CN105778995B - The method and its equipment of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil - Google Patents
The method and its equipment of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil Download PDFInfo
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- CN105778995B CN105778995B CN201610238808.2A CN201610238808A CN105778995B CN 105778995 B CN105778995 B CN 105778995B CN 201610238808 A CN201610238808 A CN 201610238808A CN 105778995 B CN105778995 B CN 105778995B
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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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
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Abstract
The invention discloses the method and its equipment of a kind of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil, method comprises the following steps：1) Fischer-Tropsch diesel is subjected to mixed hydrogen processing, being hydrogenated with mode using liquid phase circulation after the molten hydrogen of saturation carries out hydrofinishing；2) the hydrofining reaction thing that step 1) obtains is mixed with inferior feedstock oil and Fischer-Tropsch wax oil, obtains miscella, be then hydrogenated with mode using gas-liquid counter current carries out hydrofinishing to the miscella；3) the hydrofining reaction thing that step 2) obtains is hydrocracked and isomerization reaction using gas-liquid counter current hydrogenation mode；4) liquid phase production oil obtained by step 3) is fractionated, obtains fine-quality diesel oil.The invention provides a kind of be combined liquid-phase hydrogenatin with vapour-liquid countercurrent hydrogenation to be processed the process for producing fine-quality diesel oil to Fischer-Tropsch synthesis oil and poor ignition quality fuel, has obtained the diesel oil that density is qualified, Cetane number is high.
Description
Technical field
The present invention relates to diesel production technology, in particular to a kind of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining
Produce the method and its equipment of fine-quality diesel oil.
Background technology
With the environmental regulation that the in short supply and countries in the world of petroleum resources are increasingly stricter, cleaning alternative energy source technology is opened
Hair is gradually taken seriously, and wherein F- T synthesis technology using raw materials such as coal, natural gas, biomass because that can produce high cleaning combustion
Expect and receive much concern.F- T synthesis technology is divided into high temperature fischer-tropsch synthetic technology and Low Temperature Fischer Tropsch closes according to the height of reaction temperature
Into technology.Composition and the oil difference of Fischer-Tropsch synthetic are larger, because being limited by Anderson-Schulz-Flory rules,
Its product mainly contains C4-C70Hydro carbons and a small amount of oxygenatedchemicals complex mixture, have without sulphur, nitrogen-free, without metal, low
The features such as aromatic hydrocarbons, wherein, Low Temperature Fischer Tropsch synthetic product is mainly made up of linear paraffin and alkene, and contains on a small quantity oxygen-containing organic
Compound.Containing nearly 40% wax in Low Temperature Fischer Tropsch synthetic product product, although Cetane number, more than 70, condensation point pour point is too high,
Cold flow properties are too poor, it is impossible to are directly used as transporting fuel oil.One of main purpose of F- T synthesis technology produces high-quality
Diesel oil, each cut in Fischer-Tropsch synthetic need to pass through corresponding hydrogenation upgrading, can just obtain qualified product.And low temperature takes
Support synthetic product is because having the characteristics that linear paraffin is high, condensation point is high, density is low so that the diesel oil distillate condensation point after hydrogenation is high, close
Spend low, can not be sold directly as commercial Dissel oil.At the same time, in refinery's work flow, contain in secondary processing diesel oil inferior
Have substantial amounts of aromatic hydrocarbons, density is higher, but Cetane number is very low, and the secondary processing diesel oil such as catalytic diesel oil, coker gas oil due to
Containing impurity contents such as higher sulphur, nitrogen and aromatic hydrocarbons, the H of generation is reacted in hydrogenation process2S、NH3It is competing Deng gaseous impurity
Absorption is striven on the activated centre of catalyst surface, has larger inhibitory action with isomerization etc. to being hydrocracked, is hydrocracked
Required reaction temperature can be very high, and then can influence catalyst service life, energy consumption and running cost.
There are some in the prior art on how to utilize Low Temperature Fischer Tropsch synthetic product to produce the report of diesel oil, such as：It is Chinese special
Sharp CN10313468A discloses a kind of Low Temperature Fischer Tropsch artificial oil hydrofinishing and/or hydroisomerizing process method, this method
Liquid-phase hydrogenatin and lower feeding manner are used for hydrofinishing or Hydrocracking unit, this method weak point is resulting diesel oil
Density is relatively low, only 0.7586g/cm3；A kind of method for producing intermediate oil, the party are disclosed in United States Patent (USP) US6858127
For at least part artificial oil is hydrocracked coal diesel oil distillate therein is then demultiplex out, tail oil carries out hydrogenation and split again in method
Change, then the coal diesel oil distillate in separation product, wherein diesel oil distillate density is 0.78g/cm3, condensation point be -28~0 DEG C, this method
Weak point is that diesel oil distillate density is relatively low, does not reach derv fuel index.
The content of the invention
It is high-quality present invention aim to provide a kind of Low Temperature Fischer Tropsch artificial oil and the production of inferior feedstock oil Unionfining
The method of diesel oil, the diesel oil density that this method obtains is qualified, and Cetane number is high.
To achieve the above object, the Low Temperature Fischer Tropsch artificial oil designed by the present invention produces excellent with inferior feedstock oil Unionfining
The method of matter diesel oil, comprises the following steps：
1) Fischer-Tropsch diesel is subjected to mixed hydrogen processing, being hydrogenated with mode using liquid phase circulation after the molten hydrogen of saturation carries out hydrofinishing；
2) the hydrofining reaction thing that step 1) obtains is mixed with inferior feedstock oil and Fischer-Tropsch wax oil, mixed
Oil, mode is then hydrogenated with using gas-liquid counter current hydrofinishing is carried out to the miscella；
3) continue using gas-liquid counter current hydrogenation mode by the hydrofining reaction thing that step 2) obtains be hydrocracked with
Isomerization reaction；
4) liquid phase production oil obtained by step 3) is fractionated, obtains fine-quality diesel oil.
Further, in the step 2), the inferior feedstock oil and the Fischer-Tropsch wax oil in 1: 3.5~2: 1 ratio
Mixed.
Further, in the step 2), the operating condition of the hydrofining reaction is：Reaction temperature is 260~400
DEG C, reaction pressure is 2.0~15.0MPa, and volume space velocity is 0.4~3h during liquid-1, hydrogen to oil volume ratio 100~1000.
Further, in the step 3), described be hydrocracked is with the operating condition of isomerization reaction：Reaction temperature is
300~420 DEG C, reaction pressure is 2.0~15.0MPa, and volume space velocity is 0.4~3h during liquid-1, hydrogen to oil volume ratio be 100~
1000。
Further, in the step 2), the operating condition of the hydrofining reaction is：Reaction temperature is 320~380
DEG C, reaction pressure is 4.0~10MPa, and volume space velocity is 0.5~2.0h during liquid-1, hydrogen to oil volume ratio is 150~550.
Further, in the step 3), described be hydrocracked is with the operating condition of isomerization reaction：Reaction temperature is
330~390 DEG C, reaction pressure is 4.0~10MPa, and volume space velocity is 0.5~2.0h during liquid-1, hydrogen to oil volume ratio be 150~
550。
Further, in the step 1), the operating condition of the hydrofining reaction is：Reaction temperature is 260~400
DEG C, reaction pressure is 2.0~15.0MPa, and volume space velocity is 1.5~7.0h during liquid-1。
Further, in the step 1), the operating condition of the hydrofining reaction is：Reaction temperature is 320~380
DEG C, reaction pressure is 4.0~10MPa, and volume space velocity is 2.0~5.0h during liquid-1。
Further, in the step 2), the inferior feedstock oil and the Fischer-Tropsch wax oil in 1: 2~1.7: 1 ratio
Mixed.
Further, the inferior feedstock oil is secondary processing diesel oil.
Further, the secondary processing diesel oil be catalytic cracking diesel oil, coker gas oil, one kind in coal tar diesel oil or
Several, its aromatic hydrocarbons weight content is 25~75%.
Further, the aromatic hydrocarbons weight content of the secondary processing diesel oil is 30~60%.
Further, in the step 1) and step 2), Hydrobon catalyst includes carrier and hydrogenation active metals, institute
It is aluminum oxide or silicon-containing alumina to state carrier, and the hydrogenation active metals are group vib and/or group VIII metal.
