CN105778995A - Method and device for producing good-quality diesel oil through combined hydrogenation of low-temperature Fischer-Tropsch synthesis oil and inferior crude oil - Google Patents
Method and device for producing good-quality diesel oil through combined hydrogenation of low-temperature Fischer-Tropsch synthesis oil and inferior crude oil Download PDFInfo
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- CN105778995A CN105778995A CN201610238808.2A CN201610238808A CN105778995A CN 105778995 A CN105778995 A CN 105778995A CN 201610238808 A CN201610238808 A CN 201610238808A CN 105778995 A CN105778995 A CN 105778995A
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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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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
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- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
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Abstract
The invention discloses a method and device for producing good-quality diesel oil through combined hydrogenation of low-temperature Fischer-Tropsch synthesis oil and inferior crude oil. The method includes the following steps that firstly, Fischer-Tropsch synthesis oil is subjected to hydrogen mixing treatment, and hydrofining is conducted in a liquid-phase circulating hydrogenation mode after saturation hydrogen dissolving; secondly, the hydrofining reactant obtained in the first step is mixed with inferior crude oil and Fischer-Tropsch wax oil to obtain mixed oil, and then hydrofining is conducted on the mixed oil in a gas-liquid countercurrent hydrogenation mode; thirdly, the hydrofining reactant obtained in the second step is subjected to hydrocracking and isomerization reaction in a gas-liquid countercurrent hydrogenation mode; fourthly, liquid-phase production oil obtained in the third step is fractionated to obtain the good-quality diesel oil. The invention provides a technical method for processing and producing the good-quality diesel oil from Fischer-Tropsch synthesis oil and inferior diesel oil through liquid-phase hydrogenation and gas-liquid countercurrent hydrogenation. The diesel oil with qualified density and high cetane number is obtained.
Description
Technical field
The present invention relates to diesel production technology, produce method and the equipment thereof of fine-quality diesel oil in particular to a kind of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining.
Background technology
Along with the environmental regulation that the in short supply of petroleum resources and countries in the world are increasingly stricter, cleaning alternative energy source technological development comes into one's own gradually, and wherein F-T synthesis technology receives much concern because the raw materials such as coal, natural gas, biomass can be utilized producing fuel with high cleanness.The F-T synthesis technology height according to reaction temperature, is divided into high temperature fischer-tropsch synthetic technology and Low Temperature Fischer Tropsch synthetic technology.The composition of Fischer-Tropsch synthetic and oil difference are relatively big, and because of the restriction by Anderson-Schulz-Flory rule, its product is mainly containing C4-C70Hydro carbons and the complex mixture of a small amount of oxygenatedchemicals, have without sulfur, nitrogen-free, without the feature such as metal, low aromatic hydrocarbons, wherein, Low Temperature Fischer Tropsch synthetic product is mainly made up of linear paraffin and alkene, and containing a small amount of oxygen-containing organic compound.Containing the wax of nearly 40% in Low Temperature Fischer Tropsch synthetic product product, although Cetane number is more than 70, but condensation point pour point is too high, and cold flow properties is too poor, it is impossible to be directly used as transport fuel oil.One of main purpose of F-T synthesis technology is to produce the diesel oil of high-quality, and each fraction in Fischer-Tropsch synthetic need to be hydrogenated with upgrading through accordingly, just can obtain qualified product.And Low Temperature Fischer Tropsch synthetic product is because having the features such as linear paraffin height, condensation point is high, density is low so that the diesel oil distillate condensation point after hydrogenation is high, density is low, it is impossible to sell directly as commercial Dissel oil.Meanwhile, in refinery's work flow, containing substantial amounts of aromatic hydrocarbons in secondary processing diesel oil inferior, density is higher, but Cetane number is very low, and the secondary processing diesel oil such as catalytic diesel oil, coker gas oil owing to containing impurity contents such as higher sulfur, nitrogen and aromatic hydrocarbons, reacting the H of generation in hydrogenation process2S、NH3Deng gaseous impurity competitive Adsorption on the active center of catalyst surface, hydrogenation cracking and isomerization etc. being had bigger inhibitory action, the reaction temperature needed for hydrogenation cracking can be significantly high, and then can affect catalyst service life, energy consumption and running cost.
Prior art has some about the report how utilizing Low Temperature Fischer Tropsch synthetic product to produce diesel oil, as: Chinese patent CN10313468A discloses a kind of Low Temperature Fischer Tropsch artificial oil hydrofinishing and/or hydroisomerizing process method, the method is that hydrofinishing or Hydrocracking unit adopt liquid-phase hydrogenatin and lower feeding manner, the diesel oil density that the method weak point is obtained is relatively low, only 0.7586g/cm3；A kind of method producing intermediate oil disclosed in US Patent No. 6858127, the method for carrying out hydrogenation cracking by least part of artificial oil, it is then demultiplex out coal diesel oil distillate therein, tail oil carries out hydrogenation cracking again, separating the coal diesel oil distillate in product again, wherein diesel oil distillate density is 0.78g/cm3, condensation point be-28～0 DEG C, the method weak point is that diesel oil distillate density is relatively low, does not reach derv fuel index.
Summary of the invention
A kind of method that present invention aim to provide Low Temperature Fischer Tropsch artificial oil to produce fine-quality diesel oil with inferior feedstock oil Unionfining, the diesel oil density that the method obtains is qualified, and Cetane number is high.
For achieving the above object, the method that the Low Temperature Fischer Tropsch artificial oil designed by the present invention produces fine-quality diesel oil with inferior feedstock oil Unionfining, comprise the following steps:
1) Fischer-Tropsch diesel carries out mixed hydrogen to process, after saturated molten hydrogen, adopt liquid phase circulation hydrogenation mode to carry out hydrofinishing；
2) by step 1) the hydrofining reaction thing that obtains mixes with inferior feedstock oil and Fischer-Tropsch wax oil, obtains miscella, then adopt gas-liquid counter current hydrogenation mode that described miscella is carried out hydrofinishing；
3) continuing to adopt gas-liquid counter current hydrogenation mode by step 2) the hydrofining reaction thing that obtains carries out hydrogenation cracking and isomerization reaction；
4) by step 3) gained liquid phase produce oil carry out fractional distillation, obtain fine-quality diesel oil.
Further, described step 2) in, described inferior feedstock oil mixes in the ratio of 1: 3.5～2: 1 with described Fischer-Tropsch wax oil.
Further, described step 2) in, the operating condition of described hydrofining reaction is: reaction temperature is 260～400 DEG C, and reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 0.4～3h-1, hydrogen to oil volume ratio 100～1000.
Further, described step 3) in, the operating condition of described hydrogenation cracking and isomerization reaction is: reaction temperature is 300～420 DEG C, and reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 0.4～3h-1, hydrogen to oil volume ratio is 100～1000.
Further, described step 2) in, the operating condition of described hydrofining reaction is: reaction temperature is 320～380 DEG C, and reaction pressure is 4.0～10MPa, and during liquid, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio is 150～550.
Further, described step 3) in, the operating condition of described hydrogenation cracking and isomerization reaction is: reaction temperature is 330～390 DEG C, and reaction pressure is 4.0～10MPa, and during liquid, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio is 150～550.
Further, described step 1) in, the operating condition of described hydrofining reaction is: reaction temperature is 260～400 DEG C, and reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 1.5～7.0h-1。
Further, described step 1) in, the operating condition of described hydrofining reaction is: reaction temperature is 320～380 DEG C, and reaction pressure is 4.0～10MPa, and during liquid, volume space velocity is 2.0～5.0h-1。
Further, described step 2) in, described inferior feedstock oil mixes in the ratio of 1: 2～1.7: 1 with described Fischer-Tropsch wax oil.
Further, described inferior feedstock oil is secondary processing diesel oil.
Further, described secondary processing diesel oil is one or more in catalytic cracking diesel oil, coker gas oil, coal tar diesel oil, and its aromatic hydrocarbons weight content is 25～75%.
Further, the aromatic hydrocarbons weight content of described secondary processing diesel oil is 30～60%.
Further, described step 1) and step 2) in, Hydrobon catalyst includes carrier and hydrogenation active metals, and described carrier is aluminium oxide or silicon-containing alumina, and described hydrogenation active metals is group vib and/or group VIII metal.
