CN105419865B - A kind of method for producing jet fuel - Google Patents
A kind of method for producing jet fuel Download PDFInfo
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- CN105419865B CN105419865B CN201410464733.0A CN201410464733A CN105419865B CN 105419865 B CN105419865 B CN 105419865B CN 201410464733 A CN201410464733 A CN 201410464733A CN 105419865 B CN105419865 B CN 105419865B
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Abstract
The invention discloses a kind of method for producing jet fuel, including：By hydrogen and feedstock oil and Hydrobon catalyst haptoreaction, the effluent of Hydrobon catalyst is direct or isolates after gaseous stream, with hydrocracking catalyst haptoreaction, jet fuel and diesel oil are isolated from the effluent of hydrocracking catalyst, at least part diesel oil is mixed with feedstock oil, or at least part diesel oil is mixed with the liquid feedstock of hydrocracking catalyst；The arene content of the feedstock oil is more than 40 weight %；The haptoreaction condition of step (1) causes in feedstock oil double ring arene saturation factor to be 70 90%, and the haptoreaction condition of step (3) make it that mononuclear aromatics saturation factor is 75 95% in the liquid feedstocks of step (3).This method can be using catalytic cracking diesel oil as raw material, to produce the High-Density Jet for meeting No. 6 jet fuel standards of GJB1603 in high yield.
Description
Technical field
The present invention relates to a kind of method for producing jet fuel, in particular it relates to which one kind handles hydrocarbon ils in presence of hydrogen
Method to produce jet fuel.
Background technology
High-Density Jet is also known as big proportion boat coal, is that a class has high density (generally 0.835g/cm3More than),
High volume calorific value (generally 35.8MJ/m3More than) jet fuel.(density is generally 0.77- with common jet fuel
0.81g/cm3) compare, High-Density Jet can improve the calorific value of units of fuel volume, can in the timing of fuel tank capacity one
It is the high speed of a ship or plane of aerospace craft, the important leverage of remote flight to be effectively increased the energy that fuel tank carries fuel.For example：
Density is 845kg/m3(volume calorific value is about 36 × 103MJ/m3) fuel and density be 780kg/m3(volume calorific value is about
For 33 × 103MJ/m3) fuel compare, equally carry oil volume under the conditions of can make the energy of aircraft overloading about 9%.
Therefore, exploitation High-Density Jet turns into one of study hotspot.
CN102304387B discloses a kind of production method of coal-based high-density jet fuel, and this method includes following step
Suddenly：It is anti-that coalification light oil and liquefaction distillate from DCL/Direct coal liquefaction process enter the expanded bed hydrotreating with pressure interior circulation
Device is answered, is contacted with hydrogen, hydrotreating catalyst, the outlet streams of expanded bed hydrotreating reactor are obtained after separation, fractionation
To light fraction is oily, middle matter distillate and heavy distillate；Enter deep hydrogenation after the oily and middle matter distillate mixing of light fraction
Refined fixed bed reactors, contact with hydrogen, Hydrobon catalyst, react, the outlet of deep hydrofinishing fixed bed reactors
Logistics obtains High-Density Jet after separation, fractionation；Wherein, the top inside the hydrotreating reactor is set
There are liquid collection cups, collected liquid to be re-fed into the hydrotreating reaction after being boosted through pipeline and through forced circulation pump
The bottom of device.Method disclosed in CN102304387B is successively anti-in expanded bed hydrotreating when carrying out hydrotreating to charging
Answer in device and fixed bed reactors and carry out, add the complexity of technique.
US4875992 discloses a kind of method that big proportion boat coal is produced from condensed-nuclei aromatics and hydrogenation of aromatics raw material.The party
Raw material is the oil rich in di pah and two hydrogenated aromatic hydrocarbons in method.Raw material initially enters first paragraph progress desulfurization and denitrogenation is anti-
Should, product enters second segment and carries out selective hydrogenation saturated bicyclic aromatic hydrocarbons and two hydrogenated aromatic hydrocarbons generation cycloalkane, and generation is to the greatest extent
The few low molecular hydrocarbon of amount.Obtained big proportion boat coal weight index number (API °) is between 25 ° -35 °, and arene content is less than
50%.But, this method is more harsh to ingredient requirement, it is desirable to which the cut scope of raw material is at 350 °F -700 °F, while in raw material
Di pah containing more than 60 weight % and two hydrogenated aromatic hydrocarbons.
The content of the invention
It is an object of the invention to overcome the method for existing production High-Density Jet high to raw material and/equipment requirement
Technical problem there is provided a kind of method for producing jet fuel, this method technological process is succinct, to equipment and ingredient requirement not
Height, even on conventional fixed bed reactors, using the inferior feedstock oil of such as catalytic cracking diesel oil as charging, can also obtain
Obtain High-Density Jet.
The invention provides a kind of method for producing jet fuel, this method comprises the following steps：
Step (1)：By hydrogen and feedstock oil and Hydrobon catalyst haptoreaction；
Optional step (2)：Gaseous stream is isolated in the effluent obtained from step (1), liquid phase stream is obtained；
Step (3)：The effluent that the liquid phase stream and hydrogen or step (1) that step (2) is obtained are obtained splits with hydrogenation
Change catalyst haptoreaction；
Step (4)：Jet fuel and diesel oil are isolated in the effluent obtained from step (3)；
Step (5)：Mixed at least part diesel oil feeding step (1) that step (4) is obtained with feedstock oil, or will step
Suddenly the effluent obtained at least part diesel oil feeding step (3) that (4) are obtained with the liquid phase stream or step (1) is mixed；
Wherein, the arene content of the feedstock oil is more than 40 weight %；The haptoreaction condition of step (1) causes raw material
The saturation factor of double ring arene is 70-90% in oil, and the haptoreaction condition of step (3) causes total in the liquid feedstocks of step (3)
The saturation factor of aromatic hydrocarbons is 75-95%.
The method according to the invention has the following advantages that.
(1) the high density jet combustion for meeting No. 6 jet fuel standards of GJB1603 can be produced using the method for the present invention
Material, its density reaches 0.835g/cm3More than, weight heat value meets or exceeds 42.9MJ/kg.
(2) jet fuel produced using the method for the present invention, bicyclic above arene content is extremely low, reduces engine
Coke deposit rate, can effectively extend engine life.Meanwhile, using the jet fuel of the method production of the present invention, sulfur content
It is low with nitrogen content, reduce the amount of environmental contaminants.
(3) catalytic cracking diesel oil is a kind of poor-quality diesel-oil by cut fraction, and its sulphur nitrogen impurity content is high, and Cetane number is low；Also, urge
If changing cracked diesel oil produces cleaning diesel product using hydrogenation modifying process, one side hydrogen consumption is high, and economic benefit is low；It is another
The Cetane number of aspect product can only be improved to 40-45 or so, and density can only be reduced to 0.86-0.88g/cm3, still can only make
For diesel oil blending component.Even if the method that the present invention is provided, as raw material, can also produce high density using catalytic cracking diesel oil
Jet fuel, a kind of new processing technology routine is provided for the catalytic cracking diesel oil production high-value product of low value.
(4) using the method production jet fuel of the present invention, the utilization rate of feedstock oil is high, can realize 100% conversion, together
When can also obtain high jet fuel yield.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.
Fig. 1 is used for the first embodiment for illustrating the method according to the invention.
Fig. 2 is used for second of embodiment for illustrating the method according to the invention.
Fig. 3 is used for the third embodiment for illustrating the method according to the invention.
Fig. 4 is used for the 4th kind of embodiment for illustrating the method according to the invention.
Fig. 5 is used for the 5th kind of embodiment for illustrating the method according to the invention.
Description of reference numerals
1：Feedstock oil 2：Heat exchanger
3：Heating furnace 4：First hydroconversion reaction zone
5：Second hydroconversion reaction zone 6：The effluent of second hydroconversion reaction zone
7：Exchange heat back end hydrogenation charging 8：Separative element
9：Hydrogen-rich gas 10：Liquid phase component
11：Fractionation unit 12：Gaseous product
13：Naphtha cut 14：Jet fuel fraction
15：Heavy diesel fuel cut 16：Purification unit
17：Recycle hydrogen compression unit 18：Recycle hydrogen
19：Supplement hydrogen 20：Light diesel fuel cut
21：Diesel oil distillate 22：Steam stripping unit
23：Stripping fluid 24：Liquid phase stream
25：Gaseous stream
Embodiment
The invention provides a kind of method for producing jet fuel, this method comprises the following steps：
Step (1)：By hydrogen and feedstock oil and Hydrobon catalyst haptoreaction；
Optional step (2)：Gaseous stream is isolated in the effluent obtained from step (1), liquid phase stream is obtained；
Step (3)：The effluent that the liquid phase stream and hydrogen or step (1) that step (2) is obtained are obtained splits with hydrogenation
Change catalyst haptoreaction；
Step (4)：Jet fuel and diesel oil are isolated in the effluent obtained from step (3)；
Step (5)：Mixed at least part diesel oil feeding step (1) that step (4) is obtained with feedstock oil, or will step
Suddenly the effluent obtained at least part diesel oil feeding step (3) that (4) are obtained with the liquid phase stream or step (1) is mixed.
In the present invention, it is " optional " represent it is inessential, it can be understood as including or do not include, with or without.
The method according to the invention, the arene content of the feedstock oil is more than 40 weight %." arene content " is
Mononuclear aromatics, bicyclic and above aromatic hydrocarbons total content in feedstock oil.The arene content of the feedstock oil is generally 40-90 weights
Measure %.Preferably, the arene content of the feedstock oil is more than 60 weight %.In the method according to the invention, the feedstock oil,
On the basis of the total amount of aromatic hydrocarbons, the content of mononuclear aromatics is preferably 20-40 weight %.The method according to the invention, the raw material
In oil, the total content of cycloalkane and aromatic hydrocarbons is generally more than 60 weight %, preferably 60-95 weight %.It is highly preferred that the original
In material oil, the total content of cycloalkane and aromatic hydrocarbons is more than 70 weight %.
The density of the feedstock oil is generally 0.90-0.98g/cm3.Preferably, the density of the feedstock oil is 0.92g/
cm3More than.It is highly preferred that the density of the feedstock oil is 0.93g/cm3More than.
The initial boiling point of the feedstock oil is generally more than 100 DEG C, more preferably preferably more than 150 DEG C, more than 180 DEG C.
The end point of distillation of the feedstock oil is generally less than 410 DEG C, more preferably preferably less than 400 DEG C, less than 380 DEG C.Feedstock oil
Initial boiling point and the end point of distillation use method specified in ASTM D-86 to determine.
The method according to the invention, is not particularly limited for the sulphur nitrogen content in feedstock oil.Even sulphur nitrogen content compared with
The feedstock oil of high (especially nitrogen content is higher) can also be used as liquid feedstock of the invention.
The method according to the invention, the feedstock oil can be catalytic cracking diesel oil.The method according to the invention, the original
Material oil for catalytic cracking diesel oil and can also mix the miscella of oil refining, and described to mix oil refining can be heavy catalytic cycle oil, coal
One or more in tar and liquefied coal coil.The composition of the miscella with enable to the miscella arene content and
The total content of cycloalkane and aromatic hydrocarbons meets requirement described previously and is defined.Usually, it is described on the basis of the total amount of the miscella
The content of catalytic cracking diesel oil can be 30-90 weight %, preferably 60-90 weight %.
The catalytic cracking diesel oil can be the diesel oil distillate that Conventional catalytic cracking technique is obtained.According to the side of the present invention
Method, the catalytic cracking diesel oil is more preferably the catalytic cracking diesel oil that high severity catalytic cracking process is obtained, such as voluminous isomery
The catalytic cracking that the catalytic cracking process (that is, MIP techniques) and/or Deep catalytic cracking technology (that is, DCC techniques) of alkane are obtained
Diesel oil.
The method according to the invention, the Hydrobon catalyst can be with aromatic hydrocarbons saturation, hydrodesulfurization and hydrogenation
The catalyst of denitrogenation catalytic activity, can be noble metal catalyst, or non-precious metal catalyst.Preferably, it is described to add
Hydrogen catalyst for refining is non-precious metal catalyst.
Specifically, the Hydrobon catalyst can contain the vib gold of carrier and load on the carrier
Belong to component and group VIII metal component.On the basis of the total amount of Hydrobon catalyst and in terms of oxide, the vib
The content of metal component can be 5-50 weight %, preferably 7-35 weight %；The content of the group VIII metal component can
Think 1-10 weight %, preferably 1.5-7 weight %.Preferably, the Hydrobon catalyst can also contain at least one
Auxiliary agent, the auxiliary agent can be more than one or both of phosphorus, fluorine and boron.Using the total amount of the Hydrobon catalyst as base
Accurate and in terms of element, the content of the auxiliary agent can be 1-10 weight %.
The carrier of the Hydrobon catalyst can be silica, aluminum oxide and silica-alumina in one kind or
It is two or more.
In the Hydrobon catalyst, vib metals can be more than one or both of Cr, Mo and W, the
Group VIII metal can be more than one or both of Fe, Co and Ni.
In the Hydrobon catalyst, vib metals component and group VIII metal component can be with oxides
Form exist.The present invention it is a kind of preferred embodiment in, in the Hydrobon catalyst, vib metals group
Point exist in the form of the oxide, group VIII metal component exists in the form of metal salt, the Hydrobon catalyst for
Aromatic hydrocarbons saturation, hydrodesulfurization and hydrodenitrogeneration have more preferable catalytic effect, can more effectively remove the sulphur nitrogen in feedstock oil
Deng impurity, moreover it is possible to further promote aromatic hydrocarbons saturation, arene content, particularly polycyclic aromatic hydrocarbon content is greatly reduced, so as to reduce
With the haptoreaction temperature and/or raising Feed space velocities of Hydrobon catalyst.This preferred embodiment in, the hydrogenation
The carrier of catalyst for refining is preferably silica.It is further preferred that the specific surface area of the silica is 100-450m2/ g,
Preferably 150-300m2/ g, such as 160-200m2/g；The pore volume of the silica is 0.4-1.6mL/g, preferably 0.5-1mL/g.
The specific surface area and pore volume are determined using nitrogen adsorption methods.
It can be prepared according to the Hydrobon catalyst of the preferred embodiment using the method comprised the following steps：
(I) with the solution impregnating carrier of the water soluble compound containing vib metals, then it is dried and is calcined, institute
The condition for stating roasting is enough to make the water soluble compound containing vib metals be transformed into oxide；
(II) carrier obtained with the water soluble salt impregnation steps (I) of the metal containing group VIII, is then dried, described
Dry condition, which is insufficient to allow the water soluble salt of the metal containing group VIII to decompose, turns into oxide.
In step (I), the temperature of the drying can be 100-250 DEG C, and the duration of the drying can be according to dry
Dry temperature is selected, and typically can be 2-8 hours.In step (I), the temperature of the roasting is can will contain vib
The water soluble compound of metal is transformed into oxide and is defined, and typically can be 400-500 DEG C.The duration of the roasting with
It typically can be 3-6 hours depending on the temperature of roasting.
In step (II), the temperature of the drying turns into oxide decompose the water soluble salt of the metal containing group VIII
It is defined.Usually, in step (II), the temperature of the drying can be 60-200 DEG C, preferably 100-150 DEG C；The drying
Duration can be 2-6 hours.
