CN105419865A - Jet fuel production method - Google Patents
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- CN105419865A CN105419865A CN201410464733.0A CN201410464733A CN105419865A CN 105419865 A CN105419865 A CN 105419865A CN 201410464733 A CN201410464733 A CN 201410464733A CN 105419865 A CN105419865 A CN 105419865A
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Abstract
The present invention discloses a jet fuel production method, which comprises that (1) hydrogen gas, raw material oil and a hydrorefining catalyst are subjected to a contact reaction; (3) the effluent of the hydrorefining catalyst and a hydrocracking catalyst are directly subjected to a contact reaction, or after the gas phase stream is separated, a contact reaction is performed with a hydrocracking catalyst; (4) the effluent of the hydrocracking catalyst is separated to obtain a jet fuel and diesel oil; and (5) at least partial diesel oil and the raw material oil are mixed, or at least partial diesel oil and the feeding liquid of the hydrocracking catalyst are mixed, wherein the aromatic hydrocarbon content of the raw material oil is more than or equal to 40 wt%, the contact reaction condition of the step (1) makes the bicyclic aromatic hydrocarbon saturation rate in the raw material oil be 70-90%, and the contact reaction conditions of the step (3) makes the monocyclic aromatic hydrocarbon saturation rate in the feeding liquid of the step (3) be 75-95%. According to the present invention, the catalytic cracking diesel oil can be used as the raw material so as to achieve the high yield production of the high density jet fuel meeting the GJB1603 6# jet fuel standard.
Description
Technical field
The present invention relates to a kind of method of producing rocket engine fuel, particularly, relate to a kind of hydrocarbon ils that processes in presence of hydrogen to produce the method for rocket engine fuel.
Background technology
High-Density Jet, also known as large proportion boat coal, is that a class has high-density and (is generally 0.835g/cm
3above), high volume calorific value (is generally 35.8MJ/m
3rocket engine fuel above).(density is generally 0.77-0.81g/cm with common rocket engine fuel
3) compare, High-Density Jet can improve the calorific value of units of fuel volume, in fuel tank capacity one timing, effectively can increase the energy that fuel container carries fuel, is the important leverage of the aerospacecraft height speed of a ship or plane, flight far away.Such as: density is 845kg/m
3(volume calorific value is about 36 × 10
3mJ/m
3) fuel and density be 780kg/m
3(volume calorific value is about 33 × 10
3mJ/m
3) fuel compare, same carry oil volume condition under can make the energy of aircraft overloading about 9%.
Therefore, develop High-Density Jet and become one of study hotspot.
CN102304387B discloses a kind of production method of coal-based high-density jet fuel, the method comprises the following steps: the coalification light oil from DCL/Direct coal liquefaction process enters with liquefaction distillate the expanded bed hydrotreating reactor that internal recycle forced by band, contact with hydrogen, hydrotreating catalyst, the outlet streams of expanded bed hydrotreating reactor, after separation, fractionation, obtains light ends oil, middle matter distillate and heavy distillate; Enter deep hydrofinishing fixed-bed reactor after light ends oil and the mixing of middle matter distillate, contact with hydrogen, Hydrobon catalyst, react, deep hydrofinishing fixed-bed reactor outlet streams, after separation, fractionation, obtains High-Density Jet; Wherein, above described hydrotreating reactor inside, be provided with liquid collecting cup, collected liquid is through Cemented filling and send into the bottom of described hydrotreating reactor again after forced circulation pump boosting.Method disclosed in CN102304387B, when carrying out hydrotreatment to charging, is successively carried out in expanded bed hydrotreating reactor and fixed-bed reactor, adds the complicacy of technique.
US4875992 discloses a kind of method of the coal that navigates from condensed-nuclei aromatics and the large proportion of hydrogenation of aromatics raw material production.The method Raw is the oil being rich in di pah and two hydrogenated aromatic hydrocarbons.First raw material enters first paragraph and carries out desulfurization and denitrification reaction, and product enters second segment and carries out selective hydrogenation saturated bicyclic aromatic hydrocarbons and two hydrogenated aromatic hydrocarbons generation naphthenic hydrocarbon, and generates as far as possible few low molecular hydrocarbon.Large proportion boat coal weight index number (API °) obtained is between 25 °-35 °, and aromaticity content is less than 50%.But the method is comparatively harsh to ingredient requirement, require that the cut scope of raw material is at 350 °F-700 °F, in raw material, contain di pah and the two hydrogenated aromatic hydrocarbons of more than 60 % by weight simultaneously.
Summary of the invention
The method that the object of the invention is to overcome existing production High-Density Jet is to raw material and/technical problem that equipment requirements is high, a kind of method of producing rocket engine fuel is provided, the method technical process is succinct, to equipment and ingredient requirement not high, even on the fixed-bed reactor of routine, adopt if the inferior feedstock oil of catalytic cracking diesel oil is as charging, also can obtain High-Density Jet.
The invention provides a kind of method of producing rocket engine fuel, the method comprises the following steps:
Step (1): by hydrogen and stock oil and Hydrobon catalyst contact reacts;
Optional step (2): isolate gaseous stream from the effluent that step (1) obtains, obtain liquid phase stream;
Step (3): the effluent that the liquid phase stream obtain step (2) and hydrogen or step (1) obtain and hydrocracking catalyst contact reacts;
Step (4): isolate rocket engine fuel and diesel oil from the effluent that step (3) obtains;
Step (5): at least part of diesel oil step (4) obtained is sent in step (1) and mixed with stock oil, or mix with the effluent that described liquid phase stream or step (1) obtain at least part of diesel oil feeding step (3) that step (4) is obtained;
Wherein, the aromaticity content of described stock oil is more than 40 % by weight; The contact reacts condition of step (1) makes the saturation exponent of double ring arene in stock oil be 70-90%, and the contact reacts condition of step (3) makes the saturation exponent of total aromatic hydrocarbons in the liquid feeding of step (3) be 75-95%.
Method tool according to the present invention has the following advantages.
(1) adopt method of the present invention can produce the High-Density Jet meeting GJB16036 rocket engine fuel standard, its density reaches 0.835g/cm
3above, weight heat value meets or exceeds 42.9MJ/kg.
(2) rocket engine fuel adopting method of the present invention to produce, the above aromaticity content of dicyclo is extremely low, reduces the coke deposit rate of engine, effectively can extend engine life.Meanwhile, adopt the rocket engine fuel that method of the present invention is produced, sulphur content and nitrogen content low, decrease the amount of environmental pollutant.
(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 value is low; Further, if catalytic cracking diesel oil adopts hydrogenation modifying process to produce clean diesel product, hydrogen consumption is high on the one hand, and economic benefit is low; The cetane value of product can only be increased to about 40-45 on the other hand, and density can only be reduced to 0.86-0.88g/cm
3, still can only as diesel oil blending component.Even if method provided by the invention adopts catalytic cracking diesel oil as raw material, also can produce High-Density Jet, the catalytic cracking diesel oil for low value is produced high-value product and is provided a kind of new processing technology routine.
(4) adopt method of the present invention to produce rocket engine fuel, the utilization ratio of stock oil is high, can realize 100% conversion, can also obtain high jet fuel yield simultaneously.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.
Fig. 1 is for illustration of the first embodiment of method according to the present invention.
Fig. 2 is for illustration of the second embodiment of method according to the present invention.
Fig. 3 is for illustration of the third embodiment of method according to the present invention.
Fig. 4 is for illustration of the 4th kind of embodiment of method according to the present invention.
Fig. 5 is for illustration of the 5th kind of embodiment of method according to the present invention.