Further, with the gross weight of described hydrogen catalyst for refining for benchmark, in hydrogenation active metals oxide, the weight content of described group vib metal-oxide is 10～30%, and the weight content of described group VIII metal oxide is 5～15%.
Further, described step 3) in, described hydrogenation cracking and isomerization catalyst are the hydroisomerization catalyst containing beta molecular sieve, and its carrier is amorphous silica-alumina, and its hydrogenation active metals is group vib metal and/or group VIII metal.
Further, described hydrogenation cracking and isomerization catalyst include beta molecular sieve, carrier and hydrogenation active metals, described carrier is amorphous silica-alumina, described hydrogenation active metals is W and Ni, with the gross weight of described hydrogenation cracking and isomerization catalyst for benchmark, in hydrogenation active metals oxide, WO3Weight content be 10～35%, the weight content of NiO is 5～15%, and the weight content of beta molecular sieve is 8～30%.
The present invention realizes Low Temperature Fischer Tropsch artificial oil that said method designs and inferior feedstock oil Unionfining to produce the equipment of fine-quality diesel oil, including mixed hydrogen tank, liquid phase hydrogenation reactor, gas-liquid counter current reactor, dephlegmator, it is characterized in that: having Fischer-Tropsch diesel import, recycle hydrogen import and the outlet of saturated molten hydrogen diesel oil on described mixed hydrogen tank, the outlet of described saturated molten hydrogen diesel oil is connected with the oil-in of described liquid phase hydrogenation reactor；Described gas-liquid counter current reactor includes the hydrofining reaction district at top and the hydrogenation cracking of bottom and isomerization reaction zone, the top of described gas-liquid counter current reactor has oil-in and gas outlet, the bottom of described gas-liquid counter current reactor has hydrogen inlet and oil-out, the oil-out of described liquid phase hydrogenation reactor is connected with the oil-in of described gas-liquid counter current reactor, and the oil-out of described gas-liquid counter current reactor is connected with the oil-in of described dephlegmator.
Further, it also includes gas-liquid separator, the gas-liquid import of described gas-liquid separator is connected with the gas outlet of described gas-liquid counter current reactor, and the gas outlet of described gas-liquid separator is connected with the recycle hydrogen import of described mixed hydrogen tank and the hydrogen inlet of described gas-liquid counter current reactor respectively.
Further, the tail oil outlet of described dephlegmator is connected with the oil-in of described gas-liquid counter current reactor.
Compared with prior art, the invention have the advantages that
One, the present invention is directed to the deficiencies in the prior art part and Low Temperature Fischer Tropsch artificial oil and the respective feature of inferior feedstock oil, provide a kind of liquid-phase hydrogenatin being combined with vapour-liquid countercurrent hydrogenation and Fischer-Tropsch synthesis oil and poor ignition quality fuel are processed producing the process of fine-quality diesel oil, obtain density qualified, the diesel oil that Cetane number is high, solve the diesel component density that Low Temperature Fischer Tropsch artificial oil obtains after hydrotreatment and hydrogenation cracking and isomerization relatively low, it is difficult to meet the technical problem of derv fuel standard, the present invention both produces qualified diesel oil for Fischer-Tropsch synthesis oil and provides a kind of production method reliably, provide outlet for inferior feedstock oil again simultaneously.
Its two, such as the secondary processing diesel oil such as catalytic cracking diesel oil, coker gas oil, coal tar diesel oil is due to containing impurity such as the sulfur of high level, nitrogen and aromatic hydrocarbons for inferior feedstock oil, in existing hydrogenation process, reaction generate H2S、NH3Deng gaseous impurity competitive Adsorption on the active center of catalyst surface, the courses of reaction such as hydrogenation cracking and isomerization there is bigger inhibitory action, reaction temperature needed for hydrogenation cracking can be significantly high, and then catalyst service life can be affected, increase energy consumption and running cost, the present invention is then hydrogenated with mode by gas-liquid counter current, utilizes the H that reaction is generated by the hydrogen flowed up2S、NH3Take away Deng gaseous impurity, thus avoiding H2S、NH3Deng the gaseous impurity inhibitory action to hydrogenation cracking and isomerization catalyst.
