CN103374403A - 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 take bio-oil and diesel oil distillate as stock oil, the combined hydrogenation method of direct production low freezing point diesel fuel.
Background technology
The energy in the global range is mainly derived from fossil energy at present, 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 the aggravation of in poor quality degree.Sustained economic development, environmental regulation increasingly stringent along with the world, various countries are very vigorous to the demand of light clean fuel, when all requiring existing oil Refining Technologies improved, these increase new oil substitutes, and produce satisfactory product, the especially development and utilization of renewable resources with minimum cost.
Bio-oil derives from plant, animal or microorganism etc., is renewable resources, and its comprehensive utilization obtains worldwide extensive attention, and each research unit and energy company all are being devoted to take its research as the raw material production cleaning product.Utilizing the method production biofuel (being generally fatty acid methyl ester) of transesterify has been proven technique, but because oxygen level is high in this class biofuel, although many countries and regions have been put into effect the standard of biofuel successively, can not be applicable to all oil engines.If bio oil, fat are produced automotive fuel by the method for deep hydrogenation, be about to that oxygen is all removed or major part is removed and produced the product that meets the automotive fuel standard, this method can directly satisfy the requirement of existing market.
Existing bio-oil hydrogenation method is produced the processing technology of automotive fuel, US20060186020, EP1693432, CN101321847A, CN200710012090.6, CN200680045053.9, CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and CN101029245A etc. disclose the vegetables oil hydroconversion process, adopt the coker gasoline cut, diesel oil distillate (straight-run diesel oil, LCO and coker gas oil), petroleum hydrocarbon cut and the bio oil such as wax oil cut, fat directly is mixed into hydroconversion reaction zone, under the effect of hydrogen, by beds, produce the raw material of diesel product or preparing ethylene by steam cracking etc.US5705722 discloses vegetables oil such as containing unsaturated fatty acids, fat and animal oil mixing back end hydrogenation is produced the diesel oil blending component of diesel oil distillate scope.
EP1741767 and EP1741768 disclose a kind of method of producing diesel oil distillate with animal-plant oil, be mainly animal-plant oil and at first pass through hydrotreatment, then by the isomerization catalyst bed layer, obtain the low freezing point diesel fuel component, but owing to generate water in the hydrotreatment process, isomerization catalyst is caused very adverse influence, and device can not long-period stable operation.
Comprise in the bio-oil hydrogenation process of aforesaid method that one of subject matter that runs into is that the bed carbon distribution causes that the pressure drop rising makes shorten the more catalyst changeout of need to often stopping work running period.Particularly separately take bio oil, fat as raw material or bio-oil blending ratio when higher, more be subject to obvious impact the running period of hydrogenation catalyst.Carry out conventional raw material according to this area general knowledge and add hydrogen pretreatment (such as the saturated or shallow degree hydrofining of hydrogenation of routine etc.), although prolong to some extent (generally can reach 500 hours) running period, but still can not solve long period steady running problem.Contain multiple different organo-functional group in the bio-oil, the reaction of these organo-functional groups in hydrogenation process is comparatively complicated, influence each other between the different reactions, the major cause that affects bio-oil raw material hydrogenation process stability is still indefinite, and therefore improving run stability is the major issue that this area need to solve.Simultaneously when producing the low freezing point diesel fuel cut also because of the catalyst activity shortcomings such as the running period that causes is short that are affected.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of combined hydrogenation method of producing low freezing point diesel fuel, take bio-oil and diesel oil distillate as stock oil, the diesel product of direct production high-quality super low sulfur, low condensation point under the condition of combined hydrogenation, the characteristics such as it is stable to have hydrogenation process, and 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 the bio-oil are the first stock oil, and one or more of straight-run diesel oil or secondary processing diesel oil cut are the second stock oil;
(b) under the hydrotreatment operational condition, the first stock oil is by the first reaction zone of at least two hydrogenators, load hydrogenation catalyst in the hydrogenator, bio-oil and hydrogen is the hydrogenator by cold operation at first, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or the Pd of reduction-state, the first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration recycles after processing;
(c) under the hydrofining operational condition, by the second reaction zone of filling Hydrobon catalyst, second reaction zone hydrogenation effluent is separated into gas phase and liquid phase to the second stock oil under hydroconversion condition, and gas phase recycles;
(d) after the first reaction zone hydrogenation effluent separates the liquid phase obtain and second reaction zone hydrogenation effluent separates the liquid-phase mixing that obtains under the hydroisomerizing condition by comprising at least the 3rd reaction zone of hydroisomerization catalyst;
(e) gas phase of the 3rd reaction zone reaction effluent recycles, and the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and 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 that uses can comprise vegetables oil or animal grease, vegetables oil comprises one or more in soybean oil, peanut oil, Viscotrol C, rapeseed oil, Semen Maydis oil, sweet oil, plam oil, Oleum Cocois, tung oil, oleum lini, sesame oil, Oleum Gossypii semen, sunflower seed oil and the rice bran wet goods, and animal grease comprises butter, lard, sheep oil, fish oil and roasts in the grease that other animals obtain etc. one or more.
In the inventive method step (a), straight-run diesel oil is generally the diesel oil distillate that normal vacuum fractionation obtains, the straight-run diesel oil of preferred intermediate base crude oil and naphthenic base crude.Secondary processing diesel oil is generally the secondary petroleum refining process, the diesel oil distillate that obtains such as technological processs such as hydrocracking, catalytic cracking, hydrotreatment, coking, thermally splitting, viscosity breaking, ethene, 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 condition of the hydrogenator of cold operation is generally reaction pressure 3.0MPa ~ 20.0MPa, is preferably 5.0MPa ~ 15.0MPa, and hydrogen to oil volume ratio is 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; 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 than the hydrogenator of cold operation high 50 ℃ ~ 300 ℃, preferred high 80 ~ 220 ℃.Between the hydrogenator of cold operation and the hydrogenator of high-temperature operation process furnace or interchanger are set, with the temperature of reaction of the hydrotreating reactor of adjusting high-temperature operation.
At first by in the hydrogenator of cold operation, the active ingredient of the hydrogenation catalyst of use is in the element quality of precious metals pt and/or Pd for bio-oil, and the content of noble metal hydrogenation active ingredient is 0.01%～0.50%.Reaction mass continues the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses in the hydrogenator of high-temperature operation 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%.The active component content of catalyzer is higher than the catalyzer in the cold operation hydrogenator in the hydrogenator of preferred high-temperature operation, preferred high 0.1 ~ 3 percentage point (in the element quality).Reactor generally can arrange 2 ~ 5, is preferably 2.A kind of catalyzer can be loaded in each hydrogenator, also multiple catalysts can be loaded.The carrier of hydrogenation catalyst is generally aluminum oxide, amorphous silicon aluminium, silicon oxide, titanium oxide etc., can contain other auxiliary agent simultaneously, such as P, Si, B, Ti, Zr etc.Can adopt the commercial catalyst, also can be by the existing method preparation in this area.Noble metal catalyst such as Fushun Petrochemical Research Institute (FRIPP) develop the HDO-18 catalyzer, also can be by described method preparations such as CN00123141.3.Catalyzer in the first reaction zone carries out conventional reduction before use to be processed.The catalyzer of other reaction zone carries out conventional sulfidizing before use.The reduction treatment condition are generally 200～400 ℃ of pressure 2～15MPa and temperature, with hydrogen to catalyst reduction 1～15 hour.
In the inventive method step (c), the hydroprocessing condition 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, can be not identical yet, hydrogen to oil volume ratio is 200:1 ~ 3000:1, volume space velocity is 0.3h
-1~ 6.0h
-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, 200 ℃ ~ 445 ℃ of average reaction temperature.
In the inventive method step (c), second should distinguish the catalyzer that uses is the Hydrobon catalyst of routine, commercial hydrogenation catalyst mainly contains, FH-5 such as Fushun Petrochemical Research Institute (FRIPP) development, 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 catalyst such as DN3330 and DN2318.
In the inventive method step (d), the hydroprocessing condition 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, can be not identical with first, second reaction zone yet, hydrogen to oil volume ratio is 200:1 ~ 3000:1, volume space velocity is 0.3h
-1~ 6.0h
-1, 180 ℃ ~ 465 ℃ of average reaction temperature; Preferred operational condition is hydrogen to oil volume ratio 300:1 ~ 2500:1, volume space velocity 0.4h
-1~ 4.0h
-1, 200 ℃ ~ 445 ℃ of average reaction temperature.
In the inventive method step (d), the hydroisomerization catalyst of the 3rd reaction zone (or claiming catalyst for hydro-upgrading), contain the components such as beta-molecular sieve, SAPO-11 molecular sieve, SAPO-41, NU-10 molecular sieve or ZSM-22 molecular sieve, the weight content of described molecular sieve in catalyzer is generally 3%～30%, is preferably 5%～20%.The hydrogenation active metals component of catalyst for hydro-upgrading (one or more among W, Mo, Ni and the Co) is generally 10%～40% in the weight content of oxide compound.The commercial catalysts that the 3rd reaction zone uses mainly contains, FC-14, the FC-16 that develops such as Fushun Petrochemical Research Institute (FRIPP), FC-20 etc.
In the inventive method, three reaction zones can use independent recycle hydrogen system, also can the common recycle hydrogen system, and also can any two reaction zone common recycle hydrogen systems.Preferred the first reaction zone uses separately the recycle hydrogen system, because the reduction-state catalyzer that uses in the first reaction zone needs to use under without the sulphur condition.Second reaction zone and the 3rd reaction zone use conventional sulphided state catalyzer.
In the inventive method, can be at an amount of Hydrobon catalyst that replenishes of arranging at last of the 3rd reaction zone catalyst for hydro-upgrading bed, with material hydrogenation such as issuable a small amount of alkene in the hydro-upgrading process.
The bio-oil hydrogenation is produced the method for automotive fuel in the prior art, generally need to the petroleum fractions hybrid process of larger proportion, otherwise can not guarantee running period, perhaps directly by hydrofining-catalyst for hydro-upgrading bed, the component poor stability of cracking catalyst activity can not long-term operation.The present invention is by optimizing grating technology and the operational condition of using catalyzer, the first reaction zone hydrotreatment (hydrogenation catalyst of grating and the operational condition of optimization), the second reaction zone diesel oil hydrofining, the 3rd reaction zone hydro-upgrading pour point depression, can be directly take bio-oil and diesel oil as raw material production high-grade low-freezing point diesel product, solved the problem that the bio-oil hydrogenation unit can not the long period steady running, condensation point that simultaneously can the decrease diesel oil distillate.And the conventional hydrogen pretreatment that adds does not still reach required stability, the conventional hydrogen pretreatment that adds generally can be realized running period about 500 hours, the use properties of catalyzer obviously descends, and obvious rising falls in the reacting system pressure when using fixed bed, needs more catalyst changeout.And the present invention program, after 1000 hours, the Pressure Drop of catalyst performance and reactive system does not all have considerable change in steady running, and according to this trend, estimating fully can steady running 1～3 year.
Description of drawings
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 with the difference of Fig. 1 second reaction zone and the 3rd reaction zone use independently recycle hydrogen system separately.
Embodiment
Method of the present invention is specific as follows: the mixing oil of one or more in the bio-oil is as stock oil, under the hydroprocessing condition, stock oil and the hydrogen reactor by comprising cold operation and the first reaction zone of the reactor of high-temperature operation, the hydrotreatment that obtains generates logistics and separates the gas circulation use that obtains in high-pressure separator, also can go out system, the liquid distillate that obtains; Diesel raw material and hydrogen are mixed into and comprise hydrorefined second reaction zone, and the hydrofining that obtains generates logistics and separates the gas circulation use that obtains in high-pressure separator, also can go out system, the liquid distillate that obtains; 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 that obtains generates logistics and separate the gas circulation use that obtains in high-pressure separator, also can go out system, the liquid fractionation obtains following products: one or more in gas, petroleum naphtha, the low freezing point diesel fuel.The bio-oil that embodiment uses is the commercially available prod, filtering solid impurity before using.
Further specify particular case of the present invention below by embodiment.Wherein modifying catalyst contains beta-molecular sieve, and this catalyzer has the isomery function.
The chief component 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 |
| The cut scope, ℃ | 155~375 | 160~365 |
| Sulphur content, wt% | 2.0 | 1.2 |
| Nitrogen content, μ g/g | 1020 | 600 |
| Condensation point, ℃ | 5 | 13 |
| Cetane value | 18 | 38 |
Table 3 embodiment processing condition and test-results.
| The first reaction zone processing condition | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Stock oil | Oleum Gossypii semen | Soybean oil | Plam oil |
| The cold operation reactor | ? | ? | ? |
| Catalyzer | Catalyzer 3 | Catalyzer 3 | Catalyzer 3/ catalyzer 1 |
| The catalyst volume ratio | 100 | 100 | 30:70 |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 |
| The 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, ℃ | 130 | 180 | 260 |
| The high-temperature operation reactor | ? | ? | ? |
| Catalyzer | Catalyzer 1 | Catalyzer 2 | Catalyzer 2 |
| Reaction pressure, MPa | 17.0 | 5.0 | 10.0 |
| The 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, ℃ | 280 | 350 | 300 |
| The second reaction zone processing condition | ? | ? | ? |
| Catalyzer | Catalyst for refining | Catalyst for refining | 8 doses of refining catalytics |
| Stock oil | Catalytic diesel oil | Catalytic diesel oil | Medium diesel oil |
| Reaction pressure, MPa | 13.0 | 8.0 | 10.0 |
| The 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, ℃ | 360 | 350 | 370 |
| The 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 |
| The 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, ℃ | 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, ℃ | -20 | -30 | -25 |
| Cetane value | 55 | 52 | 64 |
Table 4 embodiment processing condition and test-results.
| The 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 |
| The stock oil ratio | 100 | 40:60 | 40:60 | 40:60 |
| The 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 |
| The 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 |
| The 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, ℃ | 180 | 350 | 360 | 380 |
| The high-temperature operation reactor | ? | ? | ? | ? |
| Catalyzer | Catalyzer 2 | ? | ? | ? |
| Reaction pressure, MPa | 10.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 800:1 | ? | ? | ? |
| Volume space velocity, h -1 | 1.6 | ? | ? | ? |
| Average reaction temperature, ℃ | 300 | ? | ? | ? |
| The second reaction zone processing condition | ? | ? | ? | ? |
| Catalyzer | Catalyst for refining | ? | ? | ? |
| Stock oil | Catalytic diesel oil | ? | ? | ? |
| Reaction pressure, MPa | 10.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 1.5 | ? | ? | ? |
| Average reaction temperature, ℃ | 350 | ? | ? | ? |
| The 3rd reaction zone processing condition | ? | — | — | — |
| Catalyzer | Modifying catalyst | ? | ? | ? |
| Stock oil | Two reaction liquid phases produce volume ratio 40:60 | ? | ? | ? |
| Reaction pressure, MPa | 10.0 | ? | ? | ? |
| The entrance hydrogen to oil volume ratio | 1000:1 | ? | ? | ? |
| Volume space velocity, h -1 | 2.0 | ? | ? | ? |
| Average reaction temperature, ℃ | 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, ℃ | -25 | -25 | -10 | 5 |
| Cetane value | 53 | 53 | 46 | 38 |
Can be found out by embodiment, bio-oil and diesel raw material oil can be produced high-grade low-freezing point diesel product by the combined hydrogenation method of present technique, perhaps high-grade low-freezing point diesel oil blending component, and can realize long-period stable operation, turn round after 1000 hours, the reactive system pressure drop is not risen substantially, and carbon deposition quantity only has about 3.5wt% on the catalyzer, belong to the balance carbon deposition quantity, do not affect the catalyzer use properties.
