CN103374410B - Hydrogenation method for producing high-quality kerosene - Google Patents
Hydrogenation method for producing high-quality kerosene Download PDFInfo
- Publication number
- CN103374410B CN103374410B CN201210130687.1A CN201210130687A CN103374410B CN 103374410 B CN103374410 B CN 103374410B CN 201210130687 A CN201210130687 A CN 201210130687A CN 103374410 B CN103374410 B CN 103374410B
- Authority
- CN
- China
- Prior art keywords
- oil
- reaction zone
- reaction
- kerosene
- hydrogenator
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a hydrogenation method for producing high-quality kerosene. The hydrogenation method comprises the steps that firstly, under the condition of hydrogenation, biolipid and recycle hydrogen are mixed and pass through a hydrotreating reaction zone, the gas obtained by separating a hydrotreating generated material flow is recycled, the liquid obtained by separation, the raw kerosene and the recycle hydrogen are mixed and pass through a hydrofining reaction zone and then enter a hydro-upgrading reaction zone at least comprising hydrogenation catalysts with isomerization performance, and the liquid obtained by separating a hydro-upgrading generated material flow is continuously fractionated, thus obtaining naphtha and kerosene products, wherein in the reaction state, the hydrogenation active components of the hydrogenation catalysts used in the hydrotreating reaction zone are one or more of W, Mo, Ni and Co in the reduction state. Compared with the prior art, the method has the advantages that not only can the storage stability of the biolipid as fuel oil be effectively improved but also the high-quality kerosene can be directly produced.
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 method for hydrotreating 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.
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.
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 kerosene fuel product under the condition of hydrogenation, has hydrogenation process and stablizes, the features such as running period is long.
A kind of method of hydrotreating producing high-quality burning oil of the present invention, 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 one or more in W, Mo, Ni and Co of reduction-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 hydroisomerizing condition, then continue to enter the 3rd reaction zone at least comprising hydroisomerizing performance catalyzer;
(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 product 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 the bio-oil of C12 ~ C16, 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 etc. 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 ~ 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 first by the hydrogenator of cold operation, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%.Multiple catalysts grating can be used in the hydrogenator of cold operation to use.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 3 ~ 25 percentage points.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent, as P, Si, B, Ti, Zr etc. simultaneously.Can commercial catalyst be adopted, also can by the existing method preparation in this area.The business hydrogenation catalyst that first reaction zone uses mainly contains, as Fushun Petrochemical Research Institute (FRIPP) develop 3926, 3936, CH-20, FF-14, FF-18, FF-24, FF-26, FF-36, FH-98, FH-UDS, the hydrogenation catalysts such as FZC-41, the HR-416 of Inst Francais Du Petrole, the hydrogenation catalysts such as HR-448, the ICR174 of CLG company, ICR178, the hydrogenation catalysts such as ICR179, Uop Inc. is newly developed HC-P, HC-K UF-210/220, the TK-525 of Topsor company, TK-555, the hydrogenation catalysts such as TK-557, the KF-752 of AKZO company, KF-840, KF-848, KF-901, the hydrogenation catalysts such as KF-907.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, as containing components such as beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieves, 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 is used alone 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.
Accompanying drawing explanation
Fig. 1 is the method for hydrotreating principle flow chart that 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 | |||||
| MoO 3，wt% | 8.5 | 5.0 | 23.0 | 16.0 | 18.5 |
| NiO，wt% | 2.5 | 4.5 | 3.2 | 3.9 | |
| CoO，wt% | 1.8 | ||||
| Beta-molecular sieve, wt% | 5.9 | ||||
| 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 kerosene feedstock oil.