Further, it is described in terms of hydrogenation active metals oxide on the basis of the gross weight of the hydrogen catalyst for refining
The weight content of group vib metal oxide is 10~30%, and the weight content of the group VIII metal oxide is 5~15%.
Further, in the step 3), described be hydrocracked with isomerization catalyst is the hydrogenation containing beta molecular sieve
Heterogeneous catalyst, its carrier are amorphous silica-alumina, and its hydrogenation active metals is group vib metal and/or group VIII metal.
Further, described be hydrocracked includes beta molecular sieve, carrier and hydrogenation activity gold with isomerization catalyst
Category, the carrier is amorphous silica-alumina, and the hydrogenation active metals are W and Ni, is hydrocracked and isomerization catalyst with described
Gross weight on the basis of, in terms of hydrogenation active metals oxide, WO3Weight content be 10~35%, NiO weight content be
5~15%, the weight content of beta molecular sieve is 8~30%.
The present invention is excellent to realize Low Temperature Fischer Tropsch artificial oil that the above method designs and the production of inferior feedstock oil Unionfining
The equipment of matter diesel oil, including mixed hydrogen tank, liquid phase hydrogenation reactor, gas-liquid counter current reactor, fractionator, it is characterised in that：It is described
Be provided with Fischer-Tropsch diesel import, recycle hydrogen import and the molten hydrogen diesel oil outlet of saturation in mixed hydrogen tank, the molten hydrogen diesel oil outlet of saturation with
The oil inlet connection of the liquid phase hydrogenation reactor；The gas-liquid counter current reactor includes the hydrofining reaction area and bottom at top
Portion be hydrocracked and isomerization reaction zone, the top of the gas-liquid counter current reactor are provided with oil inlet and gas outlet, the gas
The bottom of liquid counter-current reactor is provided with hydrogen inlet and oil-out, and the oil-out of the liquid phase hydrogenation reactor and the gas-liquid are inverse
The oil inlet connection of flow reactor, the oil-out of the gas-liquid counter current reactor are connected with the oil inlet of the fractionator.
Further, it also includes gas-liquid separator, and the gas-liquid import of the gas-liquid separator and the gas-liquid counter current are anti-
The gas outlet of device is answered to connect, the gas outlet of the gas-liquid separator recycle hydrogen import with the mixed hydrogen tank and the gas-liquid respectively
The hydrogen inlet connection of counter-current reactor.
Further, the tail oil outlet of the fractionator is connected with the oil inlet of the gas-liquid counter current reactor.
Compared with prior art, the present invention has advantages below：
First, the present invention in view of the deficiencies of the prior art and Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil it is respective
Feature, there is provided liquid-phase hydrogenatin is combined by one kind with vapour-liquid countercurrent hydrogenation is processed life to Fischer-Tropsch synthesis oil and poor ignition quality fuel
The process of fine-quality diesel oil is produced, has obtained the diesel oil that density is qualified, Cetane number is high, solves Low Temperature Fischer Tropsch artificial oil process
Hydrotreating and it is hydrocracked relatively low with the diesel component density that is obtained after isomerization, it is difficult to meet the technology of derv fuel standard
Problem, the present invention both produced qualified diesel oil for Fischer-Tropsch synthesis oil and provide a kind of reliable production method, while be inferior raw material again
Oil provides outlet.
Second, the inferior feedstock oil such as secondary processing diesel oil such as catalytic cracking diesel oil, coker gas oil, coal tar diesel oil due to containing
There are the impurity such as the sulphur, nitrogen and aromatic hydrocarbons of high level, in existing hydrogenation process, react the H of generation2S、NH3It is miscellaneous Deng gas
Matter competitive Adsorption has larger suppression to make on the activated centre of catalyst surface, to being hydrocracked with courses of reaction such as isomerization
With, being hydrocracked required reaction temperature can be very high, and then can influence catalyst service life, increase energy consumption and running cost,
And the present invention will react the H generated using the hydrogen flowed up then by way of gas-liquid counter current hydrogenation2S、NH3Deng gaseous impurity
Take away, so as to avoid H2S、NH3Deng gaseous impurity to being hydrocracked the inhibitory action with isomerization catalyst.
Third, the present invention liquid-phase hydrogenatin mode is combined with vapour-liquid countercurrent hydrogenation mode, liquid phase circulation hydrogenation technique according to
The dissolved hydrogen that reaction system is entrained into when largely being circulated by liquid-phase product to provide required hydrogen for hydrogenation reaction, not only hydrogen
Consume small, and reduce equipment investment and operating cost, and then required hydrogen-oil ratio is smaller for gas-liquid counter current hydrogenation technique, therefore this hair
The load of recycle compressor can be greatly reduced for bright method and energy consumption is low, technological process is simple.
Brief description of the drawings
Fig. 1 is the equipment connection structure that a kind of Low Temperature Fischer Tropsch artificial oil produces fine-quality diesel oil with inferior feedstock oil Unionfining
Schematic diagram.
Embodiment
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings, is easy to more clearly understand this
Invention, but they do not form to the present invention and limited.
The equipment of Low Temperature Fischer Tropsch artificial oil shown in Fig. 1 and inferior feedstock oil Unionfining production fine-quality diesel oil, including mixed hydrogen
Tank 1, liquid phase hydrogenation reactor 2, gas-liquid counter current reactor 3, fractionator 4, be provided with the mixed hydrogen tank 1 Fischer-Tropsch diesel import 1-1,
Recycle hydrogen import 1-2 and saturation molten hydrogen diesel oil outlet 1-3, the molten hydrogen diesel oil outlet 1-3 of saturation and liquid-phase hydrogenatin reaction
The oil inlet 2-1 connections of device 2；The gas-liquid counter current reactor 3 includes the hydrofining reaction area 3-1 at top and the hydrogenation of bottom
Cracking and isomerization reaction zone 3-2, the top of the gas-liquid counter current reactor 3 is provided with oil inlet 3-3 and gas outlet 3-4, described
The bottom of gas-liquid counter current reactor 3 is provided with hydrogen inlet 3-5 and oil-out 3-6, the oil-out 2- of the liquid phase hydrogenation reactor 2
2 are connected with the oil inlet 3-3 of the gas-liquid counter current reactor 3, the oil-out 3-6 of the gas-liquid counter current reactor 3 with described point
Evaporate the oil inlet 4-1 connections of device 4；Gas-liquid separator 5, the gas-liquid are connected with the gas outlet 3-4 of the gas-liquid counter current reactor 3
The gas outlet 3-4 of counter-current reactor 3 is connected with the gas-liquid import 5-1 of the gas-liquid separator 5, and the gas-liquid separator 5 goes out
Gas port 5-2 connects with the recycle hydrogen import 1-2 of the mixed hydrogen tank 1 and the hydrogen inlet 3-5 of the gas-liquid counter current reactor 3 respectively
Connect；The tail oil outlet 4-2 of the fractionator 4 is connected with the oil inlet 3-3 of the gas-liquid counter current reactor 3.
Above-mentioned Low Temperature Fischer Tropsch artificial oil and the course of work of the equipment of inferior feedstock oil Unionfining production fine-quality diesel oil are as follows：
Fischer-Tropsch diesel and recycle hydrogen enter mixed hydrogen tank 1 from the Fischer-Tropsch diesel import 1-1 in mixed hydrogen tank 1 and recycle hydrogen import 1-2 respectively and entered
The mixed hydrogen of row is handled, and the liquid phase hydrogenation reactor 2 equipped with Hydrobon catalyst is entered after the molten hydrogen of saturation and is hydrogenated with bar in liquid phase circulation
Hydrofining reaction is carried out under part, hydrofining reaction product flows out from the oil-out 2-2 of liquid phase hydrogenation reactor 2, through gas-liquid
The oil inlet 3-3 of counter-current reactor 3 enters gas-liquid counter current reactor 3, meanwhile, draw from the oil inlet 3-3 of gas-liquid counter current reactor 3
Enter Fischer-Tropsch wax oil and inferior feedstock oil, Fischer-Tropsch wax oil, inferior feedstock oil enter hydrogenation together with the Fischer-Tropsch diesel after the molten hydrogen of saturation
Refining reaction area 3-1 carries out hydrofining reaction, then, liquid phase effluent after hydrofining reaction enter be hydrocracked with it is different