Description of reference numerals
1: stock oil 2: interchanger
3: process furnace 4: the first hydroconversion reaction zone
The effluent of 5: the second hydroconversion reaction zone, hydroconversion reaction zones 6: the second
7: heat exchange back end hydrogenation charging 8: separating unit
9: hydrogen-rich gas 10: liquid phase component
11: fractionation unit 12: gaseous product
13: naphtha fraction 14: jet fuel fraction
15: heavy gas oil cut 16: purification unit
17: recycle hydrogen compressed element 18: recycle hydrogen
19: hydrogen make-up 20: solar oil 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 of producing rocket engine fuel, the method comprises the following steps:
Step (1): by hydrogen and stock oil and Hydrobon catalyst contact reacts;
Optional step (2): isolate gaseous stream from the effluent that step (1) obtains, obtain liquid phase stream;
Step (3): the effluent that the liquid phase stream obtain step (2) and hydrogen or step (1) obtain and hydrocracking catalyst contact reacts;
Step (4): isolate rocket engine fuel and diesel oil from the effluent that step (3) obtains;
Step (5): at least part of diesel oil step (4) obtained is sent in step (1) and mixed with stock oil, or mix with the effluent that described liquid phase stream or step (1) obtain at least part of diesel oil feeding step (3) that step (4) is obtained.
In the present invention, " optionally " represents inessential, can be understood as and comprises or do not comprise, and contains or does not contain.
According to method of the present invention, the aromaticity content of described stock oil is more than 40 % by weight.Described " aromaticity content " is the total content of mononuclear aromatics, dicyclo and above aromatic hydrocarbons in stock oil.The aromaticity content of described stock oil is for being generally 40-90 % by weight.Preferably, the aromaticity content of described stock oil is more than 60 % by weight.According to method of the present invention, in described stock oil, with the total amount of aromatic hydrocarbons for benchmark, the content of mononuclear aromatics is preferably 20-40 % by weight.According to method of the present invention, in described stock oil, the total content of naphthenic hydrocarbon and aromatic hydrocarbons is generally more than 60 % by weight, is preferably 60-95 % by weight.More preferably, in described stock oil, the total content of naphthenic hydrocarbon and aromatic hydrocarbons is more than 70 % by weight.
The density of described stock oil is generally 0.90-0.98g/cm
3.Preferably, the density of described stock oil is 0.92g/cm
3above.More preferably, the density of described stock oil is 0.93g/cm
3above.
The initial boiling point of described stock oil is generally more than 100 DEG C, is preferably more than 150 DEG C, is more preferably more than 180 DEG C.The final boiling point of described stock oil is generally less than 410 DEG C, is preferably less than 400 DEG C, is more preferably less than 380 DEG C.The initial boiling point of stock oil and final boiling point adopt the method specified in ASTMD-86 to measure.
According to method of the present invention, the sulphur nitrogen content in stock oil is not particularly limited.Even the stock oil of sulphur nitrogen content higher (especially nitrogen content is higher) also can as liquid feeding of the present invention.
According to method of the present invention, described stock oil can be catalytic cracking diesel oil.According to method of the present invention, described stock oil for catalytic cracking diesel oil and can also mix the mixing oil of oil refining, described in mix oil refining can be one or more in heavy catalytic cycle oil, coal tar and liquefied coal coil.Described mixing oil composition is as the criterion so that the total content of the aromaticity content of this mixing oil and naphthenic hydrocarbon and aromatic hydrocarbons can be made to meet described requirement above.Usually, with the total amount of described mixing oil for benchmark, the content of described catalytic cracking diesel oil can be 30-90 % by weight, is preferably 60-90 % by weight.
Described catalytic cracking diesel oil can be the diesel oil distillate that Conventional catalytic cracking technique obtains.According to method of the present invention, described catalytic cracking diesel oil is more preferably the catalytic cracking diesel oil that high severity catalytic cracking process obtains, as maximizing iso-paraffins catalytic cracking process (namely, MIP technique) and/or the catalytic cracking diesel oil that obtains of Deep catalytic cracking technology (that is, DCC technique).
According to method of the present invention, described Hydrobon catalyst can for having the catalyzer of aromatic saturation, hydrogenating desulfurization and hydrodenitrification catalytic activity, and can be noble metal catalyst, also can be non-precious metal catalyst.Preferably, described Hydrobon catalyst is non-precious metal catalyst.
Particularly, described Hydrobon catalyst can containing carrier and load group vib metal component on the carrier and group VIII metal component.With the total amount of Hydrobon catalyst for benchmark and with oxide basis, the content of described group vib metal component can be 5-50 % by weight, is preferably 7-35 % by weight; The content of described group VIII metal component can be 1-10 % by weight, is preferably 1.5-7 % by weight.Preferably, described Hydrobon catalyst can also contain at least one auxiliary agent, and described auxiliary agent can be one or more in phosphorus, fluorine and boron.In the total amount of described Hydrobon catalyst for benchmark and with element, the content of described auxiliary agent can be 1-10 % by weight.
The carrier of described Hydrobon catalyst can be one or more in silicon oxide, aluminum oxide and silica-alumina.
In described Hydrobon catalyst, group vib metal can be one or more in Cr, Mo and W, and group VIII metal can be one or more in Fe, Co and Ni.
In described Hydrobon catalyst, group vib metal component and group VIII metal component can exist all in the form of the oxide.One of the present invention preferred embodiment in, in described Hydrobon catalyst, group vib metal component exists in the form of the oxide, group VIII metal component exists with the form of metal-salt, this Hydrobon catalyst is for aromatic saturation, hydrogenating desulfurization and hydrodenitrification have better catalytic effect, more effectively can remove the impurity such as the sulphur nitrogen in stock oil, aromatic saturation can also be promoted further, significantly reduce aromaticity content, particularly polycyclic aromatic hydrocarbon content, thus can reduce with the contact reacts temperature of Hydrobon catalyst and/or improve Feed space velocities.This preferred embodiment in, the carrier of described Hydrobon catalyst is preferably silicon oxide.Further preferably, the specific surface area of described silicon oxide is 100-450m
2/ g, is preferably 150-300m
2/ g, as 160-200m
2/ g; The pore volume of described silicon oxide is 0.4-1.6mL/g, is preferably 0.5-1mL/g.Described specific surface area and pore volume adopt nitrogen adsorption methods to measure.
The method preparation comprised the following steps can be adopted according to the Hydrobon catalyst of this preferred implementation:
(I) with the solution impregnating carrier of the water-soluble cpds containing group vib metal, then carry out drying and roasting, the condition of described roasting is enough to make the described water-soluble cpds containing group vib metal be transformed into oxide compound;
(II) with the carrier that the water-soluble salt impregnation steps (I) containing group VIII metal obtains, then carry out drying, the condition of described drying is not enough to that the described water-soluble salt containing group VIII metal is decomposed becomes oxide compound.
In step (I), the temperature of described drying can be 100-250 DEG C, and the time length of described drying can be selected according to the temperature of drying, can be generally 2-8 hour.In step (I), the temperature of described roasting is as the criterion the water-soluble cpds containing group vib metal can be transformed into oxide compound, can be generally 400-500 DEG C.The time length of described roasting is fixed with the temperature of roasting, can be generally 3-6 hour.
In step (II), the temperature of described drying is as the criterion not make the water-soluble salt decomposition containing group VIII metal become oxide compound.Usually, in step (II), the temperature of described drying can be 60-200 DEG C, preferred 100-150 DEG C; The time length of described drying can be 2-6 hour.
According to method of the present invention, described hydrocracking catalyst can be non-precious metal catalyst.Particularly, described hydrocracking catalyst can containing carrier and the load group vib metal component on carrier and group VIII metal component.With the total amount of described hydrocracking catalyst for benchmark and with oxide basis, the content of described group VIII metal component is 1-10 % by weight, is preferably 1.5-6 % by weight; The content of described group vib metal component is 5-50 % by weight, is preferably 10-40 % by weight.
The carrier of described hydrocracking catalyst can be one or more in silicon oxide, aluminum oxide, silica-alumina and zeolite molecular sieve.Described zeolite molecular sieve can be one or more in faujusite, mordenite, zeolite L, omega zeolite, y-type zeolite and β zeolite.In described hydrocracking catalyst, group vib metal can be Mo and/or W, and group VIII metal can be Co and/or Ni.
One of the present invention preferred embodiment in, the carrier of described hydrocracking catalyst contains y-type zeolite, and described y-type zeolite contains Mo and Ni, with the total amount of y-type zeolite for benchmark, with MoO
3the content of the Mo of meter is 0.5-10 % by weight, is preferably 2-9 % by weight; In the content of the Ni of NiO for 0.1-5 % by weight, be preferably 0.2-3 % by weight.It should be noted that, when calculating the group vib metal of hydrocracking catalyst and group VIII metal content, the content according to Mo and Ni in this y-type zeolite preferred embodiment also counts.
According to this preferred embodiment, described y-type zeolite can adopt the method preparation comprised the following steps:
(A) by y-type zeolite and containing Mo compound with containing Ni compound, a kind of mixture is obtained;
(B) in the atmosphere described mixture formed at the gas by moisture vapor, in 200-700 DEG C of process 1-24 hour.
In step (A), describedly containing Mo compound and the described consumption containing Ni compound, the content of Mo and Ni in the y-type zeolite finally obtained is within above-mentioned scope to be respectively as the criterion.
Can by by y-type zeolite with containing containing Mo compound with contact containing the aqueous solution of Ni compound after, carry out solid-liquid separation, the solid matter that collection obtains carried out drying, thus obtains described mixture.
Described can be common water-solublely contain Mo compound containing Mo compound, its specific examples can include but not limited in molybdenum oxide, molybdate and paramolybdate one or more.Described can be common water-solublely contain Ni compound containing Ni compound, its specific examples can include but not limited in nickelous nitrate, nickel acetate, basic nickel carbonate, nickelous chloride and nickeliferous complex compound one or more.
In step (B), described process is preferably carried out at the temperature of 300-650 DEG C.The time length of described process is preferably 2-24 hour.The gas of described moisture vapor can containing water vapor and optional carrier gas.Described carrier gas can be one or more in nitrogen, neutral element gas (as argon gas), air and hydrogen.The volume ratio of water vapor and described carrier gas can be 1:10-100, is preferably 1:20-90.
Described process can be carried out by continuing to pass into the gas of described moisture vapor in described mixture.Now, the flow of the gas of described moisture vapor can be 0.3-2 standard cubic meter/(kilogram hour).
According to this preferred embodiment, with the total amount of the carrier of hydrocracking catalyst for benchmark, the content of described y-type zeolite is preferably 5-85 % by weight, is preferably 5.5-40 % by weight.
According to this preferred embodiment, the carrier of described hydrocracking catalyst can also contain at least one heat-resistant inorganic oxide.Described heat-resistant inorganic oxide refers to that maximum operation (service) temperature is not less than the porous material of 600 DEG C.The specific examples of described heat-resistant inorganic oxide can include but not limited in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, zirconium white, Thorotrast and beryllium oxide one or more.Preferably, described heat-resistant inorganic oxide is one or more in aluminum oxide, silicon oxide and silica-alumina.
According to method of the present invention, the ratio between described Hydrobon catalyst and described hydrocracking catalyst can be selected according to concrete reaction conditions.Preferably, the volume ratio of described Hydrobon catalyst and described hydrocracking catalyst is 1:0.1-5, as 1:0.4-2.
According to method of the present invention; in step (1); with the flow direction of described stock oil for benchmark; the upstream of described Hydrobon catalyst is preferably provided with hydrogenation protecting agent; to avoid the coke precursor coking on Hydrobon catalyst such as alkene and/or colloid in stock oil; cause Hydrobon catalyst coking and deactivation, the metal in stock oil can also be avoided to cause Hydrobon catalyst poisoning simultaneously.The consumption of described hydrogenation protecting agent can be selected according to raw material oil composition.Preferably, described hydrogenation protecting agent is the 5-30 volume % of the total amount of described Hydrobon catalyst, as 20-30 volume %.
Described hydrogenation protecting agent can for realizing the various catalyzer of above-mentioned effect.Particularly; described hydrogenation protecting agent contains carrier and load vib metal component on the carrier and group VIII metal component; with the total amount of hydrogenation protecting agent for benchmark and with oxide basis; the content of described group vib metal component can be 5.5-10 % by weight, and the content of described group VIII metal component can be 1-5 % by weight.Described group VIII metal is preferably Ni, and described group vib metal is preferably Mo.Described carrier is preferably aluminum oxide, is more preferably the aluminum oxide with diplopore distribution.
According to method of the present invention, from the angle of the content of the alkene reduced further in the effluent of hydrocracking catalyst and mercaptan sulfur, in step (3), with the flow direction of described stock oil for benchmark, the downstream of described hydrocracking catalyst is preferably provided with supplementary Hydrobon catalyst.The consumption of described supplementary Hydrobon catalyst is as the criterion the alkene in the effluent of hydrocracking catalyst and mercaptan sulfur content can be reduced to expection content.Usually, the amount of described supplementary Hydrobon catalyst is the 10-50 volume % of the total amount of Hydrobon catalyst and hydrocracking catalyst, as 10-20 volume %.The kind of described supplementary Hydrobon catalyst is identical with previously described Hydrobon catalyst, no longer describes in detail herein.Described supplementary Hydrobon catalyst and described Hydrobon catalyst can be identical, also can be different.
Described Hydrobon catalyst, hydrocracking catalyst, optional hydrogenation protecting agent and the optional Hydrobon catalyst that supplements can be located in the differential responses district of same reactor; also different reactors can be arranged in; can select according to concrete device, be not particularly limited.
According to method of the present invention, step (1) and step (3) are preferably carried out in fixed-bed reactor.
According to method of the present invention, the contact reacts condition of step (1) makes the saturation exponent of double ring arene in stock oil be 70-90%, is preferably more than 75%.The saturation exponent of double ring arene adopts following formulae discovery to obtain:
In the effluent that in the saturation exponent=﹝ ﹙ stock oil of double ring arene, the quality-step (1) of double ring arene obtains double ring arene Zhi Liang ﹚/stock oil in Zhi Liang ﹞ × 100% of double ring arene.
Particularly, in step (1), temperature can be 250-450 DEG C, is preferably 300-410 DEG C, as 340-380 DEG C; Hydrogen dividing potential drop can be 7-16MPa, is preferably 10-15MPa; Hydrogen to oil volume ratio (that is, standard state hydrogen to oil volume ratio) can be 100-2000Nm
3/ m
3, be preferably 300-1500Nm
3/ m
3, as 800-1300Nm
3/ m
3; During liquid, volume space velocity can be 0.2-10h
-1, be preferably 0.5-5h
-1.
According to method of the present invention, the contact reacts condition of step (3) makes the saturation exponent of total aromatic hydrocarbons in the liquid feeding of step (3) be 75-95%, is preferably more than 80%.The saturation exponent of total aromatic hydrocarbons adopts following formulae discovery to obtain:
In the effluent that the quality-step (3) of the total aromatic hydrocarbons in the liquid feeding of saturation exponent=﹝ ﹙ step (3) of total aromatic hydrocarbons obtains the Zhi Liang ﹚/step (3) of total aromatic hydrocarbons liquid feeding in Zhi Liang ﹞ × 100% of total aromatic hydrocarbons.
Particularly, in step (3), temperature can be 250-450 DEG C, is preferably 310-430 DEG C, as 350-380 DEG C; Hydrogen dividing potential drop can be 3-25MPa, is preferably 6-20MPa, as 10-15MPa; Hydrogen to oil volume ratio (that is, standard state hydrogen to oil volume ratio) can be 100-2000Nm
3/ m
3, be preferably 300-1500Nm
3/ m
3; During liquid, volume space velocity can be 0.2-10h
-1, be preferably 1-5h
-1.
According to method of the present invention, the effluent that step (1) obtains can without separation directly send in step (3) with hydrocracking catalyst contact reacts, also after can isolating the gaseous stream in the effluent that step (1) obtains, then to send in step (3) together with hydrogen with hydrocracking catalyst contact reacts.Preferably, step (2) is also comprised: obtain going out to isolate gaseous stream effluent from step (1) according to method of the present invention, obtain liquid phase stream, and described liquid phase stream and hydrogen are sent in step (3) with hydrocracking catalyst contact reacts.The hydrogen sulfide, ammonia and the small molecule hydrocarbon (carbonatoms is the hydrocarbon of less than 5) that generate in unifining process can be isolated by step (2), thus extend the work-ing life of hydrocracking catalyst further, temperature of reaction when contacting with hydrocracking catalyst can also be reduced simultaneously.The effluent obtained with step (1) is without being separated directly compared with hydrocracking catalyst contact reacts, to isolate after gas-phase product wherein again with hydrocracking catalyst contact reacts, can make to reduce 10-30 DEG C with the Contact Temperature of hydrocracking catalyst, thus reduction plant energy consumption, optimize the temperature distribution in hydrocracking catalyst bed.Meanwhile, isolate the gas-phase product in the effluent that step (1) obtains, can also improve and hydrogen dividing potential drop during hydrocracking catalyst contact reacts and hydrogen effective rate of utilization.
In step (2), the condition of separation make the sulfocompound (as hydrogen sulfide) that generates in the hydrofining reaction process of step (1) and nitrogenous compound (as ammonia) be arranged in as described in gaseous stream.Ordinary method can be adopted from the effluent that step (1) obtains to isolate gaseous stream.Particularly, by carrying out flash distillation and/or stripping to the effluent that step (1) obtains, thus gaseous stream wherein can be isolated.Described flash distillation and steam stripped condition are isolating gaseous stream, and hydrogen sulfide and the ammonia of particularly unifining process generation are as the criterion.Usually, the condition of described flash distillation comprises: temperature can be 30-400 DEG C, is preferably 200-380 DEG C; In gauge pressure, pressure can be 3-20MPa, is preferably 8-16MPa.Described steam stripped condition comprises: temperature can be 30-400 DEG C, is preferably 200-380 DEG C; In gauge pressure, pressure can be 3-20MPa, is preferably 10-16MPa.
According to method of the present invention, isolated gaseous stream contains hydrogen, can carry out purifying and recycle after removing sulphur nitrogen wherein.
According to method of the present invention, in step (4), conventional various methods can be adopted from the effluent that step (3) obtains to isolate rocket engine fuel and diesel oil.In one embodiment, be separated into gaseous stream and liquid phase stream in the effluent that can first step (3) be obtained, then described liquid phase stream carried out fractionation, obtain gaseous product, naphtha fraction, jet fuel fraction and diesel oil distillate.The gaseous stream separated is hydrogen-rich gas, can use after being further purified as recycle hydrogen.
According to method of the present invention, the initial boiling point of jet fuel fraction and final boiling point are with the kind difference to some extent of stock oil.Usually, the initial boiling point of jet fuel fraction can be a temperature of more than 140 DEG C, as 140 DEG C, 150 DEG C or 170 DEG C.The final boiling point of rocket engine fuel can be a temperature of less than 300 DEG C, as 300 DEG C, 280 DEG C or 270 DEG C.Described diesel oil refers to the cut (that is, the final boiling point of jet fuel fraction be distillation cut point jet fuel fraction and diesel oil distillate between) of initial boiling point higher than the final boiling point of rocket engine fuel.Usually, the initial boiling point of described diesel oil can be a temperature higher than 270 DEG C, as higher than the temperature of 290 DEG C, higher than a temperature of 300 DEG C.Can using initial boiling point higher than whole cuts of rocket engine fuel as diesel oil distillate, also can using initial boiling point higher than the part cut in the cut of rocket engine fuel as diesel oil distillate, using final boiling point be such as not higher than the cut of 360 DEG C as diesel oil distillate.The initial boiling point of rocket engine fuel and diesel oil and final boiling point adopt the method specified in ASTMD2887 to measure.
According to method of the present invention, in step (5), the charging mixed with stock oil as Hydrobon catalyst sent in step (1) by least part of diesel oil that step (4) can be obtained; The charging mixed with the liquid phase stream that step (2) obtains as hydrocracking catalyst sent in step (3) by least part of diesel oil that also step (4) can be obtained; The effluent that at least part of diesel oil that step (4) can also be obtained and step (1) obtain mixes the charging as hydrocracking catalyst.At least part of diesel oil step (4) obtained is sent in step (1), can reduce aromaticity content and the sulphur nitrogen content of the rocket engine fuel of final preparation further; At least part of diesel oil step (4) obtained is sent in step (2), can improve the yield of rocket engine fuel further.
In step (5), can whole diesel oil be sent in step (1) or step (3), also part diesel oil can be sent in step (1) or step (3).From the further angle improving the yield of rocket engine fuel, whole diesel oil distillate is sent in step (1) or step (3).When part diesel oil is sent into step (1) or step (3), can be 330 DEG C by final boiling point, be preferably in fraction section feeding step (1) of 310 DEG C or step (3), send in step (1) or step (3) by solar oil cut, like this can work-ing life of extending catalyst further, and obtain the higher rocket engine fuel of quality.
Adopt method of the present invention to produce rocket engine fuel, the rocket engine fuel obtained is High-Density Jet, and its density can reach 0.835g/cm
3above, generally at 0.835-0.850g/cm
3scope in.The rocket engine fuel adopting method of the present invention to produce has higher net thermal value, can reach more than 42.9MJ/kg, generally in the scope of 42.9-43.3MJ/kg.
Fig. 1 to Fig. 5 exemplarily gives five kinds of embodiments of the method for production rocket engine fuel provided by the invention, but it will be appreciated by persons skilled in the art that method provided by the invention is not limited to this five kinds of embodiments.Below in conjunction with Fig. 1 to Fig. 5, these five kinds of embodiments are described.
As shown in Figure 1, stock oil 1, recycle hydrogen 18 and hydrogen make-up 19 are mixed, obtains hydrogenation charging.The effluent 6 of hydrogenation charging through interchanger 2 and the second hydroconversion reaction zone 5 carries out heat exchange, heat exchange back end hydrogenation charging 7 then enters in process furnace 3 heats, then the first hydroconversion reaction zone 4 and Hydrobon catalyst contact reacts is entered, the effluent of the first hydroconversion reaction zone 4 directly enters the second hydroconversion reaction zone 5 without separation and contacts with hydrocracking catalyst, after the effluent 6 of the second hydroconversion reaction zone 5 carries out heat exchange with hydrogenation charging in interchanger 2, enter in separating unit 8, isolate hydrogen-rich gas 9 and liquid phase component 10.Hydrogen-rich gas 9 enters in recycle hydrogen compressed element 17 Posterior circle that boosts after entering the impurity (as hydrogen sulfide) that purification unit 16 removes wherein and uses.Liquid phase component 10 enters fractionation unit 11, is separated into gaseous product 12, naphtha fraction 13, jet fuel fraction 14, solar oil cut 20 and heavy gas oil cut 15.Send in the second hydroconversion reaction zone 5 after solar oil cut 20 and the effluent of the first hydroconversion reaction zone 4 are mixed and contact with hydrocracking catalyst.
Fig. 2 shows the second embodiment according to method of the present invention, and only the difference of composition graphs 2 to the first embodiment shown in this embodiment and Fig. 1 is described below.As shown in Figure 2, in fractionation unit 11, diesel oil distillate is not cut into solar oil cut and heavy gas oil cut, but sends in the second hydroconversion reaction zone 5 after whole diesel oil distillate 21 and the effluent of the first hydroconversion reaction zone 4 are mixed and contact with hydrocracking catalyst.
Fig. 3 shows the third embodiment according to method of the present invention, and only the difference of composition graphs 3 to the first embodiment shown in this embodiment and Fig. 1 is described below.As shown in Figure 3, the effluent of the first hydroconversion reaction zone 4 is not directly enter the second hydroconversion reaction zone 5 and hydrocracking catalyst contact reacts, but enter in steam stripping unit 22, by stripping fluid 23, the effluent of the first hydroconversion reaction zone 4 is separated into liquid phase stream 24 and gaseous stream 25.Wherein, gaseous stream 25 is rich in hydrogen, purified unit 16 and recycle hydrogen compressed element 17 carry out purifying and boosting after can use as recycle hydrogen 18, liquid phase stream 24 enter in the second hydroconversion reaction zone 5 with hydrocracking catalyst contact reacts.
Fig. 4 shows the 4th kind of embodiment according to method of the present invention, and only the difference of composition graphs 4 to the third embodiment shown in this embodiment and Fig. 3 is described below.As shown in Figure 4, in fractionation unit 11, diesel oil distillate is not cut into solar oil cut and heavy gas oil cut, but whole diesel oil distillate 21 and the liquid phase stream 24 coming from steam stripping unit 22 are mixed in rear feeding second hydroconversion reaction zone 5 contacts with hydrocracking catalyst.
Fig. 5 shows the 5th kind of embodiment according to method of the present invention.Below only the difference of composition graphs 5 to the first embodiment shown in this embodiment and Fig. 1 is described.As shown in Figure 5, solar oil cut 20 to be mixed with stock oil 1 after rear elder generation after interchanger 2 and process furnace 3, enter the first hydroconversion reaction zone 4 and Hydrobon catalyst contact reacts.
Describe the present invention in detail below in conjunction with embodiment, but therefore do not limit the scope of the invention.
In following examples and comparative example, jet fuel fraction yield is defined as the weight percent of jet fuel fraction that full cut product fractionated out by separation column and stock oil.
In following examples and comparative example, adopt the method specified in SH/T0606-94 to measure stock oil, the first fixed-bed reactor effluent and the liquid feeding of the second fixed-bed reactor and the composition of effluent respectively, adopt the saturation exponent of following formulae discovery double ring arene and the saturation exponent of total aromatic hydrocarbons:
In the saturation exponent=﹝ ﹙ stock oil of double ring arene quality-the first fixed-bed reactor of double ring arene effluent in double ring arene Zhi Liang ﹚/stock oil in Zhi Liang ﹞ × 100% of double ring arene;
In the liquid feeding of saturation exponent=﹝ ﹙ second fixed-bed reactor of total aromatic hydrocarbons quality-the second fixed-bed reactor of total aromatic hydrocarbons effluent in total aromatic hydrocarbons Zhi Liang ﹚/the second fixed-bed reactor liquid feeding in Zhi Liang ﹞ × 100% of total aromatic hydrocarbons.
Embodiment 1-6 is for illustration of method of the present invention.
Embodiment 1
The stock oil A used in the present embodiment is catalytic cracking diesel oil, and its character is listed in Table 1.
The present embodiment carries out in two fixed-bed reactor, in the first fixed-bed reactor, load Hydrobon catalyst; With the flow direction of liquid material for benchmark, in the second fixed-bed reactor, load hydrocracking catalyst and supplementary Hydrobon catalyst successively.The admission space of Hydrobon catalyst, hydrocracking catalyst and supplementary Hydrobon catalyst is than being 40:60:10.
Hydrobon catalyst and supplementary Hydrobon catalyst all adopt following methods to prepare.
By 3000 grams of SilicaGel955 commercial silica gel (U.S. DavisonChemical Products, SiO
2content is 99.8 % by weight) and after 75 grams of sesbania powder mix, then mix with 84 milliliters of nitric acid (concentration 65-68 % by weight, analytical pure, Xi Long chemical plant, Shantou product) and 4200 ml waters.The mixture obtained is continued on double screw banded extruder kneading even, be then extruded into the butterfly bar of Φ 1.3 millimeters, wet bar after 4 hours, in 600 DEG C of roastings 3 hours, obtains silica support S through 120 DEG C of dryings.Determine through nitrogen adsorption methods, the specific surface area of this carrier is 180m
2/ g, pore volume is 0.78mL/g.
Dilute ammonia solution (the NH of 21.9 grams of ammonium paramolybdates is contained with 200 milliliters
3concentration be 10 % by weight) dipping 200 grams of silica support S, dipping time is 2 hours, then in 120 DEG C of dryings 4 hours, then 460 DEG C of roastings 4 hours, obtain load molybdenum oxide containing molybdenum carrier.Then, contain molybdenum carrier 2 hours with 156 milliliters of aqueous impregnation containing 13.3 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs and 4.4 grams of nickelous nitrates, then in 120 DEG C of dryings 4 hours, obtain Hydrobon catalyst.Adopt the composition of this catalyzer of x-ray fluorescence spectrometry, wherein, MoO
3the content of content to be the content of 8.0 % by weight, NiO be 0.6 % by weight, CoO be 1.5 % by weight.
Hydrocracking catalyst adopts following methods preparation.
Get 50 grams of USY zeolite (Changling Branch, Chinese Petro-Chemical Co Ltd's products, lattice constant is 24.50 dusts, degree of crystallinity is 88%, sodium oxide content is 0.8 % by weight, butt is 75 % by weight), under normal temperature condition (being 25 DEG C), join 60mL containing ammonium molybdate (with MoO with stirring
3meter, concentration is 27g/L) and the ammoniacal liquor (NH of nickelous nitrate (in NiO, concentration is 5.4g/L)
3concentration be 10 % by weight) in mixing solutions, abundant stirring, then in 120 DEG C of dryings 4 hours, then tube furnace flat-temperature zone is placed in, in hydrogen and water vapour atmosphere, in 300 DEG C of roastings 24 hours, thus obtain molecular sieve MNY-1, wherein, the actual conditions of roasting is: gas flow is 0.5Nm
3/ (kgh), the volume ratio of water vapor and hydrogen is 1:40.Adopt the composition of x-ray fluorescence spectrometry molecular sieve MNY-1, wherein, MoO
3content be the content 0.6 % by weight of 3.0 % by weight, NiO.
By 185.7 grams of pseudo-boehmite (Changling Branch, Chinese Petro-Chemical Co Ltd's products, butt is 70 % by weight) mix with 93.3 grams of MNY-1 type molecular sieves (butt is 75 % by weight), be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, wet bar was in 120 DEG C of dryings 3 hours, then 450 DEG C of roastings 4 hours, carrier Z1 is obtained.
With 88 milliliters of ammonium metawolframates (with WO
3meter, concentration is 422 grams per liters) and nickelous nitrate (in NiO, concentration is 64.9 grams per liters) mixed aqueous solution flood 100 grams of carrier Z1, dipping time is 1 hour, then in 120 DEG C of dryings 2 hours, then 450 DEG C of roastings 3 hours, catalytic cracking catalyst is obtained.Adopt the composition of this catalytic cracking catalyst of x-ray fluorescence spectrometry, wherein, MoO
3content be 0.75 % by weight, WO
3content be the content of 26 % by weight, NiO be 4.1 % by weight.
The concrete technology flow process of the present embodiment is as follows.
Stock oil and hydrogen mix and after carrying out preheating, send in the first fixed-bed reactor, with Hydrobon catalyst (that is, the first reaction zone) contact reacts.The effluent of the first fixed-bed reactor without separation directly to enter in the second fixed-bed reactor successively with hydrocracking catalyst (namely, second reaction zone) and supplementary Hydrobon catalyst contact reacts, wherein, concrete reaction conditions is as shown in table 2 shows.After the effluent of the second fixed-bed reactor carries out gas-liquid separation, isolated liquid phase component is carried out fractionation, collects gaseous product, jet fuel fraction, solar oil cut (boiling range is 270-330 DEG C) and heavy gas oil cut (initial boiling point is be greater than the cut of 330 DEG C).To send into after solar oil cut is mixed with the effluent of the first fixed-bed reactor in the second fixed-bed reactor successively with hydrocracking catalyst and supplementary Hydrobon catalyst contact reacts.
The character of the rocket engine fuel obtained is listed in table 2.
Embodiment 2
The method identical with embodiment 1 is adopted to produce rocket engine fuel, unlike, Hydrobon catalyst used and supplementary Hydrobon catalyst used adopt following methods preparation:
Dilute ammonia solution (the NH of 21.9 grams of ammonium paramolybdates is contained with 200 milliliters
3concentration be 10 % by weight) dipping 200 grams of silica support S, dipping time is 2 hours, then in 120 DEG C of dryings 4 hours, then 460 DEG C of roastings 4 hours, obtain load molybdenum oxide containing molybdenum carrier.Then, contain molybdenum carrier 2 hours with 156 milliliters of aqueous impregnation containing 13.3 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs and 4.4 grams of nickelous nitrates, then in 120 DEG C of dryings 4 hours, then 470 DEG C of dryings 4 hours, obtain described Hydrobon catalyst.Adopt the composition of this catalyzer of x-ray fluorescence spectrometry, wherein, MoO
3the content of content to be the content of 8.0 % by weight, NiO be 0.6 % by weight, CoO be 1.5 % by weight.
The character of the rocket engine fuel obtained is listed in table 2.
Embodiment 3
The method identical with embodiment 1 is adopted to produce rocket engine fuel, unlike, hydrocracking catalyst used adopts following methods preparation:
By 185.7 grams of pseudo-boehmite (Changling Branch, Chinese Petro-Chemical Co Ltd's products, butt is 70 % by weight) and 93.3 grams of USY zeolite (Changling Branch, Chinese Petro-Chemical Co Ltd's products, lattice constant is 24.50 dusts, degree of crystallinity is 88%, sodium oxide content is 0.8 % by weight, butt is 75 % by weight) mixing, be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, wet bar was in 120 DEG C of dryings 3 hours, then 450 DEG C of roastings 4 hours, thus carrier DZ1 is obtained.
With 88 milliliters of ammonium metawolframates (with WO
3meter, concentration is 422 grams per liters), ammonium molybdate is (with MoO
3meter, concentration is 24.3 grams per liters) and nickelous nitrate (in NiO, concentration is 69.8 grams per liters) mixed aqueous solution flood 100 grams of carrier DZ1, dipping time is 1 hour, then in 120 DEG C of dryings 2 hours, then 450 DEG C of roastings 3 hours, described catalytic cracking catalyst is obtained.Adopt the composition of this catalytic cracking catalyst of x-ray fluorescence spectrometry, wherein, MoO
3content be 0.75 % by weight, WO
3content be the content of 26 % by weight, NiO be 4.1 % by weight.
The character of the rocket engine fuel obtained is listed in table 2.
Comparative example 1
The method identical with embodiment 1 is adopted to produce rocket engine fuel, unlike, the effluent of solar oil cut with the first reaction zone is not mixed, but directly export.The character of the rocket engine fuel obtained is listed in table 2.
Comparative example 2
The method identical with embodiment 1 is adopted to produce rocket engine fuel, unlike, reaction conditions is as shown in table 2.The character of the rocket engine fuel obtained is as shown in table 2.
Comparative example 3
The method identical with embodiment 1 is adopted to produce rocket engine fuel, unlike, reaction conditions is as shown in table 2.The character of the rocket engine fuel obtained is as shown in table 2.
Comparative example 4
The method identical with embodiment 1 is adopted to produce rocket engine fuel, unlike, adopt stock oil DA, its character is listed in Table 1.Reaction conditions is as shown in table 2 with the character of the rocket engine fuel obtained.
Table 1
Table 2
*: with the total amount of Hydrobon catalyst and hydrocracking catalyst for benchmark.
Embodiment 4
The stock oil B used in the present embodiment is catalytic cracking diesel oil, and its character is listed in table 3.
The present embodiment carries out in two fixed-bed reactor, in the first fixed-bed reactor, load Hydrobon catalyst; With the flow direction of liquid material for benchmark, in the second fixed-bed reactor, load hydrocracking catalyst and supplementary Hydrobon catalyst successively.The admission space of Hydrobon catalyst, hydrocracking catalyst and supplementary Hydrobon catalyst is than being 40:60:10.Hydrocracking catalyst is be the catalyzer of RHC-5 purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd.
Described Hydrobon catalyst is identical with supplementary Hydrobon catalyst, adopts following methods preparation.
With 200 milliliters containing 70.5 grams of ammonium paramolybdates aqueous impregnation 200 grams of silica support S (adopting the method identical with embodiment 1 to prepare) with 23.2 grams of phosphoric acid, dipping time is 2 hours, then in 120 DEG C of dryings 4 hours, then 460 DEG C of roastings 4 hours, what obtain load molybdenum oxide contains molybdenum carrier.Then, contain molybdenum carrier 2 hours with 118 milliliters of aqueous impregnation containing 11.4 grams of Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs and 45.7 grams of nickelous nitrates, then in 120 DEG C of dryings 4 hours, obtain Hydrobon catalyst.Adopt the composition of this catalyzer of x-ray fluorescence spectrometry, wherein, MoO
3the content of content to be the content of 20.2 % by weight, NiO be 4.0 % by weight, CoO be 1.0 % by weight, P
2o
5content be 5.0 % by weight.
The concrete technology flow process of the present embodiment is as follows.
Stock oil and hydrogen mix and after carrying out preheating, send in the first fixed-bed reactor, with Hydrobon catalyst (that is, the first reaction zone) contact reacts.The effluent of the first fixed-bed reactor without separation directly to enter in the second fixed-bed reactor successively with hydrocracking catalyst (namely, second reaction zone) and supplementary Hydrobon catalyst contact reacts, wherein, concrete reaction conditions is as shown in table 4 shows.After the effluent of the second fixed-bed reactor carries out gas-liquid separation, isolated liquid phase component is carried out fractionation, collect gaseous product, jet fuel fraction, diesel oil distillate (initial boiling point is be greater than whole cuts of 300 DEG C).Diesel oil distillate and fresh feed oil mixs send into afterwards in the first fixed-bed reactor with Hydrobon catalyst contact reacts.
The character of the rocket engine fuel obtained is listed in table 4.
Table 3
Table 4
*: with the total amount of Hydrobon catalyst and hydrocracking catalyst for benchmark.
Embodiment 5
The stock oil C used in the present embodiment is the mixing oil of catalytic cracking diesel oil C1 and coal tar lighting end C2, and wherein, the mass ratio of C1 and C2 is 2:1, and its character is listed in table 5.
The present embodiment carries out in two fixed-bed reactor, in the first fixed-bed reactor, load Hydrobon catalyst; With the flow direction of liquid material for benchmark, in the second fixed-bed reactor, load hydrocracking catalyst and supplementary Hydrobon catalyst successively.The admission space of Hydrobon catalyst, hydrocracking catalyst and supplementary Hydrobon catalyst is than being 65:35:10.Hydrobon catalyst and supplementary Hydrobon catalyst are be the catalyzer of RS-2000 purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd.
Hydrocracking catalyst adopts following methods preparation.
Get 50 grams of USY zeolites (Sinopec Group's catalyzer Chang Ling branch office product, lattice constant is 24.54 dusts, degree of crystallinity is 89%, sodium oxide content is 0.7 % by weight, butt is 75 % by weight), under normal temperature condition (being 25 DEG C), join 75mL containing ammonium molybdate (with MoO with stirring
3meter, concentration is 103.3g/L) and the ammoniacal liquor (NH of nickelous nitrate (in NiO, concentration is 20.4g/L)
3concentration be 10 % by weight) in mixing solutions, fully stir, then in 120 DEG C of dryings 4 hours, then tube furnace flat-temperature zone is placed in, in hydrogen and water vapour atmosphere, in 550 DEG C of roastings 2 hours, thus obtain molecular sieve MNY-2, wherein, the actual conditions of roasting is: gas flow is 1.2Nm
3/ (kgh), the volume ratio of water vapor and hydrogen is 1:50.Adopt the composition of x-ray fluorescence spectrometry molecular sieve MNY-2, wherein, MoO
3content be the content 1.8 % by weight of 9.0 % by weight, NiO.
By 245.5 grams of pseudo-boehmites (Sinopec Group's catalyzer Chang Ling branch office product, butt is 70 % by weight) mix with 13.5 grams of MNY-2 type molecular sieves (butt is 75 % by weight), be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, wet bar was in 120 DEG C of dryings 3 hours, then 600 DEG C of roastings 4 hours, carrier Z2 is obtained.
Ammonium metawolframate is contained (with WO with 85 milliliters
3meter, concentration is 478.8 grams per liters) and nickelous nitrate (in NiO, concentration is 54.7 grams per liters) and the mixing solutions of 162.3 grams of ethylene glycol flood 100 grams of carrier Z2, dipping time is 1 hour, then in 120 DEG C of dryings 2 hours, then 450 DEG C of roastings 3 hours, catalytic cracking catalyst is obtained.Adopt the composition of this catalytic cracking catalyst of x-ray fluorescence spectrometry, wherein, MoO
3content be 0.3 % by weight, WO
3content be the content of 26 % by weight, NiO be 3.3 % by weight.
The concrete technology flow process of the present embodiment is as follows.
Stock oil and hydrogen mix and after carrying out preheating, send in the first fixed-bed reactor, with Hydrobon catalyst (that is, the first reaction zone) contact reacts.The effluent of the first fixed-bed reactor enters in stripping tower and carries out stripping, obtains the gaseous stream containing hydrogen sulfide and ammonia and liquid phase stream.Wherein, adopt hydrogen as stripping fluid, the pressure in stripping tower is 10MPa (gauge pressure), and temperature is 260 DEG C.Liquid phase stream and hydrogen to enter in the second fixed-bed reactor successively with hydrocracking catalyst (that is, second reaction zone) and supplementary Hydrobon catalyst contact reacts.After the effluent of the second fixed-bed reactor carries out gas-liquid separation, isolated liquid phase component is carried out fractionation, collect gaseous product, jet fuel fraction, diesel oil distillate (initial boiling point is be greater than whole cuts of 300 DEG C).To send into after diesel oil distillate is mixed with the liquid phase stream from stripping tower in the second fixed-bed reactor successively with hydrocracking catalyst and supplementary Hydrobon catalyst contact reacts.
Concrete reaction conditions and the character of rocket engine fuel obtained are listed in table 6.
Table 5
Table 6
*: with the total amount of Hydrobon catalyst and hydrocracking catalyst for benchmark.
Embodiment 6
The stock oil D used in the present embodiment is the mixing oil of catalytic cracking diesel oil C1 and direct liquefying diesel oil of coal E1, and wherein, the mass ratio of C1 and E1 is 2:1, and its character is listed in table 7.
The present embodiment carries out in two fixed-bed reactor, with the flow direction of liquid material for benchmark, in the first fixed-bed reactor, loads hydrogenation protecting agent and Hydrobon catalyst successively; With the flow direction of liquid material for benchmark, in the second fixed-bed reactor, load hydrocracking catalyst and supplementary Hydrobon catalyst successively.The admission space of Hydrobon catalyst, hydrocracking catalyst and supplementary Hydrobon catalyst is than being 70:30:10.Hydrobon catalyst and supplementary Hydrobon catalyst are be the catalyzer of RS-1000 purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd.Hydrogenation protecting agent is be the catalyzer of RG-30A and RG-30B purchased from the trade mark of Changling Branch, Chinese Petro-Chemical Co Ltd; hydrogenation protecting agent is 30 volume % of the total amount of Hydrobon catalyst; with the flow direction of liquid material for benchmark; RG-30A is positioned at the upstream of RG-30B, and the weight ratio of RG-30A and RG-30B is 2:1.
Hydrocracking catalyst adopts following methods preparation.
(Sinopec Group's catalyzer Chang Ling branch office product, lattice constant is 24.65 dusts, and degree of crystallinity is 95%, Na to get 100 grams of NaY zeolite
2o content is 5.3 % by weight), exchange 1 hour with the ammonium nitrate solution of 0.1mol/L at 80 DEG C, then filter, the molecular sieve collected obtains HNaY in 4 hours in 560 DEG C of roastings in retort furnace.
By 50 grams of HNaY and 0.53 gram molybdic oxides, 0.12 gram of nickel oxide ground and mixed in agate mortar, then, to mixture be obtained be placed in the flat-temperature zone of tube furnace, in hydrogen and water vapour atmosphere, in 600 DEG C of roastings 8 hours, thus obtain molecular sieve MNY-3, wherein, the actual conditions of roasting is: gas flow is 1.8Nm
3/ (kgh), the volume ratio of water vapor and hydrogen is 1:90.Adopt the composition of x-ray fluorescence spectrometry molecular sieve MNY-3, wherein, MoO
3content be the content 0.2 % by weight of 1.0 % by weight, NiO.
By 171.4 grams of pseudo-boehmites (Sinopec Group's catalyzer Chang Ling branch office product, butt is 70 % by weight) mix with 106.7 grams of MNY-3 type molecular sieves (butt is 75 % by weight), be extruded into the trilobal bar that circumscribed circle diameter is 1.6 millimeters, wet bar is dried 3 hours in 120 DEG C, then 600 DEG C of roastings 4 hours, carrier Z3 is obtained.
