CN103059930B - A kind of method preparing rocket engine fuel - Google Patents
A kind of method preparing rocket engine fuel Download PDFInfo
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- CN103059930B CN103059930B CN201110319485.7A CN201110319485A CN103059930B CN 103059930 B CN103059930 B CN 103059930B CN 201110319485 A CN201110319485 A CN 201110319485A CN 103059930 B CN103059930 B CN 103059930B
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Abstract
The invention provides a kind of method preparing rocket engine fuel, the method comprises: boiling point is obtain mixture after the last running of more than 260 DEG C mixes with the normal paraffin of C8-C24 by (1); Under hydroisomerization condition, described mixture, hydrogen are contacted the product after obtaining isomery with hydroisomerisation catalysts; (2) under Hydrofinishing conditions, the product after described isomery, hydrogen are contacted aftercut with Hydrobon catalyst and obtain the last running that rocket engine fuel and described boiling point are more than 260 DEG C.Method of the present invention is adopted not only to effectively raise the yield of rocket engine fuel in preparation process, and, make traditional last running obtained in rocket engine fuel of preparing obtain effective utilization.And the rocket engine fuel adopting method of the present invention to prepare almost all is made up of saturated alkane, stable in properties, be enough to meet the requirement as No. 3 rocket engine fuels.
Description
Technical field
The present invention relates to a kind of method preparing rocket engine fuel.
Background technology
Along with traditional fossil energy supply is becoming tight, the pressure of carbon dioxide discharge-reduction increases day by day, develops renewable, clean substitute energy and has become whole world common recognition.Because bioenergy has recyclability, green, come into one's own especially in recent years, be considered to one of most desirable route solving global energy crisis.
Along with the demand of rocket engine fuel constantly increases, the technology preparing rocket engine fuel from renewable raw materials is more and more subject to people's attention.These renewable raw materials comprise but do not limit to so, such as: vegetables oil (soybean oil, rapeseed oil, plam oil, jatropha curcas oil, Chinese vegetable tallow), animal tallow (lard, butter, fish oil), acidification oil, various lipid acid and acidifying wet goods.
At present, study more having, utilize vegetables oil and/or animal grease, prepare fatty acid methyl ester by transesterification reaction.Fatty acid methyl ester is a kind of clean renewable energy source, is the substitute products of the petroleum diesel of high-quality, is to use maximum biodiesel oil product at present.
Also there is the method by hydrotreatment, vegetables oil and/or animal grease are prepared into the research of diesel component.As US4992605A and US5705722A discloses the diesel component preparing high hexadecane value by the method for hydrogenation, but diesel component prepared by this method forms primarily of normal paraffin, and its cold filter clogging temperature is higher, have impact on its scope of application.
CN101233212A discloses a kind of method that two-step approach produces diesel oil, and the first step generates normal paraffin by hydrogenation deoxidation, and second step reduces the cold filter clogging temperature of diesel oil by isomerization reaction.
In addition, US2009/0158637A1 discloses a kind of method being prepared rocket engine fuel by renewable raw materials.Vegetables oil and/or animal grease are first obtained through hydrogenation deoxidation the normal paraffin that carbonatoms is 8-24 by the method, then through selective cracking and isomerization reaction, then are met the rocket engine fuel of requirement through fractionation.But the yield of rocket engine fuel is still lower in the method, and also there is generating portion alkene in cracking and isomerization process in the method, affects the problems such as the color of rocket engine fuel.
Hydroisomerization process plays vital effect as the important step adopting vegetables oil and/or animal grease to prepare rocket engine fuel to the whole process preparing rocket engine fuel, which determine character and the yield of the rocket engine fuel prepared, therefore, hydroisomerisation catalysts how is improved and hydroisomerization process has very important Research Significance to preparing rocket engine fuel.
Summary of the invention
The object of the invention is on the basis of existing technology, a kind of method preparing rocket engine fuel that jet fuel yield is higher is provided.
Although prior art has about using vegetables oil and/or animal grease to prepare the multinomial research of rocket engine fuel, but, in existing every research, the yield of rocket engine fuel still has much room for improvement, but the jet fuel yield how further raising uses vegetables oil and/or animal grease to prepare in rocket engine fuel process runs into bottleneck, current most of investigator attempts the yield by selecting more efficiently catalyzer (as hydroisomerisation catalysts) to improve rocket engine fuel in this preparation process, and the present inventor is devoted to improve and uses vegetables oil and/or animal grease to prepare jet fuel yield in rocket engine fuel process in years of researches process always, finally finally find, even if also effectively can not improve the yield of rocket engine fuel in preparation process by improving catalyzer, the invention thinking that the present inventor proposes is: turned back in hydroisomerization process by last running fractionation in preparation process obtained and carry out hydroisomerization the yield in preparation process namely can be made greatly to improve.Further, CN1382526A discloses a kind of preparation method of catalyst for hydrogenation de-waxing, and point out that catalyzer that this preparation method prepares may be used for the Hydrodewaxing process of content of wax lubricating oil, content of wax rocket engine fuel, content of wax diesel oil, and the present inventor finds in research process, when processing the normal paraffin obtained through hydrogenation deoxidation from animal-plant oil, this catalyzer has selective cracking and isomerized difunctional, make it may be used for preparing rocket engine fuel, and the rocket engine fuel prepared can meet the service requirements of No. 3 rocket engine fuels.Based on aforementioned invention thinking and discovery, complete the present invention.
To achieve these goals, the invention provides a kind of method preparing rocket engine fuel, the method comprises:
(1) be obtain mixture after the last running of more than 260 DEG C mixes with the normal paraffin of C8-C24 by boiling point; Under hydroisomerization condition, described mixture, hydrogen are contacted the product after obtaining isomery with hydroisomerisation catalysts;
(2) under Hydrofinishing conditions, the product after described isomery, hydrogen are contacted aftercut with Hydrobon catalyst and obtain the last running that rocket engine fuel and described boiling point are more than 260 DEG C.
Method of the present invention is adopted not only to effectively raise the yield of rocket engine fuel in preparation process, and, make traditional last running obtained in rocket engine fuel of preparing obtain effective utilization.And the rocket engine fuel adopting method of the present invention to prepare almost all is made up of saturated alkane, stable in properties, be enough to meet the requirement as No. 3 rocket engine fuels.
Embodiment
The invention provides a kind of method preparing rocket engine fuel, the method comprises:
(1) be obtain mixture after the last running of more than 260 DEG C mixes with the normal paraffin of C8-C24 by boiling point; Under hydroisomerization condition, described mixture, hydrogen are contacted the product after obtaining isomery with hydroisomerisation catalysts;
(2) under Hydrofinishing conditions, the product after described isomery, hydrogen are contacted aftercut with Hydrobon catalyst and obtain the last running that rocket engine fuel and described boiling point are more than 260 DEG C.
According to method of the present invention, object of the present invention can be realized preferably according to preceding solution, under preferable case, last running described in step (1) accounts for the 10-100 % by weight of last running described in step (2), and more preferably described in step (1), last running accounts for the 50-90 % by weight of last running described in step (2).
According to method of the present invention, the range of choices of the kind of described hydroisomerisation catalysts is wider, the conventional hydroisomerisation catalysts used all can realize object of the present invention, generally comprise carrier and metal active constituent, for the present invention, preferred described hydroisomerisation catalysts contains carrier and metal active constituent, and described carrier contains aluminium silicophosphate molecular sieve, described metal active constituent contain in group VIII metallic element one or more.
According to method of the present invention, the hydroisomerisation catalysts meeting aforementioned claim all can well realize goal of the invention of the present invention, under preferable case, aluminium silicophosphate molecular sieve in described hydroisomerisation catalysts is one or more in SAPO-11, SAPO-31, SAPO-41, ZSM-22, ZSM-23 and ZSM-48 molecular sieve, and more preferably the degree of crystallinity of described aluminium silicophosphate molecular sieve is at least 70%.
According to method of the present invention, the range of choices of the kind of described metal active constituent is wider, as long as it is one or more in group VIII metallic element, under preferable case, described metal active constituent is one or more in Fe, Co, Ni, Ru, Rh, Pb, Os, Ir, Pt, is more preferably Pt.In embodiments of the invention, that concrete use is Pt.
According to method of the present invention, in described hydroisomerisation catalysts, the range of choices of the content of various component is wider, under preferable case, with total restatement of catalyzer, described metal active constituent is in the content of element for 0.1-10 % by weight, and the content of described carrier is 90-99.9 % by weight; Wherein, in preferred vector, the content of aluminium silicophosphate molecular sieve is 5-100 % by weight.
Except containing except aluminium silicophosphate molecular sieve in the aforementioned bearer of hydroisomerisation catalysts of the present invention, the various materials that other can use as carrier of prior art can also be contained, such as the heat-resistant inorganic oxide such as aluminum oxide, silicon oxide can be contained, those skilled in the art all can know this, do not repeat them here.
According to method of the present invention, the present invention to the preparation method of described hydroisomerisation catalysts without particular requirement, as long as meet the aforementioned requirement to catalyzer of the present invention, the preferred aforementioned hydrogenation isomerization catalyst of such as the present invention can be prepared according to preparation method disclosed in CN1382526A, no longer carries out emphasis description at this.
According to method of the present invention, the range of choices of described hydroisomerization condition is wider, and for the present invention, under preferable case, described hydroisomerization condition comprises: temperature is 250-450 DEG C, is preferably 300-350 DEG C; Pressure is 1-7MPa, is preferably 3-6MPa; Volume space velocity is 0.1-5h
-1, be preferably 1-3h
-1; Hydrogen to oil volume ratio is 100-800: 1 (Nm
3/ m
3), be preferably 400-600: 1 (Nm
3/ m
3).
According to method of the present invention, the range of choices of described Hydrofinishing conditions is wider, and under preferable case, described Hydrofinishing conditions comprises: temperature is 100-250 DEG C, and pressure is 1-7MPa, and volume space velocity is 0.5-5h
-1, hydrogen to oil volume ratio is 100-500: 1 (Nm
3/ m
3).
According to method of the present invention, under preferable case, the Hydrobon catalyst that described Hydrobon catalyst can adopt this area routine to use, preferred described Hydrobon catalyst contains heat-resistant inorganic oxide carrier and load hydrogenation component on this carrier, hydrogenation component be selected from group VIII metallic element one or more, preferred described hydrogenation component is platinum and/or palladium, more preferably, with the gross weight of catalyzer for benchmark, in element, the content of platinum and/or palladium is 0.1-5 % by weight.
According to method of the present invention, the various heat-resistant inorganic oxide carriers that described heat-resistant inorganic oxide carrier can be commonly used for prior art, such as can for obtain by one or more in aluminum oxide, silicon oxide, titanium oxide, zirconium white and molecular sieve are shaping, the present invention to this without particular requirement.
According to method of the present invention, in order to effectively utilize vegetables oil and/or animal grease to be prepared rocket engine fuel, preferably, described normal paraffin by vegetables oil and/or animal grease and hydrogen, is contacted with hydrogenation deoxidation catalyst and obtains under hydrodeoxygenation conditions.
According to method of the present invention, the range of choices of described hydrodeoxygenation conditions is wider, and for the present invention, under preferable case, it is 200-400 DEG C that described hydrodeoxygenation conditions generally comprises temperature, and pressure is 1-7MPa, and volume space velocity is 0.5-5h
-1, hydrogen to oil volume ratio is 300-1500: 1 (Nm
3/ m
3).