They are three years old, liquid-phase hydrogenatin mode is combined by the present invention with vapour-liquid countercurrent hydrogenation mode, liquid phase circulation hydrogenation technique relies on liquid-phase product is entrained into response system dissolved hydrogen when circulating in a large number to carry out the hydrogen required for providing for hydrogenation reaction, not only hydrogen consumption is little, and reduce equipment investment and operating cost, gas-liquid counter current hydrogenation technique then required hydrogen-oil ratio is less, and therefore the inventive method can be greatly reduced the load of recycle compressor and energy consumption is low, technological process is simple.
Accompanying drawing explanation
Fig. 1 is the equipment connection structure schematic diagram that a kind of Low Temperature Fischer Tropsch artificial oil and inferior feedstock oil Unionfining produce fine-quality diesel oil.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, it is simple to more clearly understand the present invention, but the present invention is not constituted restriction by them.
Low Temperature Fischer Tropsch artificial oil shown in Fig. 1 produces the equipment of fine-quality diesel oil with inferior feedstock oil Unionfining, including mixed hydrogen tank 1, liquid phase hydrogenation reactor 2, gas-liquid counter current reactor 3, dephlegmator 4, having Fischer-Tropsch diesel import 1-1, recycle hydrogen import 1-2 and saturated molten hydrogen diesel oil outlet 1-3 on described mixed hydrogen tank 1, described saturated molten hydrogen diesel oil outlet 1-3 is connected with the oil-in 2-1 of described liquid phase hydrogenation reactor 2；Described gas-liquid counter current reactor 3 includes the hydrofining reaction district 3-1 at top and the hydrogenation cracking of bottom and isomerization reaction zone 3-2, the top of described gas-liquid counter current reactor 3 has oil-in 3-3 and gas outlet 3-4, the bottom of described gas-liquid counter current reactor 3 has hydrogen inlet 3-5 and oil-out 3-6, the oil-out 2-2 of described liquid phase hydrogenation reactor 2 is connected with the oil-in 3-3 of described gas-liquid counter current reactor 3, and the oil-out 3-6 of described gas-liquid counter current reactor 3 is connected with the oil-in 4-1 of described dephlegmator 4；The gas outlet 3-4 of described gas-liquid counter current reactor 3 is connected with gas-liquid separator 5, the gas outlet 3-4 of described gas-liquid counter current reactor 3 is connected with the gas-liquid import 5-1 of described gas-liquid separator 5, and the gas outlet 5-2 of described gas-liquid separator 5 is connected with the recycle hydrogen import 1-2 of described mixed hydrogen tank 1 and the hydrogen inlet 3-5 of described gas-liquid counter current reactor 3 respectively；The tail oil outlet 4-2 of described dephlegmator 4 is connected with the oil-in 3-3 of described gas-liquid counter current reactor 3.
nullAbove-mentioned Low Temperature Fischer Tropsch artificial oil is as follows with the work process of the equipment that inferior feedstock oil Unionfining produces fine-quality diesel oil: Fischer-Tropsch diesel and recycle hydrogen carry out mixed hydrogen from the mixed hydrogen tank 1 of the Fischer-Tropsch diesel import 1-1 mixed hydrogen tank 1 and recycle hydrogen import 1-2 entrance respectively and process，Enter the liquid phase hydrogenation reactor 2 equipped with Hydrobon catalyst after saturated molten hydrogen under liquid phase circulation hydroconversion condition, carry out hydrofining reaction，Hydrofining reaction product flows out from the oil-out 2-2 of liquid phase hydrogenation reactor 2，Gas-liquid counter current reactor 3 is entered through the oil-in 3-3 of gas-liquid counter current reactor 3，Simultaneously，Fischer-Tropsch wax oil and inferior feedstock oil is introduced from the oil-in 3-3 of gas-liquid counter current reactor 3，Fischer-Tropsch wax oil、Inferior feedstock oil enters hydrofining reaction district 3-1 together with the Fischer-Tropsch diesel after saturated molten hydrogen and carries out hydrofining reaction，Then，Liquid phase effluent after hydrofining reaction enters hydrogenation cracking and carries out hydrogenation cracking and