CN105647580B - F- T synthesis full distillate oil produces low solidifying intermediate oil system and method - Google Patents
F- T synthesis full distillate oil produces low solidifying intermediate oil system and method Download PDFInfo
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- CN105647580B CN105647580B CN201610176218.1A CN201610176218A CN105647580B CN 105647580 B CN105647580 B CN 105647580B CN 201610176218 A CN201610176218 A CN 201610176218A CN 105647580 B CN105647580 B CN 105647580B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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Abstract
Low solidifying midbarrel oil system is produced the invention discloses a kind of F- T synthesis full distillate oil, its Fischer-Tropsch heavy oil conveying pipeline connects the bottom input end of the first hydrogenation reactor, Fischer-Tropsch light oil conveyance conduit connects the middle part input of the first hydrogenation reactor, first hydrogen delivery tube road is connected with Fischer-Tropsch heavy oil conveying pipeline, second hydrogen delivery tube road is connected with Fischer-Tropsch light oil conveyance conduit, the output channel of the first hydrogenation reactor connects the bottom input end of the second hydrogenation reactor, the top output port of the second hydrogenation reactor connects the input of gas-liquid separator, the liquid phase output of gas-liquid separator connects the input of fractionating column, fractionating column has naphtha product delivery outlet and low-coagulation diesel oil delivery outlet.It is hydrocracked in the present invention and hydroisomerizing is all using lower feeding manner, make hydrogen concentration more reasonable to distribution along reactor axis, temperature of reactor gradient is minimum, while overcoming the big problem of beds top pressure drop.
Description
Technical field
The present invention relates to Fischer-Tropsch synthesis oil deep processing technical field, in particular to a kind of production of F- T synthesis full distillate oil
Low solidifying intermediate oil system and method.
Background technology
Low Temperature Fischer Tropsch synthesis major product is the complex mixture of the hydro carbons and a small amount of oxygenatedchemicals for containing C4~C70,
The features such as with without sulphur, nitrogen-free, without metal, low aromatic hydrocarbons.
Tradition is hydrocracked using upper feeding mode, and bed temperature gradient and pressure drop are larger, the easy coking in reactor top,
Equipment investment and operating cost are higher, and isomerization rate is not enough in addition, produce that condensation point of diesel oil is high, and chemical hydrogen consumption is high.
Fischer-Tropsch synthesis oil has relatively big difference with oil, and wherein unsaturated olefin, acid etc. focuses primarily upon light component, light component
Hydrofinishing can release substantial amounts of heat and cause coking, while temperature rise is substantially, temperature is difficult to control.
The content of the invention
Low solidifying midbarrel oil system and side are produced present invention aim to provide a kind of F- T synthesis full distillate oil
Method, is hydrocracked in the system and method and hydroisomerizing is all using lower feeding manner, makes hydrogen concentration along reactor axis to distribution
More rationally, temperature of reactor gradient is minimum, while overcoming the big problem of beds top pressure drop.
In order to achieve this, the F- T synthesis full distillate oil designed by the present invention produces low solidifying midbarrel oil system, its
It is characterised by：It includes the first hydrogenation reactor, the second hydrogenation reactor, gas-liquid separator, fractionating column, Fischer-Tropsch oil transfer pipe
Road, Fischer-Tropsch light oil conveyance conduit, the first hydrogen delivery tube road and the second hydrogen delivery tube road, wherein, first hydrogenation reaction
Device includes upper beds and lower beds, and the Fischer-Tropsch heavy oil conveying pipeline connects the middle part of the first hydrogenation reactor
Input, Fischer-Tropsch light oil conveyance conduit connects the bottom input end of the first hydrogenation reactor, the first hydrogen cracker
Bottom input end is located at the lower section of beds under the first hydrogenation reactor, the middle part input of first hydrogenation reactor
Between beds on the first hydrogenation reactor and lower beds, the first hydrogen delivery tube road is defeated with Fischer-Tropsch heavy oil
Pipeline communication, the second hydrogen delivery tube road is sent to be connected with Fischer-Tropsch light oil conveyance conduit, the output channel of the first hydrogenation reactor connects
The bottom input end of the second hydrogenation reactor is connect, the top output port of the second hydrogenation reactor connects the input of gas-liquid separator
End, the liquid phase output of gas-liquid separator connects the input of fractionating column, the fractionating column have naphtha product delivery outlet and
Low-coagulation diesel oil delivery outlet, the recycle oil output end of fractionating column connects the bottom input end of the second hydrogenation reactor.
A kind of method that utilization said system produces low solidifying intermediate oil, it is characterised in that it comprises the following steps：
Step 1：Hydrogen saturation in second hydrogen delivery tube road is dissolved in the Fischer-Tropsch light oil in Fischer-Tropsch light oil conveyance conduit, shape
Into hydrogen saturation Fischer-Tropsch light oil, the hydrogen saturation Fischer-Tropsch light oil is input into the first hydrogenation reaction by the bottom input end of the first hydrogenation reactor
Device, the hydrogen saturation in the first hydrogen delivery tube road is dissolved in the Fischer-Tropsch heavy oil in Fischer-Tropsch heavy oil conveying pipeline, is formed hydrogen saturation and is taken
Support heavy oil, the hydrogen saturation Fischer-Tropsch heavy oil is input into the first hydrogenation reactor, hydrogen saturation by the middle part input of the first hydrogenation reactor
Fischer-Tropsch light oil and hydrogen saturation Fischer-Tropsch heavy oil are hydrogenated with the presence of Hydrobon catalyst and hydrocracking catalyst respectively
Cracking reaction generates intermediate oil, and it is anti-that intermediate oil is input into the second hydrogenation by the bottom input end of the second hydrogenation reactor
Answer device；
Step 2：Intermediate oil passes through being hydrocracked for the first catalyst reaction bed respectively in the second hydrogenation reactor
The hydroisomerization catalyst of catalyst and the second catalyst reaction bed carries out hydroisomerizing reaction, generates low solidifying midbarrel
Oil；
Step 3：Low solidifying intermediate oil carries out gas-liquid separation treatment into gas-liquid separator, and the liquid phase isolated enters divides
Evaporate tower fractionation and obtain naphtha product and purpose product low-coagulation diesel oil.
Beneficial effects of the present invention：
1st, it is hydrocracked in the present invention and hydroisomerizing is all using lower feeding manner, makes hydrogen concentration along reactor axis to distribution
More rationally, temperature of reactor gradient is minimum, while overcoming the big problem of beds top pressure drop.
2nd, Fischer-Tropsch synthetic is based on saturated straight chain hydrocarbon, and saturation degree is higher, and chemical hydrogen consumption is low.
3rd, Fischer-Tropsch light oil and Fischer-Tropsch heavy oil separately feed as described herein in the present invention, and one can keep refining reaction
Bed temperature control is steady, and two reduce the temperature of Fischer-Tropsch heavy oil feed again, reduce energy consumption.
Brief description of the drawings
Fig. 1 is structural representation of the invention；
Wherein, the 1-the first hydrogenation reactor, the 2-the second hydrogenation reactor, 3-gas-liquid separator, 4-fractionating column, 5-
Fischer-Tropsch heavy oil conveying pipeline, 6-Fischer-Tropsch light oil conveyance conduit, the 7-the first hydrogen delivery tube road, the 8-the second hydrogen delivery tube road,
9-naphtha product delivery outlet, 10-low-coagulation diesel oil delivery outlet.
Specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail：
F- T synthesis full distillate oil as described in Figure 1 produces low solidifying midbarrel oil system, and it includes the first hydrogenation reaction
Device 1, the second hydrogenation reactor 2, gas-liquid separator 3, fractionating column 4, Fischer-Tropsch heavy oil conveying pipeline 5, Fischer-Tropsch light oil conveyance conduit 6,
First hydrogen delivery tube road 7 and the second hydrogen delivery tube road 8, wherein, first hydrogenation reactor 1 includes upper beds
With lower beds, the middle part input of first hydrogenation reactor 1 of the connection of Fischer-Tropsch heavy oil conveying pipeline 5, Fischer-Tropsch light oil
Conveyance conduit 6 connects the bottom input end of the first hydrogenation reactor 1, the bottom input end position of the first hydrogen cracker 1
In the lower section of 1 time beds of the first hydrogenation reactor, the middle part input of first hydrogenation reactor 1 is located at first and adds
On hydrogen reactor 1 between beds and lower beds, the first hydrogen delivery tube road 7 and Fischer-Tropsch heavy oil conveying pipeline 5
Connection, the second hydrogen delivery tube road 8 connects with Fischer-Tropsch light oil conveyance conduit 6, and the output channel of the first hydrogenation reactor 1 connects the
The bottom input end of two hydrogenation reactors 2, the top output port of the second hydrogenation reactor 2 connects the input of gas-liquid separator 3,
The liquid phase output of gas-liquid separator 3 connects the input of fractionating column 4, and the fractionating column 4 has the He of naphtha product delivery outlet 9
Low-coagulation diesel oil delivery outlet 10, the recycle oil output end of fractionating column 4 connects the bottom input end of the second hydrogenation reactor 2.
In above-mentioned technical proposal, the upper beds of first hydrogenation reactor 1 dose hydrocracking catalyst, the
The lower beds of one hydrogenation reactor 1 fill out Hydrobon catalyst.
In above-mentioned technical proposal, hydrogenation active metals are Ni and Mo in the Hydrobon catalyst, and oxygenatedchemicals contains
Amount scope is by mass percentage 1%~40%, and catalyst carrier is porous refractory oxide, such as aluminum oxide, silica or multiple
Close oxide etc..The specific surface area scope of the Hydrobon catalyst is 200~600m2/ g, the hole of Hydrobon catalyst
Appearance scope is 0.3~0.6ml/g.
In above-mentioned technical proposal, the content of the amorphous silica-alumina in the hydrocracking catalyst is by mass percentage
40%~80%, the hydrogenation active metals in hydrocracking catalyst are Ni and W, the oxygenatedchemicals in hydrocracking catalyst
Total content is by mass percentage 10%~30%.Molecular sieve in the hydrocracking catalyst is Y type molecular sieve, beta molecule
One or more in sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 mesopore molecular sieves.The hydrocracking catalyst
The content of middle molecular sieve is by mass percentage 1%~20%, the specific surface area scope of the hydrocracking catalyst for 200~
500m2/ g, the pore volume scope of hydrocracking catalyst is 0.3~0.7ml/g.
In above-mentioned technical proposal, second hydrogenation reactor 2 includes two catalyst reaction beds, distinguishes from the bottom up
It is the first catalyst reaction bed and the second catalyst reaction bed, the first catalyst reaction bed filling hydrocracking catalyst
Agent, the second catalyst reaction bed filling hydroisomerization catalyst.The cracking performance of hydroisomerization catalyst is relatively weak, with straight
Chain hydrocarbon tautomerizes to key reaction, and condensation point can be reduced substantially.
In above-mentioned technical proposal, Hydrobon catalyst, hydrocracking catalyst and hydroisomerization catalyst can be selected
The commercial catalysts of existing matching.
In above-mentioned technical proposal, the first hydrogenation reactor 1 includes refined and cracking processing procedure, the second hydrogenation reactor 2
Comprising cracking and isomery processing procedure.
A kind of method that utilization said system produces low solidifying intermediate oil, it comprises the following steps：
Step 1：Hydrogen saturation in second hydrogen delivery tube road 8 is dissolved in the Fischer-Tropsch light oil (temperature in Fischer-Tropsch light oil conveyance conduit 6
Degree 350 DEG C of ＜) in, formed hydrogen saturation Fischer-Tropsch light oil, the hydrogen saturation Fischer-Tropsch light oil by the first hydrogenation reactor 1 bottom input end
The first hydrogenation reactor 1 is input into, the hydrogen saturation in the first hydrogen delivery tube road 7 is dissolved in the Fischer-Tropsch in Fischer-Tropsch heavy oil conveying pipeline 5
In heavy oil, hydrogen saturation Fischer-Tropsch heavy oil (temperature >=350 DEG C) is formed, the hydrogen saturation Fischer-Tropsch heavy oil is by the first hydrogenation reactor 1
Portion's input is input into the first hydrogenation reactor 1, and hydrogen saturation Fischer-Tropsch light oil and hydrogen saturation Fischer-Tropsch heavy oil are catalyzed in hydrofinishing respectively
Hydrocracking reaction generation intermediate oil is carried out in the presence of agent and hydrocracking catalyst, intermediate oil adds by second
The bottom input end of hydrogen reactor 2 is input into the second hydrogenation reactor 2；
Step 2：Intermediate oil passes through being hydrocracked for the first catalyst reaction bed respectively in the second hydrogenation reactor 2
The hydroisomerization catalyst of catalyst and the second catalyst reaction bed carries out hydroisomerizing reaction, generates low solidifying midbarrel
Oil；
Step 3：Low solidifying intermediate oil carries out gas-liquid separation treatment into gas-liquid separator 3, and the liquid phase isolated enters
The fractionation of fractionating column 4 obtains naphtha product and purpose product low-coagulation diesel oil, and the gas phase isolated seldom, can make fuel gas.
Step 4, the recycle oil in fractionating column 4 returns to the bottom input end of the second hydrogenation reactor 2, and recycle oil adds second
Recycle oil dissolved hydrogen is produced in hydrogen reactor 2, part not enough in hydroisomerizing reaction hydrogen used is supplemented.
The present invention can be selected in the bottom input end of the first hydrogenation reactor 1 and middle part input filling hydrogenation protecting
Agent, it is also possible to the catalyst for refining after filling before the top output port of the second hydrogenation reactor 2.
In above-mentioned technical proposal, after the hydrogenated cracking of logistics, hydrogen partial is consumed, it is necessary to supplement hydrogen, because being that liquid phase adds
Hydrogen, therefore the hydrogen of supplement is that saturation is dissolved in logistics.
In above-mentioned technical proposal, the low solidifying diesel oil meant by being hydrocracked especially hydroisomerizing pour point depression of this paper,
Condensation point according to actual needs, as long as low solidifying less than being referred to as 0# diesel oil.
Table 1 is the experiment condition used by embodiment, experimental result.Hydrobon catalyst, hydrocracking catalyst and add
Hydrogen heterogeneous catalyst is limited all in accordance with the invention described above methods described and condition etc., is prepared by laboratory conventional method.
Table 1 is technological experiment condition and result
Table 1 illustrates that product low-coagulation diesel oil yield of the invention is good, and product property is good.
The content that this specification is not described in detail belongs to prior art known to professional and technical personnel in the field.
Claims (7)
1. a kind of F- T synthesis full distillate oil produces low solidifying midbarrel oil system, it is characterised in that：It includes that the first hydrogenation is anti-
Answer device (1), the second hydrogenation reactor (2), gas-liquid separator (3), fractionating column (4), Fischer-Tropsch heavy oil conveying pipeline (5), Fischer-Tropsch light
Oily conveyance conduit (6), the first hydrogen delivery tube road (7) and the second hydrogen delivery tube road (8), wherein, first hydrogenation reaction
Device (1) includes upper beds and lower beds, and the Fischer-Tropsch heavy oil conveying pipeline (5) connects the first hydrogenation reactor
(1) middle part input, Fischer-Tropsch light oil conveyance conduit (6) connects the bottom input end of the first hydrogenation reactor (1), described first
The bottom input end of hydrogenation reactor (1) is located at the lower section of beds under the first hydrogenation reactor (1), first hydrogenation
The middle part input of reactor (1) is located on the first hydrogenation reactor (1) between beds and lower beds, and first
Hydrogen delivery tube road (7) is connected with Fischer-Tropsch heavy oil conveying pipeline (5), the second hydrogen delivery tube road (8) and Fischer-Tropsch light oil delivery pipe
Road (6) is connected, and the output channel of the first hydrogenation reactor (1) connects the bottom input end of the second hydrogenation reactor (2), and second adds
The input of top output port connection gas-liquid separator (3) of hydrogen reactor (2), the liquid phase output of gas-liquid separator (3) connects
Connect the input of fractionating column (4), the fractionating column (4) with naphtha product delivery outlet (9) and low-coagulation diesel oil delivery outlet (10),
The recycle oil output end of fractionating column (4) connects the bottom input end of the second hydrogenation reactor (2)；
The upper beds of first hydrogenation reactor (1) dose hydrocracking catalyst, the first hydrogenation reactor (1)
Lower beds fill out Hydrobon catalyst；
Second hydrogenation reactor (2) includes two catalyst reaction beds, from the bottom up respectively the first catalyst reaction
Bed and the second catalyst reaction bed, the first catalyst reaction bed filling hydrocracking catalyst, the second catalyst reaction
Bed loads hydroisomerization catalyst；
The content of the amorphous silica-alumina in the hydrocracking catalyst is by mass percentage 40%~80%, is hydrocracked and urges
Hydrogenation active metals in agent are Ni and W, and the total oxygenate content in hydrocracking catalyst is by mass percentage
10%~30%；
The bottom input end of first hydrogenation reactor (1) and the filling hydrogenation protecting agent of middle part input.
2. F- T synthesis full distillate oil according to claim 1 produces low solidifying midbarrel oil system, it is characterised in that：Institute
It is Ni and Mo to state hydrogenation active metals in Hydrobon catalyst, oxygenates level scope by mass percentage for 1%~
40%, catalyst carrier is porous refractory oxide.
3. F- T synthesis full distillate oil according to claim 2 produces low solidifying midbarrel oil system, it is characterised in that：Institute
The specific surface area scope for stating Hydrobon catalyst is 200~600m2/ g, the pore volume scope of Hydrobon catalyst for 0.3~
0.6ml/g。
4. F- T synthesis full distillate oil according to claim 1 produces low solidifying midbarrel oil system, it is characterised in that：Institute
It is Y type molecular sieve, beta-molecular sieve, ZSM-5 molecular sieve, SAPO molecular sieve and MCM-41 to state the molecular sieve in hydrocracking catalyst
One or more in mesopore molecular sieve.
5. F- T synthesis full distillate oil according to claim 4 produces low solidifying midbarrel oil system, it is characterised in that：Institute
The content for stating molecular sieve in hydrocracking catalyst is by mass percentage 1%~20%, the ratio of the hydrocracking catalyst
Surface area is 200~500m2/ g, the pore volume scope of hydrocracking catalyst is 0.3~0.7ml/g.
6. the method that system described in a kind of utilization claim 1 produces low solidifying intermediate oil, it is characterised in that it includes as follows
Step：
Step 1：Hydrogen saturation in second hydrogen delivery tube road (8) is dissolved in the Fischer-Tropsch light oil in Fischer-Tropsch light oil conveyance conduit (6),
Hydrogen saturation Fischer-Tropsch light oil is formed, the hydrogen saturation Fischer-Tropsch light oil is added by the bottom input end input first of the first hydrogenation reactor (1)
Hydrogen reactor (1), the hydrogen saturation in the first hydrogen delivery tube road (7) is dissolved in the Fischer-Tropsch heavy oil in Fischer-Tropsch heavy oil conveying pipeline (5)
In, hydrogen saturation Fischer-Tropsch heavy oil is formed, the hydrogen saturation Fischer-Tropsch heavy oil is input into first by the middle part input of the first hydrogenation reactor (1)
Hydrogenation reactor (1), hydrogen saturation Fischer-Tropsch light oil and hydrogen saturation Fischer-Tropsch heavy oil are urged in Hydrobon catalyst and being hydrocracked respectively
Hydrocracking reaction generation intermediate oil is carried out in the presence of agent, intermediate oil is by the second hydrogenation reactor (2)
Bottom input end is input into the second hydrogenation reactor (2)；
Step 2：Intermediate oil passes through being hydrocracked for the first catalyst reaction bed respectively in the second hydrogenation reactor (2)
The hydroisomerization catalyst of catalyst and the second catalyst reaction bed carries out hydroisomerizing reaction, generates low solidifying midbarrel
Oil；
Step 3：Low solidifying intermediate oil carries out gas-liquid separation treatment into gas-liquid separator (3), and the liquid phase isolated enters divides
Evaporate tower (4) fractionation and obtain naphtha product and purpose product low-coagulation diesel oil.
7. the method for the low solidifying intermediate oil of production according to claim 6, it is characterised in that：Also wrapped after the step 3
Step 4 is included, the recycle oil in fractionating column (4) returns to the bottom input end of the second hydrogenation reactor (2), and recycle oil is in the second hydrogenation
Recycle oil dissolved hydrogen is produced in reactor (2), part not enough in hydroisomerizing reaction hydrogen used is supplemented.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610176218.1A CN105647580B (en) | 2016-03-25 | 2016-03-25 | F- T synthesis full distillate oil produces low solidifying intermediate oil system and method |
| PCT/CN2017/073864 WO2017161981A1 (en) | 2016-03-25 | 2017-02-17 | System and method for producing low-condensation-point middle distillate using fischer-tropsch synthesized whole distillate |
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| CN201610176218.1A CN105647580B (en) | 2016-03-25 | 2016-03-25 | F- T synthesis full distillate oil produces low solidifying intermediate oil system and method |
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| CN105647580B (en) * | 2016-03-25 | 2017-06-20 | 武汉凯迪工程技术研究总院有限公司 | F- T synthesis full distillate oil produces low solidifying intermediate oil system and method |
| CN107418622B (en) * | 2017-06-07 | 2019-06-18 | 神华集团有限责任公司 | Improve the device and method of F- T synthesis diesel oil density |
| CN111871333B (en) * | 2020-07-16 | 2023-06-27 | 南京延长反应技术研究院有限公司 | Micro-interface reaction system and method for anthracene oil hydrogenation |
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| US6656342B2 (en) * | 2001-04-04 | 2003-12-02 | Chevron U.S.A. Inc. | Graded catalyst bed for split-feed hydrocracking/hydrotreating |
| US20040256286A1 (en) * | 2003-06-19 | 2004-12-23 | Miller Stephen J. | Fuels and lubricants using layered bed catalysts in hydrotreating waxy feeds, including Fischer-Tropsch wax |
| CN101177624A (en) * | 2007-03-26 | 2008-05-14 | 中科合成油技术有限公司 | Hydro-cracking method for f-t synthetic oil |
| CN103131468B (en) * | 2013-02-06 | 2015-03-25 | 神华集团有限责任公司 | Hydrofining and/or hydroisomerizing cracking system and process for low-temperature Fischer-Tropsch synthetic oil |
| CN104673384B (en) * | 2015-03-02 | 2016-09-14 | 武汉凯迪工程技术研究总院有限公司 | A kind of hydrofinishing process of Low Temperature Fischer Tropsch full distillate oil fecund intermediate oil |
| CN105647580B (en) * | 2016-03-25 | 2017-06-20 | 武汉凯迪工程技术研究总院有限公司 | F- T synthesis full distillate oil produces low solidifying intermediate oil system and method |
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