Structure reaction zone 3-2 is hydrocracked and isomerization reaction, wherein, hydrogen is entered by the hydrogen of the bottom of gas-liquid counter current reactor 3
Mouth 3-5 is introduced, and is hydrocracked with the liquid product after isomerization reaction after the oil-out 3-6 outflows of gas-liquid counter current reactor 3
The oil inlet 4-1 for being fractionated into device 4 is fractionated into fractionator 4, obtains fine-quality diesel oil, dry gas and tail oil, fine-quality diesel oil, dry gas
And tail oil diesel oil outlet 4-3, the dry gas outlet 4-4 from fractionator 4 and tail oil outlet 4-2 outflows respectively, tail oil is through gas-liquid counter current
The oil inlet 3-3 circulating refluxs on the top of reactor 3 are to gas-liquid counter current reactor 3.In addition, it is hydrogenated with gas-liquid counter current reactor 3 anti-
Gas-phase product caused by after answering enters from the gas-liquid through gas-liquid separator 5 after the gas outlet 3-4 discharges on the top of gas-liquid counter current reactor 3
Mouth 5-1 enters gas-liquid separator 5 and carries out purified treatment, and the hydrogen that gas-liquid separator 5 is isolated enters circulation hydrogen system, for mixed hydrogen
Tank 1 and the circulation of gas-liquid counter-current reactor 3 provide hydrogen.Wherein, the hydrogenation of liquid phase hydrogenation reactor 2 and gas-liquid counter-current reactor 3
The Hydrobon catalyst used in refining reaction area 3-1 can be conventional commercial Hydrobon catalyst, and the hydrofinishing is urged
Agent is using aluminum oxide or silicon-containing alumina as carrier, and hydrogenation active metals are VIB and/or group VIII metal, vib metals
Generally Mo and/or W, group VIII metal is generally Co and/or Ni, on the basis of the gross weight of catalyst, in terms of oxide,
The oxidiferous content of vib metals is 10~30%, and the content of group VIII metal oxygenate is 5~15%；Gas-liquid
The Hydrobon catalyst used with isomerization reaction zone 3-2 that is hydrocracked of counter-current reactor 3 can also be that conventional commercial adds
Hydrogen cracking and isomerization catalyst, it is the hydroisomerization catalyst containing beta molecular sieve that this, which is hydrocracked with isomerization catalyst,
Carrier is amorphous silica-alumina, and hydrogenation active metal component is group vib metallic element molybdenum, tungsten, and group VIII metal element cobalt, nickel are more
Using W-Ni metallic combinations, the hydrocracking catalyst is on the basis of the gross weight of catalyst, in terms of oxide, active metal
WO3Weight content be 10~35%, NiO weight content be 5~15%, the weight content of beta molecular sieve is 8~30%.
Embodiment 1~4
Embodiment 1~4 is using Low Temperature Fischer Tropsch artificial oil shown in Fig. 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Equipment produces diesel oil, wherein, feedstock oil is mixed using Fischer-Tropsch diesel with Fischer-Tropsch wax oil and inferior feedstock oil in embodiment 1~4
Thing, raw materials used oil nature see the table below 1；Fischer-Tropsch wax oil used in embodiment 1~4 and inferior feedstock oil mixed proportion and concrete technology
Condition see the table below 2；The evaluation result of embodiment 1~4 see the table below 3.
Comparative example 1
Comparative example 1, which enters in the feedstock oil of gas-liquid counter current reactor, does not mix inferior feedstock oil, individually enters Fischer-Tropsch wax oil,
I.e.：Feedstock oil see the table below 1 using Fischer-Tropsch diesel and Fischer-Tropsch wax oil, raw material oil nature；Concrete technology condition see the table below 2；Evaluation knot
Fruit see the table below 3.
Comparative example 2
Comparative example 2 using identical raw material and controls conversion ratio consistent with embodiment 2, wherein, the feedstock oil of comparative example 2
Using Fischer-Tropsch diesel and Fischer-Tropsch wax oil and inferior raw material oil mixture, raw materials used oil nature see the table below 1；Comparative example 2 is using biography
The gas and liquid flowing technique of system, Fischer-Tropsch wax oil used see the table below 2 with inferior feedstock oil mixed proportion and concrete technology condition；Evaluation knot
Fruit see the table below 3.
The feedstock oil used in embodiment 1~4, comparative example 1 and comparative example 2 has Fischer-Tropsch diesel, Fischer-Tropsch wax oil, catalytic cracking
Diesel oil and coker gas oil, the relevant nature parameter of these feedstock oils see the table below 1：
Table 1
The concrete technology condition of embodiment 1~4, comparative example 1 and comparative example 2 see the table below 2：
Table 2
Embodiment 1~4, comparative example 1 and comparative example 2 produce obtained diesel fuel characteristicses evaluation result and see the table below 3:
Table 3
It was found from upper table 3, it can obtain low coagulating high-quality, high cetane number diesel oil, and diesel oil by the inventive method
Density is greatly improved.In addition, embodiment 2 is compareed compared with comparative example 2, it is from table 2 and table 3 as can be seen that real
Applying the comparison of example 2 and comparative example 2 can find out, when handling same materials, control identical conversion ratio, using the inventive method
Embodiment 2, it is hydrocracked wants low 20 DEG C with the reaction temperature of isomerization catalyst and comparative example 2, it can thus be seen that this hair
Bright method can be effectively reduced running cost and energy consumption etc..And from comparative example 1 it can also be seen that when feedstock oil is only Fischer-Tropsch diesel
During with Fischer-Tropsch wax oil, the diesel oil density that its production obtains is relatively low, only 0.7585g/cm3。
Claims (16)
1. a kind of method of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil, it is characterised in that：Bag
Include following steps：
1) Fischer-Tropsch diesel is subjected to mixed hydrogen processing, being hydrogenated with mode using liquid phase circulation after the molten hydrogen of saturation carries out hydrofinishing；
2) the hydrofining reaction thing that step 1) obtains is mixed with inferior feedstock oil and Fischer-Tropsch wax oil, obtains miscella,
Then hydrofinishing is carried out to the miscella using gas-liquid counter current hydrogenation mode；The operating condition of the hydrofining reaction
For：Reaction temperature is 260~400 DEG C, and reaction pressure is 2.0~15.0MPa, and volume space velocity is 0.4~3h during liquid-1, hydrogen oil body
Product ratio 100~1000；
3) continue to be hydrocracked the hydrofining reaction thing that step 2) obtains and isomery using gas-liquid counter current hydrogenation mode
Change reaction；
4) liquid phase production oil obtained by step 3) is fractionated, obtains fine-quality diesel oil；
The inferior feedstock oil is secondary processing diesel oil；The secondary processing diesel oil is catalytic cracking diesel oil, coker gas oil, coal tar
One or more in oily diesel oil, its aromatic hydrocarbons weight content are 25~75%.
2. the side of Low Temperature Fischer Tropsch artificial oil according to claim 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：In the step 2), the inferior feedstock oil presses 1: 3.5~2: 1 mass ratio with the Fischer-Tropsch wax oil
Mixed.
3. the side of Low Temperature Fischer Tropsch artificial oil according to claim 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：In the step 3), described be hydrocracked is with the operating condition of isomerization reaction：Reaction temperature is 300
~420 DEG C, reaction pressure is 2.0~15.0MPa, and volume space velocity is 0.4~3h during liquid-1, hydrogen to oil volume ratio is 100~1000.
4. Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 3 produces excellent with inferior feedstock oil Unionfining
The method of matter diesel oil, it is characterised in that：In the step 2), the operating condition of the hydrofining reaction is：Reaction temperature is
320~380 DEG C, reaction pressure is 4.0~10MPa, and volume space velocity is 0.5~2.0h during liquid-1, hydrogen to oil volume ratio be 150~
550。
5. Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 3 produces excellent with inferior feedstock oil Unionfining
The method of matter diesel oil, it is characterised in that：In the step 3), described be hydrocracked is with the operating condition of isomerization reaction：Instead
It is 330~390 DEG C to answer temperature, and reaction pressure is 4.0~10MPa, and volume space velocity is 0.5~2.0h during liquid-1, hydrogen to oil volume ratio is
150~550.
6. Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 3 produces excellent with inferior feedstock oil Unionfining
The method of matter diesel oil, it is characterised in that：In the step 1), the operating condition of the hydrofining reaction is：Reaction temperature is
260~400 DEG C, reaction pressure is 2.0~15.0MPa, and volume space velocity is 1.5~7.0h during liquid-1。
7. the side of Low Temperature Fischer Tropsch artificial oil according to claim 6 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：In the step 1), the operating condition of the hydrofining reaction is：Reaction temperature is 320~380 DEG C,
Reaction pressure is 4.0~10MPa, and volume space velocity is 2.0~5.0h during liquid-1。
8. the side of Low Temperature Fischer Tropsch artificial oil according to claim 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：In the step 2), the inferior feedstock oil presses 1: 2~1.7: 1 mass ratio with the Fischer-Tropsch wax oil
Mixed.
9. the side of Low Temperature Fischer Tropsch artificial oil according to claim 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：The aromatic hydrocarbons weight content of the secondary processing diesel oil is 30~60%.
10. the side of Low Temperature Fischer Tropsch artificial oil according to claim 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：In the step 1) and step 2), Hydrobon catalyst includes carrier and hydrogenation active metals, described
Carrier is aluminum oxide or silicon-containing alumina, and the hydrogenation active metals are group vib and/or group VIII metal.
11. the side of Low Temperature Fischer Tropsch artificial oil according to claim 10 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：On the basis of the gross weight of the hydrogen catalyst for refining, in terms of hydrogenation active metals oxide, the VIB
The weight content of family metal oxide is 10~30%, and the weight content of the group VIII metal oxide is 5~15%.
12. the side of Low Temperature Fischer Tropsch artificial oil according to claim 1 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：In the step 3), it is that the hydroisomerizing containing beta molecular sieve is urged to be hydrocracked with isomerization catalyst
Agent, its carrier are amorphous silica-alumina, and its hydrogenation active metals is group vib metal and/or group VIII metal.
13. the side of Low Temperature Fischer Tropsch artificial oil according to claim 12 and inferior feedstock oil Unionfining production fine-quality diesel oil
Method, it is characterised in that：Described be hydrocracked includes beta molecular sieve, carrier and hydrogenation active metals with isomerization catalyst, described
Carrier is amorphous silica-alumina, and the hydrogenation active metals are W and Ni, with the gross weight being hydrocracked with isomerization catalyst
On the basis of, in terms of hydrogenation active metals oxide, WO3Weight content be 10~35%, NiO weight content be 5~15%,
The weight content of beta molecular sieve is 8~30%.
It is 14. a kind of to realize Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining that claim 1 methods described designs
The equipment for producing fine-quality diesel oil, including mixed hydrogen tank (1), liquid phase hydrogenation reactor (2), gas-liquid counter current reactor (3), fractionator
(4), it is characterised in that：Fischer-Tropsch diesel import (1-1), recycle hydrogen import (1-2) and the molten hydrogen of saturation are provided with the mixed hydrogen tank (1)
Diesel oil exports (1-3), and the molten hydrogen diesel oil outlet (1-3) of saturation and the oil inlet (2-1) of the liquid phase hydrogenation reactor (2) connect
Connect；The hydrofining reaction area (3-1) of the gas-liquid counter current reactor (3) including top and bottom be hydrocracked and isomerization
Reaction zone (3-2), the top of the gas-liquid counter current reactor (3) are provided with oil inlet (3-3) and gas outlet (3-4), the gas-liquid
The bottom of counter-current reactor (3) is provided with hydrogen inlet (3-5) and oil-out (3-6), the liquid phase hydrogenation reactor (2) it is fuel-displaced
Mouth (2-2) is connected with the oil inlet (3-3) of the gas-liquid counter current reactor (3), the oil-out of the gas-liquid counter current reactor (3)
(3-6) is connected with the oil inlet (4-1) of the fractionator (4).
15. Low Temperature Fischer Tropsch artificial oil according to claim 14 is set with inferior feedstock oil Unionfining production fine-quality diesel oil
It is standby, it is characterised in that：It also includes gas-liquid separator (5), gas-liquid import (5-1) and the gas of the gas-liquid separator (5)
Gas outlet (3-4) connection of liquid counter-current reactor (3), the gas outlet (5-2) of the gas-liquid separator (5) respectively with the mixed hydrogen
The recycle hydrogen import (1-2) of tank (1) and hydrogen inlet (3-5) connection of the gas-liquid counter current reactor (3).
16. Low Temperature Fischer Tropsch artificial oil according to claim 14 is set with inferior feedstock oil Unionfining production fine-quality diesel oil
It is standby, it is characterised in that：The tail oil outlet (4-2) of the fractionator (4) and the oil inlet (3- of the gas-liquid counter current reactor (3)
3) connect.
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| PCT/CN2017/078013 WO2017181813A1 (en) | 2016-04-18 | 2017-03-24 | Method and equipment thereof for producing high-quality diesel using low-temperature fischer-tropsch synthetic oil and low-grade oil feedstock |
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| CN105778995B (en) * | 2016-04-18 | 2018-03-20 | 武汉凯迪工程技术研究总院有限公司 | The method and its equipment of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil |
| CN108003935B (en) * | 2017-12-15 | 2020-06-16 | 神华集团有限责任公司 | Method for producing clean diesel oil by Fischer-Tropsch synthesis of light and heavy product combination |
| CN109988636B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible single stage hydrocracking process |
| CN109988618B (en) * | 2017-12-29 | 2021-05-04 | 中国石油化工股份有限公司 | Flexible single-stage two-agent hydrocracking process |
| CN109988621B (en) * | 2017-12-29 | 2021-07-09 | 中国石油化工股份有限公司 | Flexible hydrocracking process |
| CN115216338B (en) * | 2021-04-15 | 2023-10-10 | 中国石油化工股份有限公司 | Coking full distillate oil processing method |
| CN115466628B (en) * | 2021-06-10 | 2023-12-12 | 中国石油化工股份有限公司 | Liquid phase hydrogenation reaction device and system and hydrocarbon oil phase hydrogenation method |
| CN115785995A (en) * | 2021-09-10 | 2023-03-14 | 中国石油化工股份有限公司 | Inferior diesel oil hydrotreating method and device |
| CN115785993B (en) * | 2021-09-10 | 2024-05-31 | 中国石油化工股份有限公司 | Diesel hydrogenation method and device |
| CN116064131A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis oil hydrotreatment device and method |
| CN115895719B (en) * | 2023-01-04 | 2024-05-28 | 中国石油大学(华东) | Process method for deep hydrogenation conversion of high aromatic catalytic cracking diesel oil |
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| US7354507B2 (en) * | 2004-03-17 | 2008-04-08 | Conocophillips Company | Hydroprocessing methods and apparatus for use in the preparation of liquid hydrocarbons |
| CN101230291B (en) * | 2007-01-23 | 2012-02-29 | 中国石油化工股份有限公司 | Low consumption energy method for processing fischer-tropsch synthesis |
| 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 |
| CN101928600B (en) * | 2009-06-25 | 2013-06-05 | 中国石油化工股份有限公司 | Method for producing diesel oil or diesel oil blending component |
| CN101942333B (en) * | 2009-07-09 | 2013-08-28 | 中国石油化工股份有限公司 | Shale oil single-stage serial hydrocracking technology method |
| CN102911722B (en) * | 2011-08-01 | 2014-10-29 | 中国石油化工股份有限公司 | Hydrogenation quality-improving method for Fischer-Tropsch synthetic oil |
| CN102911729B (en) * | 2011-08-01 | 2014-12-03 | 中国石油化工股份有限公司 | Method for producing diesel oil from Fischer-Tropsch synthetic oil |
| CN103805240B (en) * | 2012-11-07 | 2015-11-18 | 中国石油化工股份有限公司 | A kind of low cost combined hydrogenation refining technique |
| CN103146426B (en) * | 2013-03-20 | 2015-01-28 | 中科合成油工程有限公司 | Method of converting fischer-tropsch synthesis products into naphtha, diesel and liquefied petroleum gas |
| CN104611056B (en) * | 2015-02-11 | 2017-03-08 | 武汉凯迪工程技术研究总院有限公司 | A kind of hydrotreating method of Low Temperature Fischer Tropsch synthetic product |
| CN105778995B (en) * | 2016-04-18 | 2018-03-20 | 武汉凯迪工程技术研究总院有限公司 | The method and its equipment of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining production fine-quality diesel oil |
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