| Catalyzer | Virgin kerosene | Mixing kerosene |
| Density, g/cm 3 | 0.802 | 0.837 |
| Cut scope, DEG C | 130~240 | 140~260 |
| Sulphur content, μ g/g | 1200 | 600 |
| Nitrogen content, μ g/g | 13 | 80 |
| Smoke point, mm | 23 | 21 |
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 |
| Catalyst volume ratio | 100 | 30:70 | 100 | 100 |
| Reaction pressure, MPa | 15.0 | 6.0 | 10.0 | 8.0 |
| 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 1/ catalyzer 3 |
| Catalyst volume ratio | 100 | 100 | 100 | 20:80 |
| Reaction pressure, MPa | 15.0 | 6.0 | 10.0 | 8.0 |
| 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 | Two reaction liquid phases produce volume ratio 60:40 | Two reaction liquid phases produce volume ratio 50:50 | Two reaction liquid phases produce volume ratio 60:40 | Two reaction liquid phases produce 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 | 12.0 | 3.0 | 6.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 500:1 | 200:1 | 500:1 | 800:1 |
| Volume space velocity, h -1 | 2.0 | 1.0 | 6.0 | 3.5 |
| Average reaction temperature, DEG C | 310 | 270 | 340 | 32 |
| 3rd reaction zone processing condition | ||||
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 12.0 | 3.0 | 6.0 | 8.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 300:1 | 600:1 | 1000:1 |
| Volume space velocity, h -1 | 1.0 | 2.0 | 4.0 | 1.5 |
| Average reaction temperature, DEG C | 300 | 280 | 320 | 290 |
| Kerosene fuel product | ||||
| Density, g/cm 3 | 0.795 | 0.798 | 0.816 | 0.821 |
| Sulphur content, μ g/g | <0.5 | <0.5 | <0.5 | <0.5 |
| Smoke point, mm | 29 | 28 | 26 | 25 |
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 | Plam oil | Plam oil/mixing kerosene | Plam oil/mixing kerosene | Plam oil/mixing kerosene |
| Stock oil ratio | 100 | 50:50 | 50:50 | 50:50 |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 2/ catalyzer 3 | Catalyzer 3/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyst for refining/modifying catalyst |
| Catalyst volume ratio | 30:70 | 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 | 360 | 370 | 380 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 3 | |||
| Catalyst volume ratio | 100 | |||
| 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 | Two reaction liquid phases produce volume ratio 50:50 | |||
| 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 | 280 | |||
| 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 | 300 | |||
| 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 | 0.821 |
| Sulphur content, μ g/g | <0.5 | <0.5 | 52 | 530 |
| Smoke point, mm | 29 | 29 | 26 | 25 |
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. produce a method of hydrotreating 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 the W of reduction-state, Mo, one or more in Ni and Co, 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, hydrogenation active component with the weight content of oxide basis for 3% ~ 10%, 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 3 ~ 25 percentage points,
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 product 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 hydrotreating reactor 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), the catalyst for hydro-upgrading of the 3rd reaction zone contains beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve, 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210130687.1A CN103374410B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation method for producing high-quality kerosene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210130687.1A CN103374410B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation method for producing high-quality kerosene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103374410A CN103374410A (en) | 2013-10-30 |
| CN103374410B true CN103374410B (en) | 2015-07-22 |
Family
ID=49460257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210130687.1A Active CN103374410B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation method for producing high-quality kerosene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103374410B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2011224482B2 (en) * | 2010-03-09 | 2016-02-11 | Exxonmobil Research And Engineering Company | Dewaxing of renewable diesel fuel |
-
2012
- 2012-04-29 CN CN201210130687.1A patent/CN103374410B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617029A (en) * | 2007-02-20 | 2009-12-30 | 国际壳牌研究有限公司 | Produce the method for paraffinic hydrocarbons |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103374410A (en) | 2013-10-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103374403B (en) | Hydrogenation combination method for producing low-condensation-point diesel oil | |
| CN103374401B (en) | A kind of method of hydrotreating producing high-quality burning oil | |
| CN103374397B (en) | Hydrogenation combination method for producing low-condensation-point diesel oil | |
| CN103374396B (en) | Hydrogenation combination method for producing low-condensation-point diesel oil | |
| CN103374404B (en) | Hydrogenation combination method for producing high-quality diesel oil | |
| CN103374410B (en) | Hydrogenation method for producing high-quality kerosene | |
| CN103374398B (en) | Hydrogenation method for producing high-quality low-condensation-point diesel oil | |
| CN103374399B (en) | Produce the combined hydrogenation method of high-grade low-freezing point diesel oil | |
| CN103374400B (en) | Hydrogenation method produces the combined method of high-quality burning oil | |
| CN103374405B (en) | A kind of bio-oil produces the combined hydrogenation method of high-grade low-freezing point diesel oil | |
| CN103374408B (en) | Produce the method for hydrotreating of low freezing point diesel fuel | |
| CN103374379B (en) | Produce the method for hydrotreating of fine-quality diesel oil | |
| CN103102959B (en) | Residual oil hydrogenation method for high quality diesel oil yield increase | |
| CN103374409B (en) | Produce the combined hydrogenation method of high-quality burning oil | |
| CN103374412B (en) | Combination method for producing high-quality kerosene through hydrogenation | |
| CN103102902B (en) | Hydrocracking method for producing low aromatic hydrocarbon solvent oil from biological oil | |
| CN103374407B (en) | A kind of method of hydrotreating producing low freezing point diesel fuel | |
| CN103374413B (en) | Hydrogenation combination method for producing high-quality kerosene | |
| CN103102958B (en) | Residual oil hydrogenation method for high quality diesel oil yield increase | |
| CN103374406B (en) | Hydrogenation method for producing high-quality diesel oil | |
| CN103102900B (en) | Hydrogenation method for producing high quality solvent oil from biological oil | |
| CN103374378B (en) | A kind of method of hydrotreating producing high-grade low-freezing point diesel oil | |
| CN103102925B (en) | Hydrogenation method for producing high quality low freezing point motor fuel from biological oil | |
| CN103102914B (en) | Wax oil hydrotreating method for high quality diesel oil yield increase | |
| CN103102960B (en) | Residue oil hydrogenation method for diesel oil by-production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |