CN106350105B - A method of processing Fischer-Tropsch synthesis oil - Google Patents
A method of processing Fischer-Tropsch synthesis oil Download PDFInfo
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Abstract
The present invention relates to refining arts, disclose a kind of method for processing Fischer-Tropsch synthesis oil, this method comprises: Fischer-Tropsch synthesis oil is introduced into hydrofining reactor with hydrogeneous logistics, then hydrofining reaction effluent are successively separated and are fractionated；Heavy oil fraction is successively introduced into the first isomery hydrocracking reactor containing isomery hydrocracking catalyst I and the second isomery hydrocracking reactor containing isomery hydrocracking catalyst II, then the reaction effluent of the second isomery hydrocracking reactor is successively separated and is fractionated；Wherein, the cracking activity of isomerization activity of the isomerization activity of isomery hydrocracking catalyst I higher than isomery hydrocracking catalyst II and isomery hydrocracking catalyst II are higher than the cracking activity of isomery hydrocracking catalyst I.When processing Fischer-Tropsch synthesis oil using the above method of the invention, the selectivity and yield of intermediate oil can be improved.
Description
Technical field
The present invention relates to refining arts, and in particular, to a method of processing Fischer-Tropsch synthesis oil, more specifically, this hair
It is bright to be related to a kind of method that production intermediate oil is converted by hydrogenation of Fischer-Tropsch synthesis oil.
Background technique
With the rapid development of the national economy, zooming trend is presented in China's oil consumption.At the same time, with ring
Guaranteed request it is increasingly stringent, the discharge of pollutant in the composition, impurity content and process of engine fuel is proposed more
For harsh requirement.However, petroleum as the non-renewable energy, is faced with increasingly exhausted crisis, oily quality is also more next
Poorer, the trend of in poor quality and heaviness becomes clear day by day.Therefore, meet environmental requirements can with the novel of liquid fuel demand for exploitation
Continuous energy technology has become the research power for solving energy crisis and environmental crisis.
Fischer-Tropsch synthesis is found by German chemist Fischer and Tropsch in nineteen twenty-three.The reaction be with hydrogen and
Carbon monoxide is raw material, and the reaction of hydro carbons is generated under synthetic catalyst effect.Its raw material can pass through coal, natural gas, coal seam
Gas, biomass etc. are transformed, and have extensive source.In the case where crude oil price is constantly soaring, Fischer-Tropsch synthesis oil it is big
Technical scale application carrys out production section high quality engine fuel and industrial chemicals is with a wide range of applications.Using F- T synthesis
The synthetic oil that technology obtains has biggish area in the various aspects such as hydro carbons composition and main character compared with conventional oil derivative
Not, it is a kind of mixture high containing wax content, is mainly made of alkane and alkene, and sulphur, nitrogen content are extremely low, but containing certain
The oxygen of amount.Gasoline fraction is substantially free of sulphur and nitrogen, but due in its composition alkene and the alkane overwhelming majority be straight chain, therefore its
Octane number is very low；Diesel oil distillate sulphur, nitrogen and arene content are extremely low, and Cetane number is very high, but its low temperature fluidity is very poor, solidifying
Point etc. is higher.Therefore, it needs just obtain by adding hydrogen upgrading accordingly by each fraction that Fischer-Tropsch synthesis product obtains
Meet the liquid fuel using specification.
For example, US6589415 describes a kind of method for being hydrocracked Fischer-Tropsch synthesis oil, be mainly characterized by by
The heavy distillat of synthetic oil is hydrocracked, using the light fraction of synthetic oil as the cooling logistics of hydrocracking reaction bed.It should
Although Fischer-Tropsch synthesis oil is converted light component by invention and the method by being hydrocracked, it is disadvantageous in that cracking catalysis
Agent is easy inactivation, in addition, the liquid product yield of this method is low, selectivity is low.
Therefore, a kind of method for needing to find new processing Fischer-Tropsch synthesis oil in the art, to improve intermediate oil
Selectivity and obtain higher midbarrel oil yield.
Summary of the invention
The purpose of the present invention is overcoming the defect that the intermediate oil of the prior art is selectively low and yield is not high, provide
The new method by hydrogenation of Fischer-Tropsch synthesis oil upgrading production intermediate oil that a kind of intermediate oil selectivity and yield improve.
To achieve the goals above, the present invention provides a kind of method for processing Fischer-Tropsch synthesis oil, this method comprises: by Fischer-Tropsch
Synthetic oil is introduced into the hydrofining reactor containing Hydrobon catalyst with hydrogeneous logistics to be reacted, and hydrogen essence then will be added
Reaction effluent processed is successively separated and is fractionated, and the first naphtha cut, light diesel fuel fraction and heavy oil fraction are obtained；It will be described
Heavy oil fraction successively introduces the first isomery hydrocracking reactor containing isomery hydrocracking catalyst I and adds hydrogen containing isomery
In the second isomery hydrocracking reactor of Cracking catalyst II, then by the reaction of the second isomery hydrocracking reactor
Effluent is successively separated and is fractionated, and the second naphtha cut, intermediate oil and tail oil fraction are obtained, optionally will at least
The part tail oil fraction is recycled back to entering for the first isomery hydrocracking reactor and/or the second isomery hydrocracking reactor
Mouthful；Wherein, the isomery that the isomerization activity of the isomery hydrocracking catalyst I of unit volume is higher than unit volume adds
The cracking activity of the isomery hydrocracking catalyst II of the isomerization activity and unit volume of hydrogen Cracking catalyst II is high
In the cracking activity of the isomery hydrocracking catalyst I of unit volume.
When processing Fischer-Tropsch synthesis oil using the above method of the invention, the selectivity and receipts of intermediate oil can be improved
Rate.
The above method of the invention also has the advantage that relatively independent unifining process and isomery were hydrocracked
Journey enables to access the target product for different performance, meeting different product specification, and products scheme is flexible；Moreover, of the invention
The above method to existing apparatus process carry out less change in the case where can be achieved with, the capital cost of device is greatly saved
With.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.Some ancillary equipments in attached drawing are such as
Heat exchanger, preheating furnace etc. do not mark, but this is well known to those of ordinary skill in the art.In the accompanying drawings:
Fig. 1 is the flow diagram of the method for hydrogenation of Fischer-Tropsch synthesis oil upgrading provided by the invention.
Description of symbols
1 Fischer-Tropsch synthesis oil, 2 hydrofining reactor
3 first high pressure hot separator, 4 first cold high pressure separator
5 water, 6 first thermal low-pressure separators
The cold low liquid separation phase of 7 first cold low separator 8 first
Low 10 first fractionating column of liquid separation phase of 9 first heat
11 first naphtha cut, 12 light diesel fuel fraction
13 heavy oil fraction, 14 first low point of gas
15 hydrogen-rich gas, 16 circulating hydrogen compressor
17 new 18 circulating air of hydrogen
19 first isomery hydrocracking reactor, 20 second isomery hydrocracking reactor
21 second high pressure hot separator, 22 second cold high pressure separator
23 second thermal low-pressure separators, 24 second cold low separator
The low cold low liquid separation phase of liquid separation phase 26 second of 25 second heat
27 after-fractionating tower, 28 second naphtha cut
29 intermediate oil, 30 tail oil fraction
31 second low point of cold high score gas phase of gas 32 second
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methods for processing Fischer-Tropsch synthesis oil, this method comprises: by Fischer-Tropsch synthesis oil and hydrogeneous object
Stream is introduced into the hydrofining reactor containing Hydrobon catalyst and is reacted, then by hydrofining reaction effluent according to
It is secondary to be separated and be fractionated, obtain the first naphtha cut, light diesel fuel fraction and heavy oil fraction；The heavy oil fraction is successively drawn
Enter the first isomery hydrocracking reactor containing isomery hydrocracking catalyst I and containing isomery hydrocracking catalyst II's
In second isomery hydrocracking reactor, then the reaction effluent of the second isomery hydrocracking reactor is successively carried out
Separation and fractionation, obtain the second naphtha cut, intermediate oil and tail oil fraction, optionally evaporate at least partly described tail oil
Divide the entrance for being recycled back to the first isomery hydrocracking reactor and/or the second isomery hydrocracking reactor；Wherein, unit volume
The isomerization activity of the isomery hydrocracking catalyst I be higher than the isomery hydrocracking catalyst II of unit volume
The cracking activity of isomerization activity and the isomery hydrocracking catalyst II of unit volume are higher than the described of unit volume
The cracking activity of isomery hydrocracking catalyst I.
The boiling range range of first naphtha cut of the present invention is C5- 150 DEG C, the boiling range range of the light diesel fuel fraction
It is 150-320 DEG C, the heavy oil fraction is fraction of the boiling range at 320 DEG C or more.
The boiling range range of second naphtha cut of the present invention is C5- 150 DEG C, the boiling range range of the intermediate oil
It is 150-370 DEG C, the tail oil fraction is fraction of the boiling range at 370 DEG C or more.
When processing Fischer-Tropsch synthesis oil using the above method provided by the invention, the selectivity of intermediate oil can be improved,
Obtain the yield of higher intermediate oil.
In method of the present invention, particularly, the cracking activity of catalyst of the present invention can pass through control
Infrared acidity in the preparation process of isomery hydrocracking catalyst is realized.Infra-red sepectrometry is that most common analysis is solid
One of the acid process on body catalyst surface, its type of available catalyst surface acid, intensity and acid are measured simultaneously information.
The basic principle is that alkalinity probe molecule adsorbed by catalyst surface acidic site, the B acid and L acid on solid acid catalyst surface with
Alkaline probe molecule acts on forming different species, and some characteristic absorption bands are generated in infrared spectrum spectrogram or original suction occurs
Thus the displacement of take-up can measure type, intensity and the acidity of acid.Pyridine is most common alkaline probe molecule.
In method of the present invention, the hydrogeneous logistics refers to the logistics for being capable of providing hydrogen, including new hydrogen, circulation
Hydrogen, hydrogen-rich gas and other gaseous streams for being capable of providing hydrogen and it is other be capable of providing it is any in the liquid phase stream of hydrogen
It is one or more.Heretofore described hydrogeneous logistics can be the same or different, and those skilled in the art are understanding this
It can be clearly understood that heretofore described hydrogeneous logistics after the technical solution of invention.
N-alkane and isoparaffin cracking complexity is utilized in the method for above-mentioned processing Fischer-Tropsch synthesis oil of the invention
Different features further improves the selectivity and yield of the intermediate oil of Fischer-Tropsch synthesis oil isomery hydrocracking process,
Achieve the purpose that produce intermediate oil to greatest extent.
Method of the invention, which is used, adds hydrogen into the first isomery for the raw material heavy oil fraction being made of long linear n-alkane
Cracker converts band branch for n-alkane with the stronger isomery hydrocracking catalyst haptoreaction of isomerization activity
The isoparaffin of chain, while reducing generated isoparaffin cracking is light component C1-C4The probability of hydro carbons and naphtha cut,
Then the second hydrocracking reactor is mainly entered back by the reaction effluent that isoparaffin forms, it is stronger different with cracking activity
Structure hydrocracking catalyst haptoreaction obtains higher midbarrel oil yield and selection while guaranteeing higher conversion
Property.
Under preferable case, in the method for the invention, at least partly described tail oil fraction is recycled back to the first isomery and adds hydrogen
The entrance of cracker and the second isomery hydrocracking reactor, method of the invention are preferably recycled to the first isomery and hydrogen are added to split
The volume ratio for changing the tail oil fraction of reactor and the second isomery hydrocracking reactor is 1:1-10.
Another kind preferred embodiment according to the present invention, in method of the present invention, by the tail oil
Fraction is recycled back to the entrance of the second isomery hydrocracking reactor.
Method according to the present invention, under preferable case, with the tail oil in the second isomery hydrocracking reaction effluent
The total weight of fraction, the tail oil fraction for being recycled back to the isomery hydrocracking reactor entrance is 10-100 weight %；More
The tail oil fraction for being preferably recycled to the isomery hydrocracking reactor entrance is 50-100 weight %.
Method according to the present invention under preferable case, is with the isomery hydrocracking catalyst I of unit volume
The isomerization activity of benchmark, the isomery hydrocracking catalyst II of unit volume adds hydrogen to split than the isomery of unit volume
The isomerization activity at least low 15% of change catalyst I, more preferably at least low 25%.
Method according to the present invention under preferable case, is with the isomery hydrocracking catalyst I of unit volume
The cracking activity of benchmark, the isomery hydrocracking catalyst II of unit volume is hydrocracked than the isomery of unit volume
The cracking activity of catalyst I is at least high by 30%, more preferably at least high by 40%.
The inventors found that: since the charging of the first isomery hydrocracking reactor is mainly by n-alkane group
At, the stronger catalyst of isomerization activity has been loaded in the first isomery hydrocracking reactor, occur isomerization reaction it is same
When, cracking reaction inevitably occurs on a catalyst, therefore need to limit in the first hydrocracking reactor outlets products
The content of isoparaffin is can guarantee in this way while obtaining higher isoparaffin content, and generated isoparaffin is avoided to send out
Raw overcracking reaction, so as to avoid more light component C is generated1-C4Hydro carbons and naphtha cut have correspondingly improved intermediate
The selectivity and yield of distillate, and guarantee to provide for the second isomery hydrocracking reactor and be suitable for being converted into midbarrel
The raw material of oil being mainly made of isoparaffin.Therefore, in method of the present invention, the first isomery of control is hydrocracked instead
Answer the reaction condition in device, it is preferable that the content of isoparaffin is not in the reaction effluent of the first isomery hydrocracking reactor
Less than 60 weight %；More preferably it is not less than 70 weight %.
Method according to the present invention controls the reaction condition in the first isomery hydrocracking reactor, it is preferable that
C in the reaction effluent of first isomery hydrocracking reactor22-C40Fraction accounts for 50 weight % or more, is more preferably not less than 55
Weight %.Method of the invention passes through C in the first hydrocracking reactor outlets products of limitation22-C40The weight content of fraction,
It can guarantee the C in Fischer-Tropsch synthesis oil raw material in the first isomery hydrocracking reactor40+Wax slop fraction is to the full extent
It is converted into C22-C40Isomerization reaction is also carried out while light wax oil fraction, this also can effectively limit C simultaneously22-C40Fraction
Cracking level in the first isomery hydrocracker reduces and generates light component C1-C4The probability of hydro carbons and naphtha cut,
The selectivity and yield of intermediate oil accordingly are further improved, and can be further ensured that as the second isomery hydrocracking reaction
Device is upper to greatest extent to provide the C for being suitable for being converted into intermediate oil22-C40The raw material of carbon number range.
Using method provided by the invention, due to effectively controlling the cracking level in the first isomery hydrocracking reactor
And isomerisation degree, and the raw material of the second isomery hydrocracking reactor is mainly the branched isoparaffin for being easy to cracking
And the stronger catalyst of cracking activity is used, therefore the cracking more mitigated can be used in the second isomery hydrocracking reactor
Reaction condition, these measures each contribute to reduce bed temperature rise, effectively control cracker bed temperature, prevent isomery from adding hydrogen
Cracker temperature control ensure that the quiet run of device.
In the present invention, it is well known by those skilled in the art that the cracking activity in method of the invention can pass through >
The conversion ratios of 370 DEG C of fractions embodies.
In method of the present invention, the isomery hydrocracking catalyst I and isomery hydrocracking catalyst II's
Isomerization activity, cracking activity height each mean using identical F- T synthesis feedstock oil as test raw material carry out performance evaluation obtain
, the definition difference of the isomerization activity, cracking activity and intermediate oil selectivity is as follows:
Isomerization activity=(content × liquid yield-of isohydrocarbon in the reaction effluent of isomery hydrocracking reactor
The content of isohydrocarbon in Fischer-Tropsch synthesis oil raw material)/(content of normal hydrocarbon-isomery hydrocracking reaction in Fischer-Tropsch synthesis oil raw material
The content of normal hydrocarbon in the reaction effluent of device) × 100%；
Cracking activity=(content-isomery hydrocracking reactor reaction of 370 DEG C of fractions of > in Fischer-Tropsch synthesis oil raw material
Content × the liquid yield of 370 DEG C of fractions of > in effluent) in/Fischer-Tropsch synthesis oil raw material 370 DEG C of fractions of > content ×
100%；
Intermediate oil selectivity=(content × liquid of intermediate oil in the second isomery hydrocracking reactor product
The content of the fraction of intermediate oil boiling range range is corresponded in the charging of yield the-the first isomery hydrocracking reactor)/(first is different
370 DEG C of fractions of > contain in content the-the second isomery isocrackate of 370 DEG C of fractions of > in the charging of structure hydrocracking reactor
Amount × liquid yield) × 100%.
In method of the present invention, since olefin(e) centent is very high in Fischer-Tropsch synthesis oil, if alkene directly with add hydrogen
Catalyst for refining haptoreaction, meeting vigorous reaction generate a large amount of coke on Hydrobon catalyst and hydrofinishing are caused to be catalyzed
The decline of agent activity；General in Fischer-Tropsch synthesis oil also to contain a certain amount of metal, these metals are easily deposited on hydrofinishing catalysis
At the top of agent, hydrofining reactor is caused to occur pressure difference quickly, while being deposited on the metal on Hydrobon catalyst and will cause
The permanent deactivation of Hydrobon catalyst preferably loads hydrogenation protecting catalyst for the long-term operation for guaranteeing commercial plant
At the top of Hydrobon catalyst, to avoid the generation of above-mentioned phenomenon.In method of the present invention, according to reactant
The flow direction of stream successively loads hydrogenation protecting catalyst and the Hydrobon catalyst in the preferably described hydrofining reactor.
In method of the present invention, in the hydrofining reactor, preferably hydrogenation protecting catalyst and plus hydrogen
The admission space ratio of catalyst for refining is 2-30:100；Preferably 5-15:100.
Method according to the present invention includes carrier in the preferably described hydrogenation protecting catalyst and is supported on the carrier
On active component element, the active component element be group vib metallic element and/or group VIII metal element.
In method of the present invention, the amorphous as carrier is contained in the preferably described Hydrobon catalyst
The group vib metallic element and/or group VIII metal element of aluminium and load on the carrier.
In more preferred situation, in method of the present invention, in the Hydrobon catalyst, the group vib
Metallic element is Mo and/or W, and the group VIII metal element is Co and/or Ni.
Method according to the present invention, with the total weight of the isomery hydrocracking catalyst I, the preferably described isomery
The aluminium oxide of amorphous aluminum silicate, 20-65 weight % containing 10-45 weight % in hydrocracking catalyst I, in terms of oxide
The group vib metallic element of 10-40 weight %, 2-15 weight % in terms of oxide group VIII metal element.More preferably
In the case of, in the isomery hydrocracking catalyst I, with the total weight of the amorphous aluminum silicate, the amorphous silicon
SiO containing 20-50 weight % in sour aluminium2, specific surface area 200-600m2/ g, Kong Rongwei 0.8-3.5mL/g, can several aperturesInfrared acidity is 0.15-0.45mmol/g.
Method according to the present invention, it is preferably described different with the total weight of the isomery hydrocracking catalyst II
Contain in structure hydrocracking catalyst II: the amorphous aluminum silicate of 30-75 weight %, the aluminium oxide of 10-50 weight %, with oxidation
The group VIII metal element of the group vib metallic element of the 10-40 weight % of object meter, 2-15 weight % in terms of oxide.More
It is preferred that in the isomery hydrocracking catalyst II, with the total weight of the amorphous aluminum silicate, the amorphous silicic acid
SiO containing 20-50 weight % in aluminium2, specific surface area 300-650m2/ g, Kong Rongwei 0.5-2.0mL/g, can several aperturesInfrared acidity is 0.5-0.8mmol/g.
In method of the present invention, the isomery loaded in the preferably described first isomery hydrocracking reactor adds hydrogen to split
The volume ratio for changing the isomery hydrocracking catalyst II loaded in catalyst I and the second isomery hydrocracking reactor is 1:
1.1-10。
In method of the present invention, the reaction condition in the preferably described hydrofining reactor includes: that hydrogen partial pressure is
3.0-10.0MPa, reaction temperature are 280-350 DEG C, hydrogen to oil volume ratio 100-800:1, volume space velocity 1.0-6.0h-1。
In method of the present invention, the reaction condition in the preferably described first isomery hydrocracking reactor includes:
Hydrogen partial pressure is 3.0-10.0MPa, and reaction temperature is 340-400 DEG C, hydrogen to oil volume ratio 300-1000:1, volume space velocity 1.0-
6.0h-1。
In method of the present invention, the reaction condition in the preferably described second isomery hydrocracking reactor includes:
Hydrogen partial pressure is 3.0-10.0MPa, and reaction temperature is 320-380 DEG C, hydrogen to oil volume ratio 300-1000:1, volume space velocity 1.0-
8.0h-1。
Method according to the present invention, since isomery hydrocracking reaction has a small amount of alkene to generate, to ensure product
Quality stablize, preferably isomery hydrocracking reactor bottom filling it is suitable after catalyst for refining, rear catalyst for refining with
The admission space ratio of isomery hydrocracking catalyst is 2-15:100, preferably 5-10:100.Method of the invention is to rear purification
There is no particular limitation for the type of catalyst, and those skilled in the art can be using conventional use of various rear purifications in the art
Catalyst is in method of the invention.
In the method for the invention, the preferably described first isomery hydrocracking reactor and second isomery are hydrocracked
At least one catalyst bed is respectively provided in reactor, the more preferred first isomery hydrocracking reactor and described second
2-5 catalyst bed is set in isomery hydrocracking reactor.Method of the invention preferably the first isomery hydrocracking reaction
The admission space of isomery hydrocracking catalyst in each catalyst bed of device and the second isomery hydrocracking reactor
It is identical.
In method of the present invention, the preferably described Fischer-Tropsch synthesis oil is the cold-trap from syrup state bed Fischer Tropsch synthesis technology
Material, the full fraction of hot trap material and synthetic wax and/or synthesis light oil, synthesis of heavy oil and synthesis from fixed bed fischer-tropsch synthesis process
The full fraction of wax.
A kind of preferred specific implementation method according to the present invention, method of the invention are illustrated using process shown in FIG. 1
The method of figure carries out, specifically as follows:
Fischer-Tropsch synthesis oil 1 is reacted into hydrofining reactor 2, and the logistics that hydrofining reactor 2 comes out enters
First high pressure hot separator 3 carries out gas-liquid separation, and the liquid phase that the first high pressure hot separator 3 comes out enters the first thermal low-pressure separators
6, the gas phase of the first high pressure hot separator 3 enters the first cold high pressure separator 4 and is further separated into gas phase, liquid hydrocarbon and water 5, the
The gas phase that one cold high pressure separator 4 is separated is hydrogen-rich gas 15, is mixed after the boosting of circulating hydrogen compressor 16 with new hydrogen 17
Between 18 Returning reactor entrance of circulating air and bed afterwards, liquid hydrocarbon and first that the first cold high pressure separator 4 is separated
The gas phase of thermal low-pressure separators 6 enters the 7 further progress gas-liquid separation of the first cold low separator, the separation of the first cold low together
The low liquid separation phase 9 of the first heat for the first cold low liquid separation phase 8 and the first thermal low-pressure separators 6 that device 7 is separated enters first together
Fractionating column 10 is separated into the first naphtha cut 11, light diesel fuel fraction 12 and the heavy oil fraction 13 of hydrofinishing unit, and first is cold
The gas phase that the gas phase and the first fractionating column 10 that low pressure separator 7 is separated are separated is discharged as first low point of gas 14.
Heavy oil fraction 13 sequentially enters the first isomery hydrocracking reactor 19 and the second isomery hydrocracking reactor 20 again, carries out different
Structure hydrocracking reaction, the logistics that the second isomery hydrocracking reactor 20 comes out enter the second high pressure hot separator 21 and carry out gas
Liquid separation, the liquid phase that the second high pressure hot separator 21 comes out enter the second thermal low-pressure separators 23, the second high pressure hot separator 21
Gas phase enter the second cold high pressure separator 22 be further separated into gas phase and liquid phase, the second cold high pressure separator 22 is separated
The second cold high score gas phase 32 remove circulating hydrogen compressor 16, the liquid phase that the second cold high pressure separator 22 is separated is low with the second heat
The gas phase of pressure separator 23 enters the 24 further progress gas-liquid separation of the second cold low separator, the second cold low separator together
The second low liquid separation phase 25 of heat of 24 the second cold low liquid separation phases 26 and the second thermal low-pressure separators 23 separated enters the together
Two fractionating columns 27 are separated into the second naphtha cut 28, intermediate oil 29 and the tail oil fraction 30 of isomery Hydrocracking unit,
The gas phase that the gas phase and after-fractionating tower 27 that second cold low separator 24 is separated are separated is as second low point of gas
31 discharges, wherein tail oil fraction is recycled into the first isomery hydrocracking reactor 19 and/or the second isomery hydrocracking reaction
The entrance of device 20 is further converted.
The above method of the invention also has the advantages that following specific:
(1) hydrofining reaction and the relatively independent process flow of isomery hydrocracking reaction, which can respectively obtain, has difference
Performance, the purpose product for meeting different product specification, products scheme are flexible；
(2) it is provided with two isomery hydrocracking reactors in method of the invention, and loads isomerization activity and cracking
The different isomery hydrocracking catalyst of activity, takes full advantage of the spy for being easy to cracking compared with n-alkane with branched chain isomer alkane
Point reduces n-alkane and has generated the secondary cracking extent of reaction of isoparaffin, reduces light component C1-C4Hydro carbons and
The generation of naphtha cut further improves the selectivity and yield of intermediate oil；
(3) method provided by the invention can improve the selectivity and yield of intermediate oil to greatest extent, realize maximum
The purpose of amount production intermediate oil, improves the economic benefit of device；
(4) method of the invention is used, due to effectively controlling the cracking level in the first isomery hydrocracking reactor
And isomerisation degree, and the second isomery hydrocracking reactor uses the cracking reaction condition more mitigated, these measures
It each contributes to reduce bed temperature rise, effectively controls the bed temperature of isomery hydrocracking reactor, isomery is prevented to be hydrocracked instead
Device temperature control is answered, ensure that the quiet run of device.
The present invention will be described in detail by way of examples below.In following embodiment, in the feelings being not particularly illustrated
Under condition, used various raw materials are all from commercially available.
Feedstock oil used in following embodiment and comparative example is the full fraction of Fischer-Tropsch synthesis oil, and property is shown in Table shown in 1.
The trade names of Hydrobon catalyst are RTF-1 (diameter 1.4mm), and the number of isomery hydrocracking catalyst I respectively includes
CDB-39, CDB-40, CDB-41, CDB-42, CDB-46, isomery hydrocracking catalyst II trade names be RCF-1.Add hydrogen
Guard catalyst is RGF series protective agent, is the grading loading of five kinds of guard catalysts, trade names include RGF-20, RGF-
30E, RGF-30A, RGF-30B, RGF-1, the trade names of rear catalyst for refining are RTF-1 (diameter 3.4mm), the above catalyst
It is produced by China Petrochemical Corp.'s catalyst Chang Ling branch company.In the case where no explanation on the contrary, add described
In hydrogen finishing reactor, the admission space ratio of the hydrogenation protecting catalyst and the Hydrobon catalyst is 10:100；?
In the isomery hydrocracking reactor, the admission space ratio of the isomery hydrocracking catalyst and the rear catalyst for refining
For 8:100；The volume ratio of isomery hydrocracking catalyst I and isomery hydrocracking catalyst II is 1:3.
Wherein, the composition of the CDB-39 are as follows: with the total weight of the catalyst, 16.2 weights are contained in the catalyst
Measure the amorphous aluminum silicate of %, the aluminium oxide of 51.3 weight %, the tungsten oxide of 25.1 weight % in terms of oxide, with oxide
The nickel oxide of 7.4 weight % of meter, infrared acidity are 0.20mmol/g.
The composition of the CDB-40 are as follows: with the total weight of the catalyst, 26.0 weight % are contained in the catalyst
Amorphous aluminum silicate, the aluminium oxide of 41.5 weight %, the tungsten oxide of 24.8 weight % in terms of oxide, in terms of oxide
The nickel oxide of 7.7 weight %, infrared acidity are 0.25mmol/g.
The composition of the CDB-41 are as follows: with the total weight of the catalyst, 29.7 weight % are contained in the catalyst
Amorphous aluminum silicate, the aluminium oxide of 38.1 weight %, the tungsten oxide of 24.3 weight % in terms of oxide, in terms of oxide
The nickel oxide of 7.9 weight %, infrared acidity are 0.32mmol/g.
The composition of the CDB-42 are as follows: with the total weight of the catalyst, 34.4 weight % are contained in the catalyst
Amorphous aluminum silicate, the aluminium oxide of 33.6 weight %, the tungsten oxide of 24.0 weight % in terms of oxide, in terms of oxide
The nickel oxide of 8.0 weight %, infrared acidity are 0.37mmol/g.
The composition of the CDB-46 are as follows: with the total weight of the catalyst, 29.1 weight % are contained in the catalyst
Amorphous aluminum silicate, the aluminium oxide of 38.7 weight %, the tungsten oxide of 24.9 weight % in terms of oxide, in terms of oxide
The nickel oxide of 7.3 weight %, infrared acidity are 0.28mmol/g.
Table 1
| Fischer-Tropsch synthesis oil raw material | |
| Density (20 DEG C)/(g/cm3) | 0.7900 |
| Oxygen content/(μ g/g) | 0.51 |
| C content/weight % | 85.24 |
| H content/weight % | 14.66 |
| Boiling range ASTM D-1160/ DEG C | |
| IBP | 68 |
| 50% | 389 |
| 95% | 643 |
| Tenor/(μ g/g) | |
| Fe | 7.1 |
| Cu | 0.1 |
| Mg | 0.3 |
| Na | 0.8 |
| Ca | 0.2 |
| Al | 0.4 |
Embodiment 1
The method that the present embodiment is used to illustrate processing Fischer-Tropsch synthesis oil of the present invention is specifically as follows:
Fischer-Tropsch synthesis oil raw material enters hydrofining reactor, with Hydrobon catalyst RTF-1 haptoreaction, adds hydrogen smart
Reaction effluent processed sequentially enters separation and fractionating system obtains the first naphtha cut, light diesel fuel fraction and heavy oil fraction.Its
In, heavy oil fraction is successively introduced to the first isomery hydrocracking reactor and the second isomery hydrocracking reactor, respectively with it is different
Structure hydrocracking catalyst I and isomery hydrocracking catalyst II haptoreaction, by the anti-of the second isomery hydrocracking reactor
Answer that effluent sequentially enters separation and fractionating system obtains the second naphtha cut, intermediate oil and tail oil fraction, tail oil evaporates
Divide and is all recycled back to the reaction of the second isomery hydrocracking reactor entrance further progresss.Wherein, with the described different of unit volume
On the basis of structure hydrocracking catalyst I, the cracking activity of the RCF-1 catalyst of unit volume is compared with unit under the conditions of same process
The CDB-46 high 40% of volume, isomerization activity then low 25%, and control the reaction stream of the first isomery hydrocracking reactor
The content of isoparaffin is not less than 70 weight %, and C in object out22-C40The content of fraction is not less than 55 weight %.Specific reaction
Condition, reactivity worth and isomery hydrocracked product property are shown in Table 2 and table 3 respectively.Wherein, the naphtha cut in table 3 is this
Invent the second naphtha cut (similarly hereinafter) above-mentioned.
From the results shown in Table 3, the selectivity of the intermediate oil of the present embodiment is 83.20%, and two isomeries add
The bed overall temperature rise of hydrogen cracker only has 62 DEG C, this illustrates method provided by the invention, on the one hand reduces n-alkane
And the secondary cracking extent of reaction of isoparaffin, reduce light component C1-C4The generation of hydro carbons and naphtha cut, effectively mentions
The high selectivity and yield of intermediate oil；On the other hand, due to effectively limiting in the first isomery hydrocracking reactor
Reaction depth and the second isomery hydrocracking reactor use the cracking reaction condition that more mitigates, this facilitates effectively
Bed temperature is limited, temperature control is prevented, effectively promotes the quiet run of device.
Can also be seen that the second naphtha cut is mainly made of n-alkane and isoparaffin from the result of table 3, be compared with
Good steam crack material, the Cetane number of intermediate oil are 82, and sulphur, nitrogen content are very low, can be used as high cetane number
Diesel oil blending component.
Embodiment 2
The method that the present embodiment is used to illustrate processing Fischer-Tropsch synthesis oil of the present invention is specifically as follows:
Fischer-Tropsch synthesis oil raw material enters hydrofining reactor, with Hydrobon catalyst RTF-1 haptoreaction, adds hydrogen smart
Reaction effluent processed sequentially enters separation and fractionating system obtains the first naphtha cut, light diesel fuel fraction and heavy oil fraction.Its
In, heavy oil fraction is successively introduced to the first isomery hydrocracking reactor and the second isomery hydrocracking reactor, respectively with it is different
Structure hydrocracking catalyst I and isomery hydrocracking catalyst II haptoreaction, by the anti-of the second isomery hydrocracking reactor
Answer that effluent sequentially enters separation and fractionating system obtains the second naphtha cut, intermediate oil and tail oil fraction, tail oil evaporates
Divide and is all recycled back to the reaction of the first isomery hydrocracking reactor entrance further progresss.Wherein, with the described different of unit volume
On the basis of structure hydrocracking catalyst I, the cracking activity of the RCF-1 catalyst of unit volume is compared with unit under the conditions of same process
The CDB-39 high 50% of volume, isomerization activity then low 35%, and control the reaction stream of the first isomery hydrocracking reactor
The content of isoparaffin is not less than 80%, and C in object out22-C40The content of fraction is not less than 65 weight %.Specific reaction condition,
Reactivity worth and isomery hydrocracked product property are shown in Table 2 and table 3.
From the results shown in Table 3, the selectivity of the intermediate oil of the present embodiment is 82.90%, and two isomeries add
The bed overall temperature rise of hydrogen cracker only has 64 DEG C, this illustrates method provided by the invention, on the one hand reduces n-alkane
And the secondary cracking extent of reaction of isoparaffin, reduce light component C1-C4The generation of hydro carbons and naphtha cut, effectively mentions
The high selectivity and yield of intermediate oil；On the other hand, due to effectively limiting in the first isomery hydrocracking reactor
Reaction depth and the second isomery hydrocracking reactor use the cracking reaction condition that more mitigates, this facilitates effectively
Bed temperature is limited, temperature control is prevented, effectively promotes the quiet run of device.
Can also be seen that the second naphtha cut is mainly made of n-alkane and isoparaffin from the result of table 3, be compared with
Good steam crack material, the Cetane number of intermediate oil are 80, and sulphur, nitrogen content are very low, can be used as high cetane number
Diesel oil blending component.
Comparative example 1
This comparative example is carried out using method similar to Example 1, the difference is that two isomeries add hydrogen in this comparative example
Isomery hydrocracking catalyst II is loaded in cracker, and the first isomery hydrocracking reactor and the second isomery add hydrogen
The volume ratio of the isomery hydrocracking catalyst II loaded in cracker is in the same manner as in Example 1.Remaining with comparative example 1
In it is identical.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 2 and table 3 respectively.
From the results shown in Table 3, under 370 DEG C of fraction conversion ratio similar conditions of >, midbarrel in this comparative example
The selectivity of oil is 76.03%, and the bed total temperature of two isomery hydrocracking reactors is upgraded to 79 DEG C.
Comparative example 2
This comparative example is carried out using method similar with comparative example 1, the difference is that two isomeries add hydrogen in this comparative example
Isomery hydrocracking catalyst I is loaded in cracker, and the first isomery hydrocracking reactor and the second isomery add hydrogen
The volume ratio of the isomery hydrocracking catalyst I loaded in cracker is identical with comparative example 1.Remaining with comparative example 1
In it is identical.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 2 and table 3 respectively.
From the results shown in Table 3, under 370 DEG C of fraction conversion ratio similar conditions of >, midbarrel in this comparative example
The selectivity of oil is 76.36%, and the bed total temperature of two isomery hydrocracking reactors is upgraded to 77 DEG C.
Comparative example 3
This comparative example is carried out using method similar to Example 1, the difference is that the first isomery adds hydrogen in this comparative example
Isomery hydrocracking catalyst II is loaded in cracker, and loads isomery in the second isomery hydrocracking reactor and hydrogen is added to split
Change catalyst I.Remaining is identical with comparative example 1.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 2 and table 3 respectively.
From the results shown in Table 3, under 370 DEG C of fraction conversion ratio similar conditions of >, midbarrel in this comparative example
The selectivity of oil is 76.21%, and the bed total temperature of two isomery hydrocracking reactors is upgraded to 76 DEG C.
Table 2
Table 3
Embodiment 3
Fischer-Tropsch synthesis oil raw material enters hydrofining reactor, with Hydrobon catalyst RTF-1 haptoreaction, adds hydrogen smart
Reaction effluent processed sequentially enters separation and fractionating system obtains the first naphtha cut, light diesel fuel fraction and heavy oil fraction.Its
In, heavy oil fraction is successively introduced to the first isomery hydrocracking reactor and the second isomery hydrocracking reactor, respectively with it is different
Structure hydrocracking catalyst I and isomery hydrocracking catalyst II haptoreaction, by the anti-of the second isomery hydrocracking reactor
It answers that effluent sequentially enters separation and fractionating system obtains the second naphtha cut, intermediate oil and tail oil fraction, all follows
Loopback the first isomery hydrocracking reactor and the reaction of the second isomery hydrocracking reactor entrance further progress, and introduce
The tail oil weight ratio of first isomery hydrocracking reactor and the second isomery hydrocracking reactor is 1:3.Wherein, with unit bodies
On the basis of the long-pending isomery hydrocracking catalyst I, the cracking of the RCF-1 catalyst of unit volume under the conditions of same process
CDB-40 high 45% of the activity compared with unit volume, isomerization activity then low 30%, and control the first isomery hydrocracking reaction
The content of isoparaffin is not less than 75%, and C in the reaction effluent of device22-C40The content of fraction is not less than 60 weight %.Tool
Precursor reactant condition, reactivity worth and isomery hydrocracked product property are shown in Table 4 and table 5.
From the results shown in Table 5, the selectivity of the intermediate oil of the present embodiment is 83.02%, and two isomeries add
The bed overall temperature rise of hydrogen cracker only has 63 DEG C.The Cetane number of intermediate oil is 80, and sulphur, nitrogen content are very low, can
Diesel oil blending component as high cetane number.
Embodiment 4
The present embodiment is carried out using method similar to Example 1, unlike:
In the present embodiment, with the total weight of the tail oil fraction in the second isomery hydrocracking reaction effluent, it is recycled back to
The tail oil fraction of the second isomery hydrocracking reactor entrance is 40 weight %.Remaining is in the same manner as in Example 1.
Product property after specific reaction condition, reactivity worth and isomery hydrocracking reaction is shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 82.94%, the bed of cracker
Temperature rise is 63 DEG C.The Cetane number of intermediate oil is 81, and sulphur, nitrogen content are very low, can be used as the reconciliation of high cetane number diesel oil
Component.
Embodiment 5
The present embodiment is carried out using method similar to Example 2, unlike:
In the present embodiment, on the basis of the isomery hydrocracking catalyst I of unit volume, under the conditions of same process
CDB-41 high 35% of the cracking activity of the RCF-1 catalyst of unit volume compared with unit volume, isomerization activity then low 20%.Its
Yu Jun is in the same manner as in Example 2.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 82.47%, the bed of cracker
Temperature rise is 65 DEG C.The Cetane number of intermediate oil is 79, and sulphur, nitrogen content are very low, can be used as the reconciliation of high cetane number diesel oil
Component.
Embodiment 6
The present embodiment is carried out using method similar to Example 5, unlike:
In the present embodiment, on the basis of the isomery hydrocracking catalyst I of unit volume, under the conditions of same process
CDB-42 high 25% of the cracking activity of the RCF-1 catalyst of unit volume compared with unit volume, isomerization activity then low 10%.Its
Yu Jun is in the same manner as in Example 5.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 82.09%, the bed of cracker
Temperature rise is 67 DEG C.The Cetane number of intermediate oil is 78, and sulphur, nitrogen content are very low, can be used as the reconciliation of high cetane number diesel oil
Component.
Embodiment 7
The present embodiment is carried out using method similar to Example 3, unlike:
The difference is that the reaction condition in the first isomery hydrocracking reactor is controlled in the present embodiment, so that first
The content of isoparaffin is not less than 60 weight % in the reaction effluent of isomery hydrocracking reactor, and the first isomery adds hydrogen to split
The content for changing C22-C40 fraction in the reaction effluent of reactor is not less than 50 weight %.Remaining is in the same manner as in Example 3.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 82.89%, the bed of cracker
Temperature rise is 65 DEG C.The Cetane number of intermediate oil is 80, and sulphur, nitrogen content are very low, can be used as the reconciliation of high cetane number diesel oil
Component.
Embodiment 8
The present embodiment is carried out using method similar to Example 7, unlike:
The difference is that the reaction condition in the first isomery hydrocracking reactor is controlled in the present embodiment, so that first
The content of isoparaffin is not less than 50 weight % in the reaction effluent of isomery hydrocracking reactor, and the first isomery adds hydrogen to split
The content for changing C22-C40 fraction in the reaction effluent of reactor is not less than 40 weight %.Remaining is in the same manner as in Example 7.
Specific reaction condition, reactivity worth and isomery hydrocracked product property are shown in Table 4 and table 5.
As can be seen from Table 5, the selectivity of the intermediate oil of the present embodiment is 82.61%, the bed of cracker
Temperature rise is 67 DEG C.The Cetane number of intermediate oil is 79, and sulphur, nitrogen content are very low, can be used as the reconciliation of high cetane number diesel oil
Component.
Table 4
Table 5
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (17)
1. a kind of method for processing Fischer-Tropsch synthesis oil adds hydrogen this method comprises: Fischer-Tropsch synthesis oil and hydrogeneous logistics are introduced to contain
It is reacted in the hydrofining reactor of catalyst for refining, then hydrofining reaction effluent is successively separated, is obtained
To the first naphtha cut, light diesel fuel fraction and heavy oil fraction；The heavy oil fraction is successively introduced and is hydrocracked containing isomery
The first isomery hydrocracking reactor of catalyst I and the second isomery containing isomery hydrocracking catalyst II are hydrocracked instead
It answers in device, then successively separates the reaction effluent of the second isomery hydrocracking reactor, obtain the second stone brain
At least partly described tail oil fraction is optionally recycled back to the first isomery and hydrogen is added to split by oil distillate, intermediate oil and tail oil fraction
Change the entrance of reactor and/or the second isomery hydrocracking reactor；Wherein, it is hydrocracked and is urged with the isomery of unit volume
On the basis of agent I, the isomerization activity of the isomery hydrocracking catalyst II of unit volume is described more different than unit volume
The isomerization activity at least low 15% of structure hydrocracking catalyst I；The isomery hydrocracking catalyst II's of unit volume splits
It is at least higher by 30% than the cracking activity of the isomery hydrocracking catalyst I of unit volume to change activity；It controls the first isomery and adds hydrogen
Reaction condition in cracker so that in the reaction effluent of the first isomery hydrocracking reactor isoparaffin content
Not less than 60 weight %.
2. according to the method described in claim 1, wherein, with the tail in the reaction effluent of the second isomery hydrocracking reactor
The total weight of oil distillate, the tail oil fraction for being recycled back to isomery hydrocracking reactor entrance is 10-100 weight %.
3. according to the method described in claim 1, wherein, with the tail in the reaction effluent of the second isomery hydrocracking reactor
The total weight of oil distillate, the tail oil fraction for being recycled back to isomery hydrocracking reactor entrance is 50-100 weight %.
4. according to the method described in claim 1, wherein, on the basis of the isomery hydrocracking catalyst I of unit volume,
The isomerization activity of the isomery hydrocracking catalyst II of unit volume is hydrocracked than the isomery of unit volume urges
The isomerization activity of agent I at least low 25%；
The cracking activity of the isomery hydrocracking catalyst II of unit volume is hydrocracked than the isomery of unit volume
The cracking activity of catalyst I is at least high by 40%.
5. method described in any one of -4 according to claim 1, wherein in the first isomery hydrocracking reactor of control
Reaction condition, so that the content of isoparaffin is not less than 70 weight % in the reaction effluent of the first isomery hydrocracking reactor.
6. method described in any one of -4 according to claim 1, wherein in the first isomery hydrocracking reactor of control
Reaction condition, so that C in the reaction effluent of the first isomery hydrocracking reactor22-C40The content of fraction is not less than 50 weights
Measure %.
7. method described in any one of -4 according to claim 1, wherein in the first isomery hydrocracking reactor of control
Reaction condition, so that C in the reaction effluent of the first isomery hydrocracking reactor22-C40The content of fraction is not less than 55 weights
Measure %.
8. according to the method described in claim 1, wherein, according to the flow direction of reaction stream, in the hydrofining reactor according to
Secondary filling hydrogenation protecting catalyst and the Hydrobon catalyst, the filling of hydrogenation protecting catalyst and Hydrobon catalyst
Volume ratio is 2-30:100.
9. including carrier according to the method described in claim 8, wherein, in the hydrogenation protecting catalyst and being supported on the load
Active component element on body, the active component element are group vib metallic element and/or group VIII metal element.
10. according to the method described in claim 1, wherein, containing in the Hydrobon catalyst as the amorphous of carrier
The group vib metallic element and/or group VIII metal element of aluminium oxide and load on the carrier, the group vib metal member
Element is Mo and/or W, and the group VIII metal element is Co and/or Ni.
11. method described in any one of -4 according to claim 1, wherein with the total of the isomery hydrocracking catalyst I
Poidometer, the oxidation of the amorphous aluminum silicate containing 10-45 weight %, 20-65 weight % in the isomery hydrocracking catalyst I
The group VIII metal member of aluminium, the group vib metallic element of 10-40 weight % in terms of oxide, 2-15 weight % in terms of oxide
Element.
12. according to the method for claim 11, wherein described amorphous with the total weight of the amorphous aluminum silicate
SiO containing 20-50 weight % in alumina silicate2, the specific surface area of the amorphous aluminum silicate is 200-600m2/ g, Kong Rongwei
0.8-3.5mL/g, can several apertures be 72-78, infrared acidity be 0.15-0.45mmol/g.
13. method described in any one of -4 according to claim 1, wherein with the isomery hydrocracking catalyst II's
Total weight contains in the isomery hydrocracking catalyst II: the amorphous aluminum silicate of 30-75 weight %, 10-50 weight %
Aluminium oxide, the group vib metallic element of 10-40 weight % in terms of oxide, 2-15 weight % in terms of oxide VIII group gold
Belong to element.
14. according to the method for claim 13, wherein described amorphous with the total weight of the amorphous aluminum silicate
SiO containing 20-50 weight % in alumina silicate2, the specific surface area of the amorphous aluminum silicate is 300-650m2/ g, Kong Rongwei
0.5-2.0mL/g, can a few aperture 62-68, infrared acidity be 0.5-0.8mmol/g.
15. according to the method described in claim 1, wherein, the reaction condition in the hydrofining reactor includes: hydrogen partial pressure
For 3.0-10.0MPa, reaction temperature is 280-350 DEG C, hydrogen to oil volume ratio 100-800:1, volume space velocity 1.0-6.0h-1。
16. according to the method described in claim 1, wherein, the reaction condition packet in the first isomery hydrocracking reactor
Include: hydrogen partial pressure 3.0-10.0MPa, reaction temperature are 340-400 DEG C, hydrogen to oil volume ratio 300-1000:1, and volume space velocity is
1.0-6.0h-1；Reaction condition in the second isomery hydrocracking reactor includes: that hydrogen partial pressure is 3.0-10.0MPa, reaction
Temperature is 320-380 DEG C, hydrogen to oil volume ratio 300-1000:1, volume space velocity 1.0-8.0h-1。
17. according to the method described in claim 1, wherein, the Fischer-Tropsch synthesis oil is from syrup state bed Fischer Tropsch synthesis technology
Cold-trap material, the full fraction of hot trap material and synthetic wax and/or synthesis light oil from fixed bed fischer-tropsch synthesis process, synthesis of heavy oil and
The full fraction of synthetic wax.
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| CN1814703A (en) * | 2005-08-10 | 2006-08-09 | 上海兖矿能源科技研发有限公司 | Method for producing diesel or diesel composition using Fischer-Tropsch synthetic product |
| CN1854265A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Production of intermediate fractional oil from Fischer-Tropsch synthetic oil |
| CN103897718A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for production of diesel oil fraction and aviation fuel fraction by use of animal and plant oils and fats |
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| CN1854265A (en) * | 2005-04-29 | 2006-11-01 | 中国石油化工股份有限公司 | Production of intermediate fractional oil from Fischer-Tropsch synthetic oil |
| CN1814703A (en) * | 2005-08-10 | 2006-08-09 | 上海兖矿能源科技研发有限公司 | Method for producing diesel or diesel composition using Fischer-Tropsch synthetic product |
| CN103897718A (en) * | 2012-12-27 | 2014-07-02 | 中国石油天然气股份有限公司 | Method for production of diesel oil fraction and aviation fuel fraction by use of animal and plant oils and fats |
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