Claims (11)
1. combined hydrogenation method of producing low freezing point diesel fuel is characterized in that comprising following content:
(a) one or more in the bio-oil are the first stock oil, and one or more of straight-run diesel oil or secondary processing diesel oil cut are the second stock oil;
(b) under the hydrotreatment operational condition, the first stock oil is by the first reaction zone of at least two hydrogenators, load hydrogenation catalyst in the hydrogenator, bio-oil and hydrogen is the hydrogenator by cold operation at first, then by the hydrogenator of high-temperature operation, under response behaviour, the active ingredient of hydrogenation catalyst is Pt and/or the Pd of reduction-state, the first reaction zone hydrogenation effluent is separated into gas phase and liquid phase, and gas-phase dehydration recycles after processing;
(c) under the hydrofining operational condition, by the second reaction zone of filling Hydrobon catalyst, second reaction zone hydrogenation effluent is separated into gas phase and liquid phase to the second stock oil under hydroconversion condition, and gas phase recycles;
(d) after the first reaction zone hydrogenation effluent separates the liquid phase obtain and second reaction zone hydrogenation effluent separates the liquid-phase mixing that obtains under the hydroisomerizing condition by comprising at least the 3rd reaction zone of hydroisomerization catalyst;
(e) gas phase of the 3rd reaction zone reaction effluent recycles, and the liquid phase of the 3rd reaction zone reaction effluent is carried out fractionation by distillation and obtained petroleum naphtha and high-quality super low sulfur, low freezing point diesel fuel product cut.
2. in accordance with the method for claim 1, it is characterized in that: in the 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 the step (a), the straight-run diesel oil that uses 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, and perhaps is the coal tar diesel oil distillate.
4. in accordance with the method for claim 1, it is characterized in that: in the step (b), the reaction pressure 3.0MPa of the hydrogenator of cold operation ~ 20.0MPa, hydrogen to oil volume ratio are 200:1 ~ 3000:1, and volume space velocity is 0.5h
-1~ 6.0h
-1, 120 ℃ ~ 280 ℃ of average reaction temperature; 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 than the hydrogenator of cold operation high 50 ℃ ~ 300 ℃.
5. in accordance with the method for claim 1, it is characterized in that: in rapid (b), the average reaction temperature of the hydrogenator of high-temperature operation is higher 80 ~ 220 ℃ than the hydrogenator of cold operation step by step.
6. according to claim 1 and 4 described methods, it is characterized in that: in the step (b), in the hydrogenator of the cold operation that reaction mass at first passes through, the active ingredient of the hydrogenation catalyst that uses 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 the hydrogenator by high-temperature operation, and the active ingredient of the hydrogenation catalyst that uses 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%.
7. in accordance with the method for claim 6, it is characterized in that: the active component content of catalyzer is higher than 0.1 ~ 3 percentage point of catalyzer in the cold operation hydrogenator in the element quality in the hydrogenator of high-temperature operation.
8. in accordance with the method for claim 1, it is characterized in that: in the 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 ℃ ~ 465 ℃; Preferred hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 5.0h
-1, average reaction temperature is 200 ℃ ~ 445 ℃.
9. in accordance with the method for claim 1, it is characterized in that: in the 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 ℃ ~ 465 ℃; Preferred hydrogen to oil volume ratio is 300:1 ~ 2500:1, and volume space velocity is 0.4h
-1~ 4.0h
-1, average reaction temperature is 200 ℃ ~ 445 ℃.
10. in accordance with the method for claim 1, it is characterized in that: in the step (d), contain 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 is take the weight content of oxide compound as 10%～40%.
11. in accordance with the method for claim 1, it is characterized in that: it is characterized in that in the step (a), the volume ratio of the first stock oil and the second stock oil is 10:90 ~ 90:10.
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|---|---|---|---|
| CN201210130669.3A CN103374403B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation combination method for producing low-condensation-point diesel oil |
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|---|---|---|---|
| CN201210130669.3A CN103374403B (en) | 2012-04-29 | 2012-04-29 | Hydrogenation combination method for producing low-condensation-point diesel oil |
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