The method according to the invention, the hydrocracking catalyst can be non-precious metal catalyst.Specifically, it is described to add
Hydrogen Cracking catalyst can contain carrier and the vib metals being supported on carrier component and group VIII metal component.
On the basis of the total amount of the hydrocracking catalyst and in terms of oxide, the content of the group VIII metal component is 1-10
Weight %, preferably 1.5-6 weight %；The content of the vib metals component is 5-50 weight %, preferably 10-40 weights
Measure %.
The carrier of the hydrocracking catalyst can be silica, aluminum oxide, silica-alumina and zeolite molecular sieve
One or both of more than.The zeolite molecular sieve can be faujasite, modenite, zeolite L, omega zeolite, the boiling of Y types
It is more than one or both of stone and β zeolites.In the hydrocracking catalyst, vib metals can be Mo and/or W, the
Group VIII metal can be Co and/or Ni.
The present invention it is a kind of preferred embodiment in, the carrier of the hydrocracking catalyst contains y-type zeolite, and
The y-type zeolite contains Mo and Ni, on the basis of the total amount of y-type zeolite, with MoO3The Mo of meter content is 0.5-10 weight %,
Preferably 2-9 weight %；Using the NiO Ni counted content as 0.1-5 weight %, preferably 0.2-3 weight %.Need explanation
It is, when calculating the vib metals of hydrocracking catalyst and group VIII tenor, according to this preferred embodiment
Y-type zeolite in Mo and Ni content also count.
According to this preferred embodiment, the y-type zeolite can be prepared using the method comprised the following steps：
(A) y-type zeolite is mixed with compound containing Mo and compound containing Ni, obtains a kind of mixture；
(B) by the mixture in the atmosphere formed by the gas of moisture vapor, 1-24 is handled in 200-700 DEG C small
When.
In step (A), the consumption of the compound containing Mo and the compound containing Ni causes in the y-type zeolite that finally gives
Mo and Ni content is respectively within above range and is defined.
After can be by the way that y-type zeolite is contacted with the aqueous solution containing compound containing Mo and the compound containing Ni, solid-liquid be carried out
Separation, the solid matter that collection is obtained is dried, so as to obtain the mixture.
The compound containing Mo can be common water solubility compound containing Mo, and its instantiation can include but is not limited to
It is more than one or both of molybdenum oxide, molybdate and paramolybdate.The compound containing Ni can contain for common water solubility
Ni compounds, its instantiation can include but is not limited to nickel nitrate, nickel acetate, basic nickel carbonate, nickel chloride and nickeliferous
It is more than one or both of complex compound.
In step (B), the processing is carried out preferably at a temperature of 300-650 DEG C.The duration of the processing is preferred
For 2-24 hours.The gas of the moisture vapor can contain water vapour and optional carrier gas.The carrier gas can for nitrogen,
It is more than one or both of group 0 element gas (such as argon gas), air and hydrogen.Water vapour and the volume ratio of the carrier gas can
Think 1：10-100, preferably 1：20-90.
The processing can be carried out by being continually fed into the gas of the moisture vapor into the mixture.Now,
The flow of the gas of the moisture vapor can be 0.3-2 standard cubic meters/(kilogram hour).
According to this preferred embodiment, on the basis of the total amount of the carrier of hydrocracking catalyst, the y-type zeolite
Content is preferably 5-85 weight %, preferably 5.5-40 weight %.
According to this preferred embodiment, the carrier of the hydrocracking catalyst can also contain at least one heat-resisting nothing
Machine oxide.The heat-resistant inorganic oxide refers to that maximum operation (service) temperature is not less than 600 DEG C of porous material.The heat resistant inorganic
The instantiation of oxide can include but is not limited to aluminum oxide, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide and oxygen
Change more than one or both of beryllium.Preferably, the heat-resistant inorganic oxide is aluminum oxide, silica and silica-oxidation
It is more than one or both of aluminium.
The method according to the invention, ratio between the Hydrobon catalyst and the hydrocracking catalyst can be with
Selected according to specific reaction condition.Preferably, the body of the Hydrobon catalyst and the hydrocracking catalyst
Product is than being 1：0.1-5, such as 1：0.4-2.
In the method according to the invention, step (1), on the basis of the flow direction of the feedstock oil, the hydrofinishing
The upstream of catalyst is preferably provided with hydrogenation protecting agent, to avoid the coke precursors such as alkene and/or colloid in feedstock oil from existing
Coking on Hydrobon catalyst, causes Hydrobon catalyst coking and deactivation, while the metal being also avoided that in feedstock oil is led
Cause Hydrobon catalyst poisoning.The consumption of the hydrogenation protecting agent can be selected according to the composition of feedstock oil.Preferably,
The hydrogenation protecting agent is the 5-30 volume %, such as 20-30 volumes % of the total amount of the Hydrobon catalyst.
The hydrogenation protecting agent can be that can realize the various catalyst of above-mentioned effect.Specifically, the hydrogenation protecting
Agent contains carrier and loads vib metal component on the carrier and group VIII metal component, with hydrogenation protecting agent
Total amount on the basis of and in terms of oxide, the content of the vib metals component can be 5.5-10 weight %, described the
The content of group VIII metal component can be 1-5 weight %.The group VIII metal is preferably Ni, the vib metals
Preferably Mo.The carrier is preferably aluminum oxide, the aluminum oxide being more preferably distributed with diplopore.
The method according to the invention, from the alkene in the effluent of further reduction hydrocracking catalyst and mercaptan sulfur
The angle of content is set out, in step (3), on the basis of the flow direction of the feedstock oil, under the hydrocracking catalyst
Trip is preferably provided with supplement Hydrobon catalyst.The consumption of the supplement Hydrobon catalyst by being hydrocracked can urge
Alkene and mercaptan sulfur content in the effluent of agent are reduced to expected content and are defined.Usually, the supplement hydrofinishing is urged
The amount of agent is the 10-50 volume %, such as 10-20 volumes % of the total amount of Hydrobon catalyst and hydrocracking catalyst.Institute
The species for stating supplement Hydrobon catalyst is identical with previously described Hydrobon catalyst, is no longer described in detail herein.It is described to mend
It can be identical to fill Hydrobon catalyst with the Hydrobon catalyst, or different.
The Hydrobon catalyst, hydrocracking catalyst, optional hydrogenation protecting agent and optional supplement hydrogenation
Catalyst for refining can be located in the differential responses area of same reactor, can also be located in different reactors, Ke Yigen
Selected, be not particularly limited according to specific device.
The method according to the invention, step (1) and step (3) are carried out preferably in fixed bed reactors.
The method according to the invention, the haptoreaction condition of step (1) make it that the saturation factor of double ring arene in feedstock oil is
70-90%, preferably more than 75%.The saturation factor of double ring arene is calculated using below equation and obtained：
It is bicyclic in the effluent that quality-step (1) of double ring arene is obtained in the saturation factor=﹝ ﹙ feedstock oils of double ring arene
Zhi Liang ﹞ × 100% of double ring arene in Zhi Liang ﹚/feedstock oil of aromatic hydrocarbons.
Specifically, in step (1), temperature can be 250-450 DEG C, preferably 300-410 DEG C, such as 340-380 DEG C；Hydrogen point
Pressure can be 7-16MPa, preferably 10-15MPa；Hydrogen to oil volume ratio (that is, standard state hydrogen to oil volume ratio) can be 100-
2000Nm3/m3, preferably 300-1500Nm3/m3, such as 800-1300Nm3/m3；Volume space velocity can be 0.2-10h during liquid-1, it is excellent
Elect 0.5-5h as-1。
The method according to the invention, the haptoreaction condition of step (3) causes total aromatic hydrocarbons in the liquid feedstocks of step (3)
Saturation factor is 75-95%, preferably more than 80%.The saturation factor of total aromatic hydrocarbons is calculated using below equation to be obtained：
The stream that quality-step (3) of total aromatic hydrocarbons in the liquid feedstock of the saturation factor=﹝ ﹙ steps (3) of total aromatic hydrocarbons is obtained
Zhi Liang ﹞ × 100% of total aromatic hydrocarbons in the liquid feedstock for the Zhi Liang ﹚/step (3) for going out total aromatic hydrocarbons in thing.
Specifically, in step (3), temperature can be 250-450 DEG C, preferably 310-430 DEG C, such as 350-380 DEG C；Hydrogen point
Pressure can be 3-25MPa, such as preferably 6-20MPa, 10-15MPa；Hydrogen to oil volume ratio (that is, standard state hydrogen to oil volume ratio) can
Think 100-2000Nm3/m3, preferably 300-1500Nm3/m3；Volume space velocity can be 0.2-10h during liquid-1, preferably 1-5h-1。
The method according to the invention, the effluent that step (1) is obtained can be sent directly into step (3) with adding without isolation
Hydrogen Cracking catalyst haptoreaction, can also isolate after the gaseous stream in the effluent that step (1) is obtained, be re-fed into step
Suddenly (3) neutralize hydrogen together with hydrocracking catalyst haptoreaction.Preferably, the method according to the invention also includes step
(2)：From step (1) obtain effluent in go out to isolate gaseous stream, obtain liquid phase stream, and by the liquid phase stream and hydrogen
With hydrocracking catalyst haptoreaction in feeding step (3).It can be isolated in unifining process and generated by step (2)
Hydrogen sulfide, ammonia and small molecule hydrocarbon (carbon number is less than 5 hydrocarbon) so that further extension hydrocracking catalyst makes
With the life-span, while reaction temperature when being contacted with hydrocracking catalyst can also be reduced.The effluent obtained with step (1) without
Separation directly compared with hydrocracking catalyst haptoreaction, isolate after gas-phase product therein again with hydrocracking catalyst
Haptoreaction, can make the Contact Temperature with hydrocracking catalyst reduce 10-30 DEG C, so that plant energy consumption is reduced, optimization hydrogenation
Temperature Distribution in Cracking catalyst bed.Meanwhile, isolate the gas-phase product in the effluent that step (1) is obtained, moreover it is possible to carry
Hydrogen dividing potential drop and hydrogen effective rate of utilization during high and hydrocracking catalyst haptoreaction.
In step (2), the condition of separation causes the sulfur-bearing chemical combination generated during the hydrofining reaction of step (1)
Thing (such as hydrogen sulfide) and nitrogen-containing compound (such as ammonia) are located in the gaseous stream.It can be obtained using conventional method from step (1)
To effluent in isolate gaseous stream.Specifically, can by being flashed to the effluent that step (1) is obtained and/or
Stripping, so as to isolate gaseous stream therein.The flash distillation and steam stripped condition are can isolate gaseous stream, particularly
The hydrogen sulfide and ammonia of unifining process generation are defined.Usually, the condition of the flash distillation includes：Temperature can be 30-400
DEG C, preferably 200-380 DEG C；In terms of gauge pressure, pressure can be 3-20MPa, preferably 8-16MPa.The steam stripped condition bag
Include：Temperature can be 30-400 DEG C, preferably 200-380 DEG C；In terms of gauge pressure, pressure can be 3-20MPa, preferably 10-
16MPa。
The method according to the invention, the gaseous stream isolated contains hydrogen, can be purified to remove sulphur therein
Recycled after nitrogen.
In the method according to the invention, step (4), the outflow that can be obtained using conventional various methods from step (3)
Jet fuel and diesel oil are isolated in thing.In one embodiment, it is separated into the effluent that first can be obtained step (3)
For gaseous stream and liquid phase stream, then the liquid phase stream is fractionated, gaseous product, naphtha cut, jet is obtained
Fuel fraction and diesel oil distillate.The gaseous stream separated is hydrogen-rich gas, and recycle hydrogen can be used as after being further purified
Use.
The method according to the invention, the initial boiling point and the end point of distillation of jet fuel fraction with feedstock oil species difference.
Usually, the initial boiling point of jet fuel fraction can be more than 140 DEG C of a temperature, such as 140 DEG C, 150 DEG C or 170 DEG C.
The end point of distillation of jet fuel can be less than 300 DEG C of a temperature, such as 300 DEG C, 280 DEG C or 270 DEG C.The diesel oil refers to
Initial boiling point higher than jet fuel the end point of distillation cut (that is, the end point of distillation of jet fuel fraction be jet fuel fraction and diesel oil
Distillation cut point between cut).Usually, the initial boiling point of the diesel oil can be a temperature higher than 270 DEG C, such as be higher than
290 DEG C of a temperature, a temperature higher than 300 DEG C.Whole cuts that can be using initial boiling point higher than jet fuel are used as bavin
Initial boiling point, can also be higher than the part cut in the cut of jet fuel as diesel oil distillate, such as by the end point of distillation by oil distillate
To be not higher than 360 DEG C of cut as diesel oil distillate.The initial boiling point and the end point of distillation of jet fuel and diesel oil use ASTM D2887
Specified in method determine.
In the method according to the invention, step (5), at least part diesel oil feeding step (1) that step (4) can be obtained
In charging as Hydrobon catalyst is mixed with feedstock oil；At least part diesel oil feeding that step (4) can also be obtained
The liquid phase stream obtained in step (3) with step (2) mixes the charging as hydrocracking catalyst；Can also be by step (4)
Obtained at least part diesel oil mixes the charging as hydrocracking catalyst with the effluent that step (1) is obtained.By step (4)
In obtained at least part diesel oil feeding step (1), can further reduce the jet fuel finally prepared arene content and
Sulphur nitrogen content；In at least part diesel oil feeding step (2) that step (4) is obtained, the receipts of jet fuel can be further improved
Rate.
In step (5), whole diesel oil can be sent into step (1) or step (3), part diesel oil can also be sent into
In step (1) or step (3).From the angle of the further yield for improving jet fuel, whole diesel oil distillates are sent into
In step (1) or step (3).Can be 330 by the end point of distillation when part diesel oil is sent into step (1) or step (3)
DEG C, be preferably 310 DEG C fraction section feeding step (1) or step (3) in, i.e., by light diesel fuel cut feeding step (1) or
It in step (3), so can further extend the service life of catalyst, and obtain the higher jet fuel of quality.
Jet fuel is produced using the method for the present invention, obtained jet fuel is High-Density Jet, its density energy
Enough reach 0.835g/cm3More than, typically in 0.835-0.850g/cm3In the range of.Using the jet of the method production of the present invention
Fuel has higher net heating value, more than 42.9MJ/kg can be reached, typically in the range of 42.9-43.3MJ/kg.
Fig. 1 to Fig. 5 exemplarily gives five kinds of embodiments of the method for the production jet fuel that the present invention is provided, but
It is it will be appreciated by persons skilled in the art that the method that the present invention is provided is not limited to this five kinds of embodiments.Tie below
Fig. 1 to Fig. 5 is closed to illustrate this five kinds of embodiments.
As shown in figure 1, feedstock oil 1, recycle hydrogen 18 and supplement hydrogen 19 are mixed, hydrogenation charging is obtained.Hydrogenation charging is passed through
Heat exchanger 2 and the effluent 6 of the second hydroconversion reaction zone 5 are exchanged heat, and heat exchange back end hydrogenation charging 7 subsequently enters to enter in heating furnace 3
Row heating, subsequently into the first hydroconversion reaction zone 4 and Hydrobon catalyst haptoreaction, the outflow of the first hydroconversion reaction zone 4
Thing is directly entered the second hydroconversion reaction zone 5 and contacted with hydrocracking catalyst without isolation, the effluent of the second hydroconversion reaction zone 5
After 6 are exchanged heat in heat exchanger 2 with hydrogenation charging, into separative element 8, hydrogen-rich gas 9 and liquid phase component are isolated
10.Hydrogen-rich gas 9 removes impurity therein (such as hydrogen sulfide) into purification unit 16 and enters liter in recycle hydrogen compression unit 17 afterwards
Pressure Posterior circle is used.Liquid phase component 10 enters fractionation unit 11, is separated into gaseous product 12, naphtha cut 13, jet combustion
Expect cut 14, light diesel fuel cut 20 and heavy diesel fuel cut 15.Light diesel fuel cut 20 and the effluent of the first hydroconversion reaction zone 4 are mixed
Send into the second hydroconversion reaction zone 5 and contacted with hydrocracking catalyst after conjunction.
Fig. 2 shows second of embodiment of the method according to the invention, below only in conjunction with Fig. 2 to the embodiment with
The difference of the first embodiment is illustrated shown in Fig. 1.As shown in Fig. 2 in fractionation unit 11, not by diesel oil distillate
It is cut into light diesel fuel cut and heavy diesel fuel cut, but by the effluent of whole hydroconversion reaction zones 4 of diesel oil distillate 21 and first
Send into the second hydroconversion reaction zone 5 and contacted with hydrocracking catalyst after mixing.
Fig. 3 shows the third embodiment of the method according to the invention, below only in conjunction with Fig. 3 to the embodiment with
The difference of the first embodiment is illustrated shown in Fig. 1.As shown in figure 3, the effluent of the first hydroconversion reaction zone 4 is not
The second hydroconversion reaction zone 5 and hydrocracking catalyst haptoreaction are directly entered, but is entered in steam stripping unit 22, passes through stripping
The effluent of first hydroconversion reaction zone 4 is separated into liquid phase stream 24 and gaseous stream 25 by medium 23.Wherein, gaseous stream 25
Rich in hydrogen, purified unit 16 and recycle hydrogen compression unit 17 can make after being purified and being boosted as recycle hydrogen 18
Then entered with, liquid phase stream 24 in second hydroconversion reaction zone 5 with hydrocracking catalyst haptoreaction.
Fig. 4 shows the 4th kind of embodiment of the method according to the invention, below only in conjunction with Fig. 4 to the embodiment with
The difference of the third embodiment is illustrated shown in Fig. 3.As shown in figure 4, in fractionation unit 11, not by diesel oil distillate
It is cut into light diesel fuel cut and heavy diesel fuel cut, but by whole diesel oil distillates 21 and the liquid phase thing for coming from steam stripping unit 22
Send into the second hydroconversion reaction zone 5 and contacted with hydrocracking catalyst after the mixing of stream 24.
Fig. 5 shows the 5th kind of embodiment of the method according to the invention.Below only in conjunction with Fig. 5 to the embodiment with
The difference of the first embodiment shown in Fig. 1 is illustrated.As shown in figure 5, light diesel fuel cut 20 is mixed with feedstock oil 1
After conjunction after elder generation after heat exchanger 2 and heating furnace 3, into the first hydroconversion reaction zone 4 and Hydrobon catalyst haptoreaction.
Describe the present invention in detail with reference to embodiments, but and be not so limited the scope of the present invention.
In following examples and comparative example, jet fuel fraction yield is defined as full cut product and fractionated out by fractionating column
Jet fuel fraction and feedstock oil percentage by weight.
In following examples and comparative example, feedstock oil, first are determined using method specified in SH/T 0606-94 respectively
The composition of the liquid feedstock and effluent of fixed bed reactors effluent and the second fixed bed reactors, using below equation
Calculate the saturation factor of double ring arene and the saturation factor of total aromatic hydrocarbons：
The effluent of the fixed bed reactors of quality-the first of double ring arene in the saturation factor=﹝ ﹙ feedstock oils of double ring arene
Zhi Liang ﹞ × 100% of double ring arene in Zhi Liang ﹚/feedstock oil of middle double ring arene；
The quality-the second of total aromatic hydrocarbons is fixed in the liquid feedstock of saturation factor=﹝ the second fixed bed reactors of ﹙ of total aromatic hydrocarbons
Zhi Liang ﹞ of total aromatic hydrocarbons in the liquid feedstock of the fixed bed reactors of Zhi Liang ﹚ of total aromatic hydrocarbons in the effluent of bed reactor/second ×
100%.
Embodiment 1-6 is used for the method for illustrating the present invention.
Embodiment 1
The feedstock oil A used in the present embodiment is catalytic cracking diesel oil, and its property is listed in table 1.
The present embodiment is carried out in two fixed bed reactors, and hydrofinishing catalysis is loaded in the first fixed bed reactors
Agent；On the basis of the flow direction of liquid material, hydrocracking catalyst and benefit are loaded successively in the second fixed bed reactors
Fill Hydrobon catalyst.Hydrobon catalyst, hydrocracking catalyst and the admission space for supplementing Hydrobon catalyst
Than for 40：60：10.
Hydrobon catalyst and supplement Hydrobon catalyst are prepared using following methods.
By 3000 grams of commercial silica gels of Silica Gel 955 (U.S.'s Davison Chemical Products, SiO2Content
For 99.8 weight %) and 75 grams of sesbania powders it is well mixed after, then (concentration 65-68 weight % analyze pure, Shan with 84 milliliters of nitric acid
Tou Xi Gansu Province chemical plant product) and 4200 milliliters of water mixing.Obtained mixture is continued into kneading uniformly on double screw banded extruder,
Then it is extruded into 1.3 millimeters of Φ butterfly bar, after wet bar is dried 4 hours through 120 DEG C, is calcined 3 hours in 600 DEG C, obtains silica
Carrier S.Determined through nitrogen adsorption methods, the specific surface area of the carrier is 180m2/ g, pore volume is 0.78mL/g.
With 200 milliliters of dilute ammonia solution (NH containing 21.9 grams of ammonium paramolybdates3Concentration be 10 weight %) dipping 200 grams of oxygen
SiClx carrier S, dip time is 2 hours, is then dried 4 hours in 120 DEG C, is then calcined 4 hours, is loaded at 460 DEG C
The carrier containing molybdenum of molybdenum oxide.Then, carried with 156 milliliters of aqueous solution dippings containing 13.3 grams of cobalt nitrates and 4.4 grams of nickel nitrates containing molybdenum
Body 2 hours, then dries 4 hours in 120 DEG C, obtains Hydrobon catalyst.Using the x-ray fluorescence spectrometry catalysis
The composition of agent, wherein, MoO3Content be 8.0 weight %, NiO content be 0.6 weight %, CoO content be 1.5 weights
Measure %.
Hydrocracking catalyst is prepared using following methods.
Taking 50 grams of USY zeolites, (Changling Branch, Chinese Petro-Chemical Co Ltd's product, lattice constant is 24.50
Angstrom, crystallinity is 88%, and sodium oxide content is 0.8 weight %, and butt is 75 weight %), (it is 25 with stirring in normal temperature condition
DEG C) under be added to 60mL containing ammonium molybdate (with MoO3Meter, concentration is 27g/L) and nickel nitrate (in terms of NiO, concentration is 5.4g/L)
Ammoniacal liquor (NH3Concentration be 10 weight %) in mixed solution, be sufficiently stirred for, then dried 4 hours in 120 DEG C, be subsequently placed in pipe
Formula stove flat-temperature zone, in hydrogen and water vapour atmosphere, is calcined 24 hours in 300 DEG C, so that molecular sieve MNY-1 is obtained, wherein, roasting
The actual conditions of burning is：Gas flow is 0.5Nm3The volume ratio of/(kgh), water vapour and hydrogen is 1：40.Using X-ray
Fluorescence spectrum method for measuring molecular sieve MNY-1 composition, wherein, MoO3Content be 3.0 weight %, NiO the weight of content 0.6
Measure %.
By 185.7 grams of boehmites, (Changling Branch, Chinese Petro-Chemical Co Ltd's product, butt is 70 weights
Amount %) mixed with 93.3 grams of MNY-1 types molecular sieves (butt is 75 weight %), it is extruded into three leaves that circumscribed circle diameter is 1.6 millimeters
Shape bar, wet bar is dried 3 hours in 120 DEG C, is then calcined 4 hours at 450 DEG C, is obtained carrier Z1.
With 88 milliliters of ammonium metatungstates (with WO3Meter, concentration be 422 g/l) and nickel nitrate (in terms of NiO, concentration is 64.9
G/l) mixed aqueous solution 100 grams of carrier Z1 of dipping, dip time is 1 hour, then dries 2 hours, then exists in 120 DEG C
450 DEG C are calcined 3 hours, obtain catalytic cracking catalyst.Using the group of the x-ray fluorescence spectrometry catalytic cracking catalyst
Into, wherein, MoO3Content be 0.75 weight %, WO3Content be 26 weight %, NiO content be 4.1 weight %.
The concrete technology flow process of the present embodiment is as follows.
After feedstock oil and hydrogen are mixed and preheated, in the first fixed bed reactors of feeding, with Hydrobon catalyst
(that is, the first reaction zone) haptoreaction.It is anti-that the effluent of first fixed bed reactors is directly entered the second fixed bed without isolation
Answer in device successively with hydrocracking catalyst (that is, second reaction zone) and supplement Hydrobon catalyst haptoreaction, wherein, tool
Precursor reactant condition is as shown in the table of table 2.The effluent of second fixed bed reactors is carried out after gas-liquid separation, by the liquid phase group isolated
It is fractionated, collects gaseous product, jet fuel fraction, light diesel fuel cut (boiling range is 270-330 DEG C) and heavy diesel fuel cut
(initial boiling point is the cut more than 330 DEG C).Is sent into after light diesel fuel cut is mixed with the effluent of the first fixed bed reactors
In two fixed bed reactors successively with hydrocracking catalyst and supplement Hydrobon catalyst haptoreaction.
The property of obtained jet fuel is listed in table 2.
Embodiment 2
Jet fuel is produced using method same as Example 1, unlike, Hydrobon catalyst used and institute
Supplement Hydrobon catalyst is prepared using following methods：
With 200 milliliters of dilute ammonia solution (NH containing 21.9 grams of ammonium paramolybdates3Concentration be 10 weight %) dipping 200 grams of oxygen
SiClx carrier S, dip time is 2 hours, is then dried 4 hours in 120 DEG C, is then calcined 4 hours, is loaded at 460 DEG C
The carrier containing molybdenum of molybdenum oxide.Then, carried with 156 milliliters of aqueous solution dippings containing 13.3 grams of cobalt nitrates and 4.4 grams of nickel nitrates containing molybdenum
Body 2 hours, then dries 4 hours in 120 DEG C, is then dried 4 hours at 470 DEG C, obtain the Hydrobon catalyst.Using
The composition of the x-ray fluorescence spectrometry catalyst, wherein, MoO3Content be 8.0 weight %, NiO content be 0.6 weight
% is measured, CoO content is 1.5 weight %.
The property of obtained jet fuel is listed in table 2.
Embodiment 3
Jet fuel is produced using method same as Example 1, unlike, hydrocracking catalyst used is used
It is prepared by following methods：
By 185.7 grams of boehmites, (Changling Branch, Chinese Petro-Chemical Co Ltd's product, butt is 70 weights
Measure %) (Changling Branch, Chinese Petro-Chemical Co Ltd's product, lattice constant is 24.50 with 93.3 grams of USY zeolites
Angstrom, crystallinity is 88%, and sodium oxide content is 0.8 weight %, and butt is 75 weight %) mixing, it is 1.6 to be extruded into circumscribed circle diameter
The trilobal bar of millimeter, wet bar is dried 3 hours in 120 DEG C, is then calcined 4 hours at 450 DEG C, so as to obtain carrier DZ1.
With 88 milliliters of ammonium metatungstates (with WO3Meter, concentration is 422 g/l), ammonium molybdate is (with MoO3Meter, concentration be 24.3 grams/
Rise) and nickel nitrate (in terms of NiO, concentration is 69.8 g/l) mixed aqueous solution 100 grams of carrier DZ1 of dipping, dip time is 1 small
When, then dried 2 hours in 120 DEG C, be then calcined 3 hours at 450 DEG C, obtain the catalytic cracking catalyst.Using X-ray
The composition of the fluorescence spectrum method for measuring catalytic cracking catalyst, wherein, MoO3Content be 0.75 weight %, WO3Content be 26
Weight %, NiO content are 4.1 weight %.
The property of obtained jet fuel is listed in table 2.
Comparative example 1
Jet fuel is produced using method same as Example 1, unlike, light diesel fuel cut and first are not reacted
The effluent mixing in area, but directly export.The property of obtained jet fuel is listed in table 2.
Comparative example 2
Jet fuel is produced using method same as Example 1, unlike, reaction condition is as shown in table 2.Obtain
The property of jet fuel is as shown in table 2.
Comparative example 3
Jet fuel is produced using method same as Example 1, unlike, reaction condition is as shown in table 2.Obtain
The property of jet fuel is as shown in table 2.
Comparative example 4
Jet fuel is produced using method same as Example 1, unlike, using feedstock oil DA, its property is in table 1
In list.The property of reaction condition and obtained jet fuel is as shown in table 2.
Table 1
Table 2
*：On the basis of the total amount of Hydrobon catalyst and hydrocracking catalyst.
Embodiment 4
The feedstock oil B used in the present embodiment is catalytic cracking diesel oil, and its property is listed in table 3.
The present embodiment is carried out in two fixed bed reactors, and hydrofinishing catalysis is loaded in the first fixed bed reactors
Agent；On the basis of the flow direction of liquid material, hydrocracking catalyst and benefit are loaded successively in the second fixed bed reactors
Fill Hydrobon catalyst.Hydrobon catalyst, hydrocracking catalyst and the admission space for supplementing Hydrobon catalyst
Than for 40：60：10.Hydrocracking catalyst is is purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd
RHC-5 catalyst.
The Hydrobon catalyst is identical with supplement Hydrobon catalyst, is prepared using following methods.
200 grams of silica support S are impregnated with 200 milliliters of aqueous solution containing 70.5 grams of ammonium paramolybdates and 23.2 grams of phosphoric acid (to adopt
Prepared with method same as Example 1), dip time is 2 hours, is then dried in 120 DEG C 4 hours, then in 460 DEG C of roastings
Burn 4 hours, obtain loading the carrier containing molybdenum of molybdenum oxide.Then, with 118 milliliters containing 11.4 grams of cobalt nitrates and 45.7 grams of nickel nitrates
Aqueous solution dipping carrier containing molybdenum 2 hours, then dries 4 hours in 120 DEG C, obtains Hydrobon catalyst.Using XRF
The composition of the spectrographic determination catalyst, wherein, MoO3Content be 20.2 weight %, NiO content be 4.0 weight %, CoO
Content be 1.0 weight %, P2O5Content be 5.0 weight %.
The concrete technology flow process of the present embodiment is as follows.
After feedstock oil and hydrogen are mixed and preheated, in the first fixed bed reactors of feeding, with Hydrobon catalyst
(that is, the first reaction zone) haptoreaction.It is anti-that the effluent of first fixed bed reactors is directly entered the second fixed bed without isolation
Answer in device successively with hydrocracking catalyst (that is, second reaction zone) and supplement Hydrobon catalyst haptoreaction, wherein, tool
Precursor reactant condition is as shown in the table of table 4.The effluent of second fixed bed reactors is carried out after gas-liquid separation, by the liquid phase group isolated
Be fractionated, collect gaseous product, jet fuel fraction, diesel oil distillate (initial boiling point is whole cuts more than 300 DEG C).Will
Diesel oil distillate and fresh feed oil sent into after mixing in the first fixed bed reactors with Hydrobon catalyst haptoreaction.
The property of obtained jet fuel is listed in table 4.
Table 3
Table 4
*：On the basis of the total amount of Hydrobon catalyst and hydrocracking catalyst.
Embodiment 5
The feedstock oil C used in the present embodiment is catalytic cracking diesel oil C1 and coal tar light fraction C2 miscella, wherein,
C1 and C2 mass ratio is 2：1, its property is listed in table 5.
The present embodiment is carried out in two fixed bed reactors, and hydrofinishing catalysis is loaded in the first fixed bed reactors
Agent；On the basis of the flow direction of liquid material, hydrocracking catalyst and benefit are loaded successively in the second fixed bed reactors
Fill Hydrobon catalyst.Hydrobon catalyst, hydrocracking catalyst and the admission space for supplementing Hydrobon catalyst
Than for 65：35：10.Hydrobon catalyst and supplement Hydrobon catalyst is purchased from Sinopec Groups
The trade mark of Chang Ling branch company is RS-2000 catalyst.
Hydrocracking catalyst is prepared using following methods.
Taking 50 grams of USY zeolites, (Sinopec Group's catalyst Chang Ling branch company product, lattice constant is
24.54 angstroms, crystallinity is 89%, and sodium oxide content is 0.7 weight %, and butt is 75 weight %), it is adjoint to stir in normal temperature condition
75mL is added to containing ammonium molybdate (with MoO under (being 25 DEG C)3Meter, concentration is 103.3g/L) and nickel nitrate (in terms of NiO, concentration is
Ammoniacal liquor (NH 20.4g/L)3Concentration be 10 weight %) in mixed solution, be sufficiently stirred for, then dried 4 hours in 120 DEG C,
Tube furnace flat-temperature zone is subsequently placed in, in hydrogen and water vapour atmosphere, is calcined 2 hours in 550 DEG C, so as to obtain molecular sieve MNY-
2, wherein, the actual conditions of roasting is：Gas flow is 1.2Nm3The volume ratio of/(kgh), water vapour and hydrogen is 1：50.
Using x-ray fluorescence spectrometry molecular sieve MNY-2 composition, wherein, MoO3Content be 9.0 weight %, NiO content
1.8 weight %.
By 245.5 grams of boehmites (Sinopec Group's catalyst Chang Ling branch company product, butt
For 70 weight %) mixed with 13.5 grams of MNY-2 types molecular sieves (butt is 75 weight %), circumscribed circle diameter is extruded into for 1.6 millimeters
Trilobal bar, wet bar in 120 DEG C dry 3 hours, then 600 DEG C be calcined 4 hours, obtain carrier Z2.
Contain ammonium metatungstate (with WO with 85 milliliters3Meter, concentration be 478.8 g/l) and nickel nitrate (in terms of NiO, concentration is
54.7 g/l) and the mixed solution of 162.3 grams of ethylene glycol impregnate 100 grams of carrier Z2, dip time is 1 hour, then in 120
DEG C dry 2 hours, then 450 DEG C be calcined 3 hours, obtain catalytic cracking catalyst.Should using x-ray fluorescence spectrometry
The composition of catalytic cracking catalyst, wherein, MoO3Content be 0.3 weight %, WO3Content be 26 weight %, NiO content
For 3.3 weight %.
The concrete technology flow process of the present embodiment is as follows.
After feedstock oil and hydrogen are mixed and preheated, in the first fixed bed reactors of feeding, with Hydrobon catalyst
(that is, the first reaction zone) haptoreaction.The effluent of first fixed bed reactors enters to be stripped in stripper, is contained
The gaseous stream and liquid phase stream of hydrogen sulfide and ammonia.Wherein, using hydrogen as stripping fluid, the pressure in stripper is
10MPa (gauge pressure), temperature is 260 DEG C.Liquid phase stream and hydrogen enter urges with being hydrocracked successively in the second fixed bed reactors
Agent (that is, second reaction zone) and supplement Hydrobon catalyst haptoreaction.The effluent of second fixed bed reactors is carried out
After gas-liquid separation, the liquid phase component isolated is fractionated, gaseous product, jet fuel fraction, diesel oil distillate (fore-running is collected
Point is whole cuts more than 300 DEG C).The second fixed bed is sent into after diesel oil distillate is mixed with the liquid phase stream from stripper
In reactor successively with hydrocracking catalyst and supplement Hydrobon catalyst haptoreaction.
The property of specific reaction condition and obtained jet fuel is listed in table 6.
Table 5
Table 6
*：On the basis of the total amount of Hydrobon catalyst and hydrocracking catalyst.
Embodiment 6
The feedstock oil D used in the present embodiment is catalytic cracking diesel oil C1 and direct liquefying diesel oil of coal E1 miscella, its
In, C1 and E1 mass ratio are 2：1, its property is listed in table 7.
The present embodiment is carried out in two fixed bed reactors, on the basis of the flow direction of liquid material, solid first
Hydrogenation protecting agent and Hydrobon catalyst are loaded in fixed bed reactor successively；On the basis of the flow direction of liquid material,
Hydrocracking catalyst and supplement Hydrobon catalyst are loaded in second fixed bed reactors successively.Hydrobon catalyst,
The admission space ratio of hydrocracking catalyst and supplement Hydrobon catalyst is 70：30：10.Hydrobon catalyst and supplement
The catalysis that it is RS-1000 purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd that Hydrobon catalyst, which is,
Agent.It purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd is RG-30A and RG-30B that hydrogenation protecting agent, which is,
Catalyst, hydrogenation protecting agent is 30 volume % of the total amount of Hydrobon catalyst, on the basis of the flow direction of liquid material,
RG-30A is located at RG-30B upstream, and RG-30A and RG-30B weight ratio are 2：1.
Hydrocracking catalyst is prepared using following methods.
Take 100 grams of NaY zeolites (Sinopec Group's catalyst Chang Ling branch company product, lattice constant
For 24.65 angstroms, crystallinity is 95%, Na2O content is 5.3 weight %), exchange 1 at 80 DEG C with 0.1mol/L ammonium nitrate solution
Hour, then filter, the molecular sieve being collected into obtains HNaY in 4 hours in Muffle furnace in 560 DEG C of roastings.
By 50 grams of HNaY and 0.53 gram of molybdenum trioxides, 0.12 gram of nickel oxide ground and mixed in agate mortar, then, incite somebody to action
It is placed in the flat-temperature zone of tube furnace, in hydrogen and water vapour atmosphere, is calcined 8 hours in 600 DEG C, so as to be divided to mixture
Son sieve MNY-3, wherein, the actual conditions of roasting is：Gas flow is 1.8Nm3The volume ratio of/(kgh), water vapour and hydrogen
For 1：90.Using x-ray fluorescence spectrometry molecular sieve MNY-3 composition, wherein, MoO3Content be 1.0 weight %,
The NiO weight % of content 0.2.
