CN103374403B - Hydrogenation combination method for producing low-condensation-point diesel oil - Google Patents
Hydrogenation combination method for producing low-condensation-point diesel oil Download PDFInfo
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Abstract
The invention relates to a hydrogenation combination method for producing low-condensation-point diesel oil. The hydrogenation combination 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 raw diesel oil and the recycle hydrogen are mixed and pass through a hydrofining reaction zone, the liquid obtained by separating a hydrotreating generated material flow and the liquid obtained by separating a hydrofining product are mixed 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 high-quality low-condensation-point diesel oil products, wherein in the reaction state, the hydrogenation active components of the hydrogenation catalysts used in the hydrotreating reaction zone are Pt and/or Pd 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 low-condensation-point clean diesel oil 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 diesel oil distillate for stock oil, the combined hydrogenation method of direct production low freezing point diesel fuel.
Background technology
The energy in current global range is mainly derived from fossil energy, comprise coal and oil, and its PetroChina Company Limited. is the main source of automotive fuel.Oil belongs to Nonrenewable energy resources, and not only resource is day by day exhausted, and heaviness and in poor quality degree aggravation.Along with sustained economic development, the environmental regulation increasingly stringent in the world, various countries are very vigorous to the demand of light clean fuel, these increase new oil substitutes while all requiring to improve existing oil Refining Technologies, and produce satisfactory product with minimum cost, the especially development and utilization of renewable resources.
Bio-oil derives from plant, animal or microorganism etc., and be renewable resources, its comprehensive utilization obtains worldwide extensive attention, and each research unit and energy company are all being devoted to take it as the research of raw material production cleaning product.The method production biofuel (being generally fatty acid methyl ester) utilizing transesterify has been proven technique, 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 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, 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.Simultaneously when producing low freezing point diesel fuel cut also because catalyst activity is affected the shortcomings such as the running period that causes is short.
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 hydrotreatment (hydrogenation catalyst of grating and the operational condition of optimization), second reaction zone diesel oil hydrofining, 3rd reaction zone hydro-upgrading pour point depression, can directly with bio-oil and diesel oil for raw material production high-grade low-freezing point diesel product, solving bio-oil hydrogenation unit can not the problem of long period steady running, significantly can reduce the condensation point of diesel oil distillate simultaneously.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 combined hydrogenation method producing low freezing point diesel fuel, with bio-oil and diesel oil distillate for stock oil, the diesel product of direct production high-quality super low sulfur, low condensation point under the condition of combined hydrogenation, there is hydrogenation process stablize, the features such as running period is long.
The combined hydrogenation method that the present invention produces low freezing point diesel fuel comprises following content:
A one or more in () bio-oil are the first stock oil, one or more of straight-run diesel oil or secondary processing diesel oil cut 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, and gas-phase dehydration process Posterior circle uses;
C (), under hydrofining operational condition, the second stock oil is by the second reaction zone of filling Hydrobon catalyst under hydroconversion condition, and second reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas phase recycles;
(d) first reaction zone hydrogenation effluent be separated the liquid phase obtained and be separated with second reaction zone hydrogenation effluent after the liquid-phase mixing obtained under hydroisomerizing condition by least comprising the 3rd reaction zone of hydroisomerization catalyst;
(e) 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 super low sulfur, low freezing point diesel fuel product cut.
In the inventive method step (a), the bio-oil used can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and rice bran wet goods, one or more during animal grease comprises butter, lard, sheep oil, fish oil and roasts grease that other animals obtain etc.
In the inventive method step (a), straight-run diesel oil is generally the diesel oil distillate that Atmospheric vacuum fractionation obtains, the straight-run diesel oil of preferred intermediate base crude oil and naphthenic base crude.Secondary processing diesel oil is generally secondary petroleum refining process, as the diesel oil distillate that the technological processs such as hydrocracking, catalytic cracking, hydrotreatment, coking, thermally splitting, viscosity breaking, ethene obtain, and coal tar diesel oil distillate.
In the inventive method step (a), the volume ratio of the first stock oil and the second stock oil is 1:99 ~ 99:1, is preferably 5:95 ~ 95:5, is preferably 10:90 ~ 90:10.
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 5.0MPa ~ 15.0MPa, 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 5.0MPa ~ 15.0MPa, 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 hydrotreating reactor 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.Catalyzer in first reaction zone carries out conventional reduction treatment before use.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 2.0MPa ~ 20.0MPa, is preferably 5.0MPa ~ 15.0MPa, can be identical with the first reaction zone, also can not be identical, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
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 the FH-5 that Fushun Petrochemical Research Institute (FRIPP) develops, FH-5A, FH-98, FH-DS, FH-UDS series waits hydrogenation catalyst, the HR-416 of Inst Francais Du Petrole, HR-448, HR-548, the hydrogenation catalysts such as HR-568, the ICR174 of CLG company, ICR178, ICR179, the hydrogenation catalysts such as ICR417, the HC-P of Uop Inc.'s exploitation, HC-K, the catalyzer such as UF-210, the TK-525 of Topsor company, TK-559, TK-574, TK-576, TK-607, TK-907, the hydrogenation catalysts such as TK-911, the KF-756 of AKZO company, KF-757, KF-840, the hydrogenation catalysts such as KF-848, the DN2531 of Criterion company, the hydrogenation catalysts such as DN3330 and DN2318.
In the inventive method step (d), the Hydroprocessing conditions of the 3rd reaction zone is generally reaction pressure 2.0MPa ~ 20.0MPa, be preferably 5.0MPa ~ 15.0MPa, can be identical with the first reaction zone, can be identical with second reaction zone, also can not be identical with first, second reaction zone, hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature 180 DEG C ~ 465 DEG C; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, average reaction temperature 200 DEG C ~ 445 DEG C.
In the inventive method step (d), the hydroisomerization catalyst (or claiming catalyst for hydro-upgrading) of the 3rd reaction zone, 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 3rd 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, because the reduction-state catalyzer used in the first reaction zone need use under without sulphur condition.Second reaction zone and the 3rd reaction zone use conventional sulphided state catalyzer.
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.
Accompanying drawing explanation
Fig. 1 is the combined hydrogenation method principle flow chart that the present invention produces low freezing point diesel fuel.
Fig. 2 is another principle flow chart of combined hydrogenation method that the present invention produces low freezing point diesel fuel.Be that second reaction zone and the 3rd reaction zone use independently recycle hydrogen system separately with the difference of Fig. 1.
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 the first reaction zone of the reactor of the reactor and high-temperature operation that comprise cold operation, 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; Diesel raw material and hydrogen are mixed into and comprise hydrorefined second reaction zone, and the hydrofining obtained generates logistics and is separated the gas circulation use obtained in high-pressure separator, also can go out system, the liquid distillate obtained; The liquid distillate of the first reaction zone mix with the liquid distillate of second reaction zone after and hydrogen by comprising the 3rd reaction zone with 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, low freezing point diesel fuel.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.Wherein modifying catalyst contains beta-molecular sieve, and this catalyzer has isomery function.
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 | 1.2 | 0.05 | ||
| Pd，wt% | 0.1 | 0.1 | |||
| MoO 3，wt% | 20.7 | 20.5 | |||
| NiO，wt% | 3.6 | 4.6 | |||
| Beta-molecular sieve, wt% | 6.9 | ||||
| Alumina supporter, wt% | Surplus | Surplus | Surplus | Surplus | Surplus |
| The leading indicator of catalyzer | |||||
| Specific surface, m 2/g | >160 | >160 | >160 | >160 | >160 |
| Pore volume, ml/g | >0.30 | >0.30 | 0.33 | 0.32 | >0.34 |
The main character of table 2 diesel raw material oil.
| Catalyzer | Catalytic diesel oil | Medium diesel oil |
| Density, g/cm 3 | 0.945 | 0.878 |
| Cut scope, DEG C | 155~375 | 160~365 |
| Sulphur content, wt% | 2.0 | 1.2 |
| Nitrogen content, μ g/g | 1020 | 600 |
| Condensation point, DEG C | 5 | 13 |
| Cetane value | 18 | 38 |
Table 3 embodiment processing condition and test-results.
| First reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Plam oil |
| Cold operation reactor | |||
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3/ catalyzer 1 |
| Catalyst volume ratio | 100 | 100 | 30:70 |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 400:1 | 1500:1 |
| Volume space velocity, h -1 | 2.0 | 1.5 | 1.0 |
| Average reaction temperature, DEG C | 130 | 180 | 260 |
| High-temperature operation reactor | |||
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 2 |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 2000:1 | 400:1 | 1500:1 |
| Volume space velocity, h -1 | 0.4 | 1.3 | 0.6 |
| Average reaction temperature, DEG C | 280 | 350 | 300 |
| Second reaction zone processing condition | |||
| Catalyzer | Catalyst for refining | Catalyst for refining | Refining catalytic 8 doses |
| Stock oil | Catalytic diesel oil | Catalytic diesel oil | Medium diesel oil |
| Reaction pressure, MPa | 13.0 | 8.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 1000:1 | 600:1 | 800:1 |
| Volume space velocity, h -1 | 2.0 | 0.80 | 3.0 |
| Average reaction temperature, DEG C | 360 | 350 | 370 |
| 3rd reaction zone processing condition | |||
| Stock oil | Two reaction liquid phases produce volume ratio 50:50 | Two reaction liquid phases produce volume ratio 30:70 | Two reaction liquid phases produce volume ratio 60:40 |
| Catalyzer | Modifying catalyst | Modifying catalyst | Modifying catalyst |
| Reaction pressure, MPa | 13.0 | 12.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 1500:1 | 900:1 | 1100:1 |
| Volume space velocity, h -1 | 1.0 | 1.5 | 2.5 |
| Average reaction temperature, DEG C | 350 | 360 | 340 |
| Diesel product | |||
| Density, g/cm 3 | 0.835 | 0.843 | 0.821 |
| Sulphur content, μ g/g | <5 | <5 | <5 |
| Condensation point, DEG C | -20 | -30 | -25 |
| Cetane value | 55 | 52 | 64 |
Table 4 embodiment processing condition and test-results.
| First reaction zone processing condition | Embodiment 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Stock oil | Rapeseed oil | Rapeseed oil/catalytic diesel oil | Rapeseed oil/catalytic diesel oil | Rapeseed oil/catalytic diesel oil |
| Stock oil ratio | 100 | 40:60 | 40:60 | 40:60 |
| Cold operation reactor | ||||
| Catalyzer | Catalyzer 3/ catalyzer 1 | Catalyzer 3/ catalyzer 1/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyzer 1/ catalyst for refining/modifying catalyst | Catalyzer 3/ catalyzer 1/ catalyst for refining/modifying catalyst |
| Catalyst volume ratio | 40:60 | 47:24:29 | 47:24:29 | 47:24:29 |
| Reaction pressure, MPa | 10.0 | 10.0 | 10.0 | 10.0 |
| Entrance hydrogen to oil volume ratio | 800:1 | 800:1 | 800:1 | 800:1 |
| Volume space velocity, h -1 | 1.6 | 0.6 | 0.6 | 0.6 |
| Average reaction temperature, DEG C | 180 | 350 | 360 | 380 |
| High-temperature operation reactor | ||||
| Catalyzer | Catalyzer 2 | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 800:1 | |||
| Volume space velocity, h -1 | 1.6 | |||
| Average reaction temperature, DEG C | 300 | |||
| Second reaction zone processing condition | ||||
| Catalyzer | Catalyst for refining | |||
| Stock oil | Catalytic diesel oil | |||
| Reaction pressure, MPa | 10.0 | |||
| Entrance hydrogen to oil volume ratio | 1000:1 | |||
| Volume space velocity, h -1 | 1.5 | |||
| Average reaction temperature, DEG C | 350 | |||
| 3rd reaction zone processing condition | — | — | — | |
| Catalyzer | Modifying catalyst | |||
| Stock oil | Two reaction liquid phases produce volume ratio 40:60 | |||
| Reaction pressure, MPa | 10.0 | |||
| 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 | 400 | 800 |
| Total pressure drop, MPa | 0.08 | 0.08 | 0.15 | 0.28 |
| Diesel product | ||||
| Density, g/cm 3 | 0.842 | 0.842 | 0.874 | 0.92 |
| Sulphur content, μ g/g | <5 | <5 | 50 | 450 |
| Condensation point, DEG C | -25 | -25 | -10 | 5 |
| Cetane value | 53 | 53 | 46 | 38 |
As can be seen from embodiment, bio-oil and diesel raw material oil can produce high-grade low-freezing point diesel product by the combined hydrogenation method of this technology, or high-grade low-freezing point diesel oil blending 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 3.5wt%, belong to balance carbon deposition quantity, do not affect catalyzer use properties.
Claims (11)
1. produce a combined hydrogenation method for low freezing point diesel fuel, it is characterized in that comprising following content:
A one or more in () bio-oil are the first stock oil, one or more of straight-run diesel oil or secondary processing diesel oil cut 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, the hydrogenator average reaction temperature of cold operation 120 DEG C ~ 280 DEG C, the average reaction temperature of the hydrogenator of high-temperature operation is higher than the hydrogenator of cold operation 80 ~ 220 DEG C; Under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or Pd of reduction-state, and the first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration process Posterior circle uses;
C (), under hydrofining operational condition, the second stock oil is by the second reaction zone of filling Hydrobon catalyst under hydroconversion condition, and second reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas phase recycles;
(d) first reaction zone hydrogenation effluent be separated the liquid phase obtained and be separated with second reaction zone hydrogenation effluent after the liquid-phase mixing obtained under hydroisomerizing condition by least comprising the 3rd reaction zone of hydroisomerization catalyst;
(e) 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 super low sulfur, low freezing point diesel fuel product cut;
In step (b), in the hydrogenator of the cold operation that first reaction mass passes through, 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%.
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 straight-run diesel oil used comprises the diesel oil distillate that atmospheric and vacuum distillation of petroleum obtains, secondary processing diesel oil is generally the diesel oil distillate that the hydrocracking of secondary petroleum refining process, catalytic cracking, hydrotreatment, coking, thermally splitting, viscosity breaking or ethylene process process obtain, or is coal tar diesel oil distillate.
4. 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; 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.
5. in accordance with the method for claim 1, it is characterized in that: 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.
6. in accordance with the method for claim 1, it is characterized in that: in step (c), the reaction pressure of second reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is 180 DEG C ~ 465 DEG C.
7. in accordance with the method for claim 6, it is characterized in that: in step (c), the hydrogen to oil volume ratio of second reaction zone is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 5.0h
-1, average reaction temperature is 200 DEG C ~ 445 DEG C.
8. in accordance with the method for claim 1, it is characterized in that: in step (d), the reaction pressure of the 3rd reaction zone is 3.0MPa ~ 20.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.3h
-1~ 6.0h
-1, average reaction temperature is 180 DEG C ~ 465 DEG C.
9. in accordance with the method for claim 8, it is characterized in that: in step (d), the hydrogen to oil volume ratio of the 3rd reaction zone 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.
10. in accordance with the method for claim 1, it is characterized in that: in step (d), containing beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve in the hydroisomerization catalyst of the 3rd reaction zone, hydrogenation active metals component wherein with the weight content of oxide basis for 10% ~ 40%.
11. 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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| CN111349523B (en) * | 2018-12-21 | 2022-03-08 | 中国石油化工股份有限公司 | Low-freezing-point biodiesel and preparation method thereof |
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