isomerization reaction with isomerization reaction zone 3-2，Wherein，Hydrogen is introduced by the hydrogen inlet 3-5 of gas-liquid counter current reactor 3 bottom，Liquid product after hydrogenation cracking and isomerization reaction enters dephlegmator 4 through the oil-in 4-1 of dephlegmator 4 after flowing out from the oil-out 3-6 of gas-liquid counter current reactor 3 and carries out fractional distillation，Obtain fine-quality diesel oil、Dry gas and tail oil，Fine-quality diesel oil、Dry gas and tail oil export 4-3 from the diesel oil of dephlegmator 4 respectively、Dry gas outlet 4-4 and tail oil outlet 4-2 flows out，Tail oil through the oil-in 3-3 circulating reflux on gas-liquid counter current reactor 3 top to gas-liquid counter current reactor 3.Additionally, the gas-phase product produced after hydrogenation reaction in gas-liquid counter current reactor 3 enters gas-liquid separator 5 through the gas-liquid import 5-1 of gas-liquid separator 5 after discharging from the gas outlet 3-4 on gas-liquid counter current reactor 3 top and carries out purified treatment, the isolated hydrogen of gas-liquid separator 5 enters recycle hydrogen system, and circulating for mixed hydrogen tank 1 and gas-liquid counter-current reactor 3 provides hydrogen.Wherein, the Hydrobon catalyst used in the hydrofining reaction district 3-1 of liquid phase hydrogenation reactor 2 and gas-liquid counter-current reactor 3 can be conventional commercial Hydrobon catalyst, this Hydrobon catalyst is with aluminium oxide or silicon-containing alumina for carrier, hydrogenation active metals is VIB and/or group VIII metal, vib metals is generally Mo and/or W, group VIII metal is generally Co and/or Ni, with the gross weight of catalyst for benchmark, in oxide, the oxidiferous content of vib metals is 10～30%, the content of group VIII metal oxygenate is 5～15%；The hydrogenation cracking of gas-liquid counter current reactor 3 and the isomerization reaction zone 3-2 Hydrobon catalyst used can also be conventional commercial hydrogenation cracking and isomerization catalyst, this hydrogenation cracking and isomerization catalyst are the hydroisomerization catalyst containing beta molecular sieve, carrier is amorphous silica-alumina, hydrogenation active metals component is group vib metallic element molybdenum, tungsten, group VIII metal element cobalt, nickel, many employing W-Ni metallic combinations, described hydrocracking catalyst is with the gross weight of catalyst for benchmark, in oxide, active metal W O3Weight content be 10～35%, the weight content of NiO is 5～15%, and the weight content of beta molecular sieve is 8～30%.
Embodiment 1～4
Embodiment 1～4 all adopts the equipment that Low Temperature Fischer Tropsch artificial oil shown in Fig. 1 and inferior feedstock oil Unionfining produce fine-quality diesel oil to produce diesel oil, wherein, embodiment 1～4 Raw oil all adopts Fischer-Tropsch diesel and Fischer-Tropsch wax oil and inferior raw material oil mixture, and raw materials used oil nature is shown in table 1 below；Fischer-Tropsch wax oil used by embodiment 1～4 is shown in table 2 below with inferior feedstock oil mixed proportion and concrete technology condition；The evaluation result of embodiment 1～4 is shown in table 3 below.
Comparative example 1
Comparative example 1 enters in the raw oil of gas-liquid counter current reactor and does not mix inferior feedstock oil, individually enters Fischer-Tropsch wax oil, it may be assumed that raw oil adopts Fischer-Tropsch diesel and Fischer-Tropsch wax oil, and raw oil character is shown in table 1 below；Concrete technology condition is shown in table 2 below；Evaluation result is shown in table 3 below.
Comparative example 2
Comparative example 2 adopts identical raw material and control conversion ratio consistent with embodiment 2, and wherein, the raw oil of comparative example 2 adopts Fischer-Tropsch diesel and Fischer-Tropsch wax oil and inferior raw material oil mixture, and raw materials used oil nature is shown in table 1 below；Comparative example 2 adopts traditional gas and liquid flowing technique, and Fischer-Tropsch wax oil used is shown in table 2 below with inferior feedstock oil mixed proportion and concrete technology condition；Evaluation result is shown in table 3 below.
The raw 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, and the relevant nature parameter of these raw oils is shown in table 1 below:
Table 1
The concrete technology condition of embodiment 1～4, comparative example 1 and comparative example 2 is shown in table 2 below:
Table 2
Embodiment 1～4, comparative example 1 and comparative example 2 produce the diesel fuel characteristics evaluation result obtained and see table 3 below:
Table 3
From upper table 3 it can be seen that can be obtained the diesel oil of low solidifying high-quality, high cetane number by the inventive method, and the density of diesel oil is greatly improved.Additionally, embodiment 2 is compared with comparative example 2 and compares, can be seen that from table 2 and table 3, the comparison of embodiment 2 and comparative example 2 can be found out, when processing same materials, controlling identical conversion ratio, adopting the embodiment 2 of the inventive method, its hydrogenation cracking is low 20 DEG C with the reaction temperature of isomerization catalyst and comparative example 2, it can thus be seen that the inventive method can be effectively reduced running cost and energy consumption etc..And from comparative example 1 it can also be seen that when being only Fischer-Tropsch diesel and Fischer-Tropsch wax oil when raw oil, it is relatively low that it produces the diesel oil density obtained, it is only 0.7585g/cm3。
Claims (19)
1. the method that a Low Temperature Fischer Tropsch artificial oil produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterised in that: comprise the following steps:
1) Fischer-Tropsch diesel carries out mixed hydrogen to process, after saturated molten hydrogen, adopt liquid phase circulation hydrogenation mode to carry out hydrofinishing；
2) by step 1) the hydrofining reaction thing that obtains mixes with inferior feedstock oil and Fischer-Tropsch wax oil, obtains miscella, then adopt gas-liquid counter current hydrogenation mode that described miscella is carried out hydrofinishing；
3) continuing to adopt gas-liquid counter current hydrogenation mode by step 2) the hydrofining reaction thing that obtains carries out hydrogenation cracking and isomerization reaction；
4) by step 3) gained liquid phase produce oil carry out fractional distillation, obtain fine-quality diesel oil.
2. the method that Low Temperature Fischer Tropsch artificial oil according to claim 1 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterised in that: described step 2) in, described inferior feedstock oil mixes in the ratio of 1: 3.5～2: 1 with described Fischer-Tropsch wax oil.
3. the method that Low Temperature Fischer Tropsch artificial oil according to claim 1 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 2) in, the operating condition of described hydrofining reaction is: reaction temperature is 260～400 DEG C, reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 0.4～3h-1, hydrogen to oil volume ratio 100～1000.
4. the method that Low Temperature Fischer Tropsch artificial oil according to claim 1 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 3) in, the operating condition of described hydrogenation cracking and isomerization reaction is: reaction temperature is 300～420 DEG C, reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 0.4～3h-1, hydrogen to oil volume ratio is 100～1000.
5. the method that Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 4 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 2) in, the operating condition of described hydrofining reaction is: reaction temperature is 320～380 DEG C, reaction pressure is 4.0～10MPa, and during liquid, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio is 150～550.
6. the method that Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 4 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 3) in, the operating condition of described hydrogenation cracking and isomerization reaction is: reaction temperature is 330～390 DEG C, reaction pressure is 4.0～10MPa, and during liquid, volume space velocity is 0.5～2.0h-1, hydrogen to oil volume ratio is 150～550.
7. the method that Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 4 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 1) in, the operating condition of described hydrofining reaction is: reaction temperature is 260～400 DEG C, reaction pressure is 2.0～15.0MPa, and during liquid, volume space velocity is 1.5～7.0h-1。
8. the method that Low Temperature Fischer Tropsch artificial oil according to claim 7 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 1) in, the operating condition of described hydrofining reaction is: reaction temperature is 320～380 DEG C, reaction pressure is 4.0～10MPa, and during liquid, volume space velocity is 2.0～5.0h-1。
9. the method that Low Temperature Fischer Tropsch artificial oil according to claim 1 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterised in that: described step 2) in, described inferior feedstock oil mixes in the ratio of 1: 2～1.7: 1 with described Fischer-Tropsch wax oil.
10. the method that Low Temperature Fischer Tropsch artificial oil according to any one of claim 1 to 4 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterised in that: described inferior feedstock oil is secondary processing diesel oil.
