | 370 | 380 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | |||
| Reaction pressure, MPa | 8.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 2.0 | |||
| Average reaction temperature, DEG C | 350 | |||
| Stock oil | First reaction zone liquid compares 50:50 with Mixture Density Networks oil volume | |||
| Second reaction zone processing condition | ||||
| Catalyzer | Catalyst for refining | |||
| Stock oil | Virgin kerosene | |||
| Reaction pressure, MPa | 8.0 | |||
| Entrance hydrogen to oil volume ratio | 500:1 | |||
| Volume space velocity, h -1 | 2.0 | |||
| Average reaction temperature, DEG C | 260 | |||
| 3rd reaction zone processing condition | ||||
| Catalyzer | Modifying catalyst | |||
| Reaction pressure, MPa | 8.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 2.0 | |||
| Average reaction temperature, DEG C | 350 | |||
| Runtime, h | 1000 | 100 | 300 | 600 |
| Total pressure drop, MPa | 0.04 | 0.04 | 0.16 | 0.30 |
| Kerosene fuel product | ||||
| Density, g/cm 3 | 0.795 | 0.795 | 0.816 | 0.835 |
| Sulphur content, μ g/g | <0.5 | <0.5 | 50 | 630 |
| Smoke point, mm | 29 | 29 | 26 | 23 |
As can be seen from embodiment, bio-oil and kerosene feedstock oil can produce high-quality burning oil product by the method for hydrotreating of this technology, or high-quality burning oil blend component, and can long-period stable operation be realized, operate after 1000 hours, reactive system pressure drop is not risen substantially, and on catalyzer, carbon deposition quantity only has about 3.2wt%, belong to balance carbon deposition quantity, do not affect catalyzer use properties.
Claims (12)
1. hydrogenation method produces a combined method for high-quality burning oil, it is characterized in that comprising following content:
A one or more in () bio-oil are the first stock oil, one or more of virgin kerosene or secondary processing kerosene(oil)fraction are the second stock oil;
B () is under hydroprocessing operations condition, the first stock oil is by the first reaction zone of at least two hydrogenators, hydrogenation catalyst is loaded in hydrogenator, bio-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 Pt and/or Pd of reduction-state, first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, gas-phase dehydration process Posterior circle uses, wherein, in the hydrogenator of the cold operation that first reaction mass passes through, the active ingredient of the hydrogenation catalyst used is in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.01% ~ 0.50%, 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 is in the element quality of precious metals pt and/or Pd, the content of noble metal hydrogenation active ingredient is 0.10% ~ 3.50%, in the hydrogenator of high-temperature operation, the active component content of catalyzer is in element quality, higher than the catalyzer in cold operation hydrogenator 0.1 ~ 3 percentage point,
C () is under hydrofining operational condition, step (b) is separated and obtains the second reaction zone that liquid and the second stock oil pass through to load Hydrobon catalyst under hydroconversion condition, under hydroconversion condition, then continue to enter the 3rd reaction zone at least comprising catalyst for hydro-upgrading;
(d) the 3rd the gas phase of reaction zone reaction effluent recycle, the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and is obtained petroleum naphtha and high-quality burning oil cut.
2. in accordance with the method for claim 1, it is characterized in that: in step (a), the bio-oil of use comprises vegetables oil or animal grease.
3. in accordance with the method for claim 1, it is characterized in that: in step (a), the virgin kerosene used comprises the kerosene(oil)fraction that atmospheric and vacuum distillation of petroleum obtains, secondary processing kerosene(oil)fraction comprises the kerosene(oil)fraction that hydrocracking, catalytic cracking, catalytically cracked material weighted BMO spaces, coking, viscosity breaking or thermal cracker are produced, or the kerosene(oil)fraction of coal tar.
4. in accordance with the method for claim 1, it is characterized in that: in step (b), in the first reaction zone, be prohibited from entering the material of sulfur-bearing, nitrogenous impurity.
5. 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 hydrogenator of cold operation, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 6.0h
-1, average reaction temperature 120 DEG C ~ 280 DEG C; The operational condition of the hydrogenator of high-temperature operation is reaction pressure 3.0MPa ~ 20.0MPa, hydrogen to oil volume ratio 200:1 ~ 3000:1, volume space velocity 0.5h
-1~ 6.0h
-1, average reaction temperature is higher than the hydrogenator of cold operation 50 DEG C ~ 300 DEG C.
6. in accordance with the method for claim 1, it is characterized in that: step by step in rapid (b), the average reaction temperature of the hydrogenator of high-temperature operation is higher than the hydrogenator of cold operation 80 ~ 220 DEG C.
7. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second reaction zone is 1.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 150:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, average reaction temperature is 130 DEG C ~ 420 DEG C.
8. in accordance with the method for claim 7, it is characterized in that: hydrogen to oil volume ratio is 200:1 ~ 2000:1, volume space velocity is 0.4h
-1~ 8.0h
-1, average reaction temperature is 150 DEG C ~ 400 DEG C.
9. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of the 3rd reaction zone is 1.0MPa ~ 20.0MPa, compared with the low 0MPa ~ 2.0MPa of the reaction pressure of second reaction zone, hydrogen to oil volume ratio is 200:1 ~ 2500:1, and volume space velocity is 0.3h
-1~ 10.0h
-1, average reaction temperature is 130 DEG C ~ 420 DEG C.
10. in accordance with the method for claim 9, it is characterized in that: hydrogen to oil volume ratio is 300:1 ~ 2000:1, volume space velocity is 0.4h
-1~ 8.0h
-1, average reaction temperature is 150 DEG C ~ 400 DEG C.
11. in accordance with the method for claim 1, it is characterized in that: in step (c), containing beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve in the catalyst for hydro-upgrading of the 3rd reaction zone, the hydrogenation active metals component of catalyst for hydro-upgrading with the weight content of oxide basis for 10% ~ 40%.
12. in accordance with the method for claim 1, it is characterized in that: it is characterized in that in step (a), and the volume ratio of the first stock oil and the second stock oil is 10:90 ~ 90:10.
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| WO2011112660A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
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| EP1693432B1 (en) * | 2005-02-18 | 2009-09-30 | Petroleo Brasileiro S.A. - Petrobras | Vegetable oil hydroconversion process |
| CN101321847A (en) * | 2005-11-30 | 2008-12-10 | 新日本石油株式会社 | Hydrorefining process and hydrorefined oil |
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
| WO2011112660A2 (en) * | 2010-03-09 | 2011-09-15 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
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