By 171.4 grams of boehmites (Sinopec Group's catalyst Chang Ling branch company product, butt
For 70 weight %) mixed with 106.7 grams of MNY-3 types molecular sieves (butt is 75 weight %), circumscribed circle diameter is extruded into for 1.6 millimeters
Trilobal bar, wet bar in 120 DEG C dry 3 hours, then 600 DEG C be calcined 4 hours, obtain carrier Z3.
Contain ammonium metatungstate (with WO with 87 milliliters3Meter, concentration be 513.1 g/l) and nickel nitrate (in terms of NiO, concentration is
47.9 g/l) mixed aqueous solution impregnate 100 grams of carrier Z3, dip time be 1 hour, then in 120 DEG C dry 2 hours, connect
And be calcined 3 hours at 450 DEG C, obtain catalytic cracking catalyst.Using the x-ray fluorescence spectrometry catalytic cracking catalyst
Composition, wherein, MoO3Content be 0.3 weight %, WO3Content be 30 weight %, NiO content be 2.9 weight %.
The concrete technology flow process of the present embodiment is as follows.
After feedstock oil and hydrogen are mixed and preheated, in the first fixed bed reactors of feeding, successively with hydrogenation protecting agent
With Hydrobon catalyst (Hydrobon catalyst is referred to as into the first reaction zone) haptoreaction.The stream of first fixed bed reactors
Go out thing into being stripped in stripper, obtain gaseous stream and liquid phase stream containing hydrogen sulfide and ammonia.Wherein, using hydrogen
As stripping fluid, the pressure in stripper is 11.6MPa (gauge pressure), and temperature is 200 DEG C.Liquid phase stream and hydrogen enter second
It is anti-with hydrocracking catalyst (that is, second reaction zone) and supplement Hydrobon catalyst contact successively in fixed bed reactors
Should.The effluent of second fixed bed reactors is carried out after gas-liquid separation, and the liquid phase component isolated is fractionated, and collects gas
(initial boiling point is more than 330 DEG C for product, jet fuel fraction, light diesel fuel cut (boiling range is 280-330 DEG C) and heavy diesel fuel cut
Whole cuts).Sent into after light diesel fuel cut is mixed with the liquid phase stream from stripper in the second fixed bed reactors successively
With hydrocracking catalyst and supplement Hydrobon catalyst haptoreaction.
The property of specific reaction condition and obtained jet fuel is listed in table 8.
Table 7
Table 8
*：On the basis of the total amount of Hydrobon catalyst and hydrocracking catalyst.
Embodiment 1-6's as a result, it was confirmed that reaching 0.835g/ using the density of jet fuel of the method production of the present invention
cm3More than, weight heat value reaches more than 42.9MJ/kg, meets the requirement of No. 6 jet fuel standards of GJB1603.Also, by this
The sulphur nitrogen content of jet fuel prepared by the method for invention is low, and the pollutant produced during burning is few；Prepared by the method for the present invention
Jet fuel arene content it is low, reduce the coke deposit rate of engine, can effectively extend the service life of engine.
Meanwhile, jet fuel is produced using the method for the present invention, feedstock oil can realize 100% conversion, and the yield of jet fuel
Height, can reach more than 80%.
Claims (11)
1. a kind of method for producing High-Density Jet, this method comprises the following steps：
Step (1)：By hydrogen and feedstock oil and Hydrobon catalyst haptoreaction；
Optional step (2)：Gaseous stream is isolated in the effluent obtained from step (1), liquid phase stream is obtained；
Step (3)：The effluent that the liquid phase stream and hydrogen or step (1) that step (2) is obtained are obtained is urged with being hydrocracked
Agent haptoreaction；
Step (4)：Jet fuel and diesel oil are isolated in the effluent obtained from step (3)；
Step (5)：Mixed at least part diesel oil feeding step (1) that step (4) is obtained with feedstock oil, or by step
(4) effluent obtained at least part diesel oil feeding step (3) obtained with the liquid phase stream or step (1) is mixed；
Wherein, the arene content of the feedstock oil is more than 40 weight %；The haptoreaction condition of step (1) causes in feedstock oil
The saturation factor of double ring arene is 70-90%, and the haptoreaction condition of step (3) causes total aromatic hydrocarbons in the liquid feedstocks of step (3)
Saturation factor be 75-95%.
2. according to the method described in claim 1, wherein, the arene content of the feedstock oil is 40-90 weight %.
3. method according to claim 1 or 2, wherein, in the feedstock oil, on the basis of the total amount of aromatic hydrocarbons, monocyclic virtue
The content of hydrocarbon is 20-40 weight %.
4. method according to claim 1 or 2, wherein, the feedstock oil is catalytic cracking diesel oil, or the feedstock oil
For catalytic cracking diesel oil and the miscella for mixing oil refining, described mix is refined oil as heavy catalytic cycle oil, coal tar and liquefied coal coil
In one or more, on the basis of the total amount of the miscella, the content of the catalytic cracking diesel oil is 30-90 weight %.
5. method according to claim 3, wherein, the feedstock oil is catalytic cracking diesel oil, or the feedstock oil is
Catalytic cracking diesel oil and the miscella for mixing oil refining, it is described to mix oil refining in heavy catalytic cycle oil, coal tar and liquefied coal coil
One or more, on the basis of the total amount of the miscella, the content of the catalytic cracking diesel oil is 30-90 weight %.
6. according to the method described in claim 1, wherein, the Hydrobon catalyst contains carrier and is supported on the load
At least one vib metals component on body and at least one group VIII metal component, the vib metals component with
The form of metal oxide is present, and the group VIII metal component exists in the form of metal salt, and the carrier is silica.
7. method according to claim 6, wherein, on the basis of the total amount of Hydrobon catalyst and in terms of oxide,
The content of the group VIII metal component is 1-10 weight %, and the content of the vib metals component is 5-50 weight %.
8. according to the method described in claim 1, wherein, the hydrocracking catalyst contains carrier and is supported on the load
At least one group VIII metal component and at least one vib metals component on body, the carrier contain y-type zeolite,
On the basis of the total amount of the carrier, the content of the y-type zeolite is 5-85 weight %, and the y-type zeolite contains Mo and Ni, with
On the basis of the total amount of y-type zeolite, with MoO3The Mo of meter content is 0.5-10 weight %, and the content using the NiO Ni counted is 0.1-5
Weight %.
9. method according to claim 8, wherein, the preparation method of the y-type zeolite includes：
(A) y-type zeolite is mixed with compound containing Mo and compound containing Ni, obtains a kind of mixture；
(B) by the mixture in the atmosphere formed by the gas of moisture vapor, handled 1-24 hours in 200-700 DEG C.
10. method according to claim 8 or claim 9, wherein, on the basis of the total amount of the hydrocracking catalyst and with oxygen
Compound meter, the content of the group VIII metal component is 1-10 weight %, and the content of the vib metals component is 5-50
Weight %.
11. according to the method described in claim 1, wherein, in step (1), the catalytic condition includes：Temperature is
250-450 DEG C, hydrogen dividing potential drop is 7-16MPa, and hydrogen to oil volume ratio is 100-2000Nm3/m3, volume space velocity is 0.2-10h during liquid-1；
In step (3), the catalytic condition includes：Temperature is 250-450 DEG C, and hydrogen dividing potential drop is 3-25MPa, hydrogen oil volume
Than for 100-2000Nm3/m3, volume space velocity is 0.2-10h during liquid-1。
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| CN108795514B (en) * | 2018-07-12 | 2020-08-04 | 天津大学 | Heat absorption type aviation fuel and preparation method thereof |
| CN112708485B (en) * | 2020-12-27 | 2023-04-11 | 陕西延长石油（集团）有限责任公司 | Method for preparing high-calorific-value high-density jet fuel from kerosene mixed raw material |
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