11. the method that Low Temperature Fischer Tropsch artificial oil according to claim 10 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described secondary processing diesel oil is one or more in catalytic cracking diesel oil, coker gas oil, coal tar diesel oil, and its aromatic hydrocarbons weight content is 25～75%.
12. the method that Low Temperature Fischer Tropsch artificial oil according to claim 11 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterised in that: the aromatic hydrocarbons weight content of described secondary processing diesel oil is 30～60%.
13. the method that Low Temperature Fischer Tropsch artificial oil according to claim 1 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 1) and step 2) in, Hydrobon catalyst includes carrier and hydrogenation active metals, described carrier is aluminium oxide or silicon-containing alumina, and described hydrogenation active metals is group vib and/or group VIII metal.
14. the method that Low Temperature Fischer Tropsch artificial oil according to claim 13 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: with the gross weight of described hydrogen catalyst for refining for benchmark, in hydrogenation active metals oxide, the weight content of described group vib metal-oxide is 10～30%, and the weight content of described group VIII metal oxide is 5～15%.
15. the method that Low Temperature Fischer Tropsch artificial oil according to claim 1 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described step 3) in, described hydrogenation cracking and isomerization catalyst are the hydroisomerization catalyst containing beta molecular sieve, its carrier is amorphous silica-alumina, and its hydrogenation active metals is group vib metal and/or group VIII metal.
16. the method that Low Temperature Fischer Tropsch artificial oil according to claim 15 produces fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: described hydrogenation cracking and isomerization catalyst include beta molecular sieve, carrier and hydrogenation active metals, described carrier is amorphous silica-alumina, described hydrogenation active metals is W and Ni, with the gross weight of described hydrogenation cracking and isomerization catalyst for benchmark, in hydrogenation active metals oxide, WO3Weight content be 10～35%, the weight content of NiO is 5～15%, and the weight content of beta molecular sieve is 8～30%.
17. the Low Temperature Fischer Tropsch artificial oil designed for realizing method described in claim 1 and inferior feedstock oil Unionfining produce the equipment of fine-quality diesel oil, including mixed hydrogen tank (1), liquid phase hydrogenation reactor (2), gas-liquid counter current reactor (3), dephlegmator (4), it is characterized in that: described mixed hydrogen tank (1) has Fischer-Tropsch diesel import (1-1), recycle hydrogen import (1-2) and saturated molten hydrogen diesel oil outlet (1-3), described saturated molten hydrogen diesel oil outlet (1-3) is connected with the oil-in (2-1) of described liquid phase hydrogenation reactor (2)；Described gas-liquid counter current reactor (3) includes the hydrofining reaction district (3-1) at top and the hydrogenation cracking of bottom and isomerization reaction zone (3-2), the top of described gas-liquid counter current reactor (3) has oil-in (3-3) and gas outlet (3-4), the bottom of described gas-liquid counter current reactor (3) has hydrogen inlet (3-5) and oil-out (3-6), the oil-out (2-2) of described liquid phase hydrogenation reactor (2) is connected with the oil-in (3-3) of described gas-liquid counter current reactor (3), the oil-out (3-6) of described gas-liquid counter current reactor (3) is connected with the oil-in (4-1) of described dephlegmator (4).
18. Low Temperature Fischer Tropsch artificial oil according to claim 17 produces the equipment of fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterized in that: it also includes gas-liquid separator (5), the gas-liquid import (5-1) of described gas-liquid separator (5) is connected with the gas outlet (3-4) of described gas-liquid counter current reactor (3), and the gas outlet (5-2) of described gas-liquid separator (5) is connected with the described recycle hydrogen import (1-2) of mixed hydrogen tank (1) and the hydrogen inlet (3-5) of described gas-liquid counter current reactor (3) respectively.
19. Low Temperature Fischer Tropsch artificial oil according to claim 17 produces the equipment of fine-quality diesel oil with inferior feedstock oil Unionfining, it is characterised in that: tail oil outlet (4-2) of described dephlegmator (4) is connected with the oil-in (3-3) of described gas-liquid counter current reactor (3).
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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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| WO2017181813A1 (en) | 2017-10-26 |
| CN105778995B (en) | 2018-03-20 |
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