Ammonium metawolframate is contained (with WO with 87 milliliters
3meter, concentration is 513.1 grams per liters) and the mixed aqueous solution of nickelous nitrate (in NiO, concentration is 47.9 grams per liters) flood 100 grams of carrier Z3, dipping time is 1 hour, then in 120 DEG C of dryings 2 hours, then 450 DEG C of roastings 3 hours, catalytic cracking catalyst is obtained.Adopt the composition of this catalytic cracking catalyst of x-ray fluorescence spectrometry, wherein, MoO
3content be 0.3 % by weight, WO
3content be the content of 30 % by weight, NiO be 2.9 % by weight.
The concrete technology flow process of the present embodiment is as follows.
Stock oil and hydrogen mix and after carrying out preheating, send in the first fixed-bed reactor, successively with hydrogenation protecting agent and Hydrobon catalyst (Hydrobon catalyst being called the first reaction zone) contact reacts.The effluent of the first fixed-bed reactor enters in stripping tower and carries out stripping, obtains the gaseous stream containing hydrogen sulfide and ammonia and liquid phase stream.Wherein, adopt hydrogen as stripping fluid, the pressure in stripping tower is 11.6MPa (gauge pressure), and temperature is 200 DEG C.Liquid phase stream and hydrogen to enter in the second fixed-bed reactor successively with hydrocracking catalyst (that is, second reaction zone) and supplementary Hydrobon catalyst contact reacts.After the effluent of the second fixed-bed reactor carries out gas-liquid separation, isolated liquid phase component is carried out fractionation, collects gaseous product, jet fuel fraction, solar oil cut (boiling range is 280-330 DEG C) and heavy gas oil cut (initial boiling point is be greater than whole cuts of 330 DEG C).To send into after solar oil cut is mixed with the liquid phase stream from stripping tower in the second fixed-bed reactor successively with hydrocracking catalyst and supplementary Hydrobon catalyst contact reacts.
Concrete reaction conditions and the character of rocket engine fuel obtained are listed in table 8.
Table 7
Table 8
*: with the total amount of Hydrobon catalyst and hydrocracking catalyst for benchmark.
The result of embodiment 1-6 confirms, the density of the rocket engine fuel adopting method of the present invention to produce reaches 0.835g/cm
3above, weight heat value reaches more than 42.9MJ/kg, meets the requirement of GJB16036 rocket engine fuel standard.Further, the sulphur nitrogen content of the rocket engine fuel prepared by method of the present invention is low, and the pollutent produced during burning is few; The aromaticity content of the rocket engine fuel prepared by method of the present invention is low, reduces the coke deposit rate of engine, effectively can extend the work-ing life of engine.Meanwhile, adopt method of the present invention to produce rocket engine fuel, stock oil can realize 100% conversion, and the yield of rocket engine fuel is high, can reach more than 80%.
Claims (10)
1. produce a method for rocket engine fuel, the method comprises the following steps:
Step (1): by hydrogen and stock oil and Hydrobon catalyst contact reacts;
Optional step (2): isolate gaseous stream from the effluent that step (1) obtains, obtain liquid phase stream;
Step (3): the effluent that the liquid phase stream obtain step (2) and hydrogen or step (1) obtain and hydrocracking catalyst contact reacts;
Step (4): isolate rocket engine fuel and diesel oil from the effluent that step (3) obtains;
Step (5): at least part of diesel oil step (4) obtained is sent in step (1) and mixed with stock oil, or mix with the effluent that described liquid phase stream or step (1) obtain at least part of diesel oil feeding step (3) that step (4) is obtained;
Wherein, the aromaticity content of described stock oil is more than 40 % by weight; The contact reacts condition of step (1) makes the saturation exponent of double ring arene in stock oil be 70-90%, and the contact reacts condition of step (3) makes the saturation exponent of total aromatic hydrocarbons in the liquid feeding of step (3) be 75-95%.
2. method according to claim 1, wherein, the aromaticity content of described stock oil is 40-90 % by weight.
3. method according to claim 1 and 2, wherein, in described stock oil, with the total amount of aromatic hydrocarbons for benchmark, the content of mononuclear aromatics is 20-40 % by weight.
4. according to the method in claim 1-3 described in any one, wherein, described stock oil is catalytic cracking diesel oil, or described stock oil is catalytic cracking diesel oil and the mixing oil mixing oil refining, described mixing is refined oil as one or more in heavy catalytic cycle oil, coal tar and liquefied coal coil, with the total amount of described mixing oil for benchmark, the content of described catalytic cracking diesel oil is 30-90 % by weight.
5. method according to claim 1, wherein, described Hydrobon catalyst contains carrier and load at least one group vib metal component on the carrier and at least one group VIII metal component, described group vib metal component exists with the form of metal oxide, described group VIII metal component exists with the form of metal-salt, and described carrier is silicon oxide.
6. method according to claim 5, wherein, with the total amount of Hydrobon catalyst for benchmark and with oxide basis, the content of described group VIII metal component is 1-10 % by weight, and the content of described group vib metal component is 5-50 % by weight.
7. method according to claim 1, wherein, described hydrocracking catalyst contains carrier and load at least one group VIII metal component on the carrier and at least one group vib metal component, described carrier contains y-type zeolite, with the total amount of described carrier for benchmark, the content of described y-type zeolite is 5-85 % by weight, and described y-type zeolite contains Mo and Ni, with the total amount of y-type zeolite for benchmark, with MoO
3the content of the Mo of meter is 0.5-10 % by weight, in the content of the Ni of NiO for 0.1-5 % by weight.
8. method according to claim 7, wherein, the preparation method of described y-type zeolite comprises:
(A) by y-type zeolite and containing Mo compound with containing Ni compound, a kind of mixture is obtained;
(B) in the atmosphere described mixture formed at the gas by moisture vapor, in 200-700 DEG C of process 1-24 hour.
9. the method according to claim 7 or 8, wherein, with the total amount of described hydrocracking catalyst for benchmark and with oxide basis, the content of described group VIII metal component is 1-10 % by weight, and the content of described group vib metal component is 5-50 % by weight.
10. method according to claim 1, wherein, in step (1), described catalytic condition comprises: temperature is 250-450 DEG C, and hydrogen dividing potential drop is 7-16MPa, and hydrogen to oil volume ratio is 100-2000Nm
3/ m
3, during liquid, volume space velocity is 0.2-10h
-1;
In step (3), described catalytic condition comprises: temperature is 250-450 DEG C, and hydrogen dividing potential drop is 3-25MPa, and hydrogen to oil volume ratio is 100-2000Nm
3/ m
3, during liquid, volume space velocity is 0.2-10h
-1.
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| CN108277044A (en) * | 2018-03-02 | 2018-07-13 | 中国石化青岛炼油化工有限责任公司 | A kind of system and method improving hydrocracking process Air China coal, yield of gasoline |
| CN108795514A (en) * | 2018-07-12 | 2018-11-13 | 天津大学 | A kind of heat absorbing type aviation fuel and preparation method thereof |
| CN109777510A (en) * | 2017-11-14 | 2019-05-21 | 中国石油化工股份有限公司 | A kind of method for hydrogen cracking improving jet fuel yield |
| CN109988635A (en) * | 2017-12-29 | 2019-07-09 | 中国石油化工股份有限公司 | A kind of hydrotreating and hydrocracking combined process |
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| CN115612527A (en) * | 2021-07-16 | 2023-01-17 | 中国石油化工股份有限公司 | Method for processing gasoline and diesel raw materials by hydrocracking device |
| CN115612527B (en) * | 2021-07-16 | 2024-02-09 | 中国石油化工股份有限公司 | Method for processing gasoline and diesel oil raw material by hydrocracking device |
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