According to method of the present invention, the various hydrogenation deoxidation catalysts that described hydrogenation deoxidation catalyst can be commonly used for prior art, generally speaking described hydrogenation deoxidation catalyst contains heat-resistant inorganic oxide carrier and load hydrogenation active component on this carrier, containing group vib metal and group VIII metal in described hydrogenation active component, containing cobalt and/or nickel and molybdenum and/or tungsten in further preferred described hydrogenation activity composition; More preferably, with the weight of catalyzer for benchmark, with oxide basis, the content of molybdenum and/or tungsten is 5-40 % by weight, and the total amount of cobalt and/or nickel is 1-10 % by weight.
According to method provided by the invention, described hydrogenation deoxidation catalyst uses, under preferable case, in order to maintain the sulfuration form of hydrogenation deoxidation catalyst as hydrogenation deoxidation catalyst preferably through after sulfuration, sulphur can be supplemented in stock oil, also can add sulphur in recycle hydrogen.Therefore, for the present invention, contain vulcanizing agent in preferred described vegetables oil and/or animal grease, the concentration of described vulcanizing agent is 0.01-0.5 % by weight.Described vulcanizing agent can be variously can gasify under hydrodeoxygenation conditions and hydrogenation deoxidation catalyst be carried out to the S-contained substance of sulfuration, and under preferable case, described vulcanizing agent is H
2s, CS
2, dimethyl disulfide, Dimethyl sulfide, one or more in n-butyl sulfide and thiophene.Further, in order to reduce the water that generates in hydrogenation deoxidation process to the impact of catalyzer and the temperature rise that reduces in preparation process in reactor, can using the thinner of the product after hydrogenation deoxidation as charging (as vegetables oil and/or animal grease), by the product after hydrogenation deoxidation return mix with charging after enter in reactor together and contact, for the present invention, the volume ratio of the back amount of the product after preferred hydrogenation deoxidation and charging (as vegetables oil and/or animal grease) is 2-10: 1.Therefore, under preferable case, the contact of vegetables oil and/or animal grease, hydrogen and hydrogenation deoxidation catalyst is carried out in the presence of a diluent in step (1), and described thinner is product after step (1) gained hydrogenation deoxidation (dewaters or after not dewatering).Under aforementioned hydrogenation deoxygenation conditions of the present invention, olefins hydrogenation may be comprised, hydrogenation deoxidation, hydrogenation decarbonylation base, hydrogenation decarboxylation and direct decarboxylation are in interior various reactions, the hydrogenation deoxidation reaction product finally obtained is mainly the normal paraffin of C8-C24, water and on a small quantity other gaseous matter are as propane, carbon monoxide and carbonic acid gas etc., therefore the general product obtained through dehydration by product after hydrogenation deoxidation is substantially all normal paraffin (99-100 % by weight), the hydroisomerization of step (2) directly can be carried out without separating gaseous sub-stances (gaseous matter is direct volatilization generally).Those skilled in the art all can know this, in this no longer emphasis description.The hydrogenation deoxidation catalyst used in the specific embodiment of the present invention is the hydrogenation deoxidation catalyst after over cure, and the method for sulfuration can be carried out with reference to prior art, and in the present invention, no longer emphasis describes.
According to method of the present invention, the kind of described heat-resistant inorganic oxide carrier describes aforementioned, does not repeat them here.
According to method of the present invention, described vegetables oil can be that various herbaceous plant is oily and xylophyta is oily or its mixture, such as, can be soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Rice pollard oil, sunflower oil, peanut oil, Viscotrol C, sesame oil, Fructus Zanthoxyli oil, tea oil, Oleum Cocois, sweet oil, coptis wood oil, plam oil, tung oil, one or more in rosin oil and Chinese vegetable tallow.The preferred described vegetables oil of the present invention is one or more in soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Fructus Zanthoxyli oil, coptis wood oil and plam oil.
According to method of the present invention, described animal grease can be the grease of various animal, such as, can be one or more in lard, butter, sheep oil, fish oil.
Vegetables oil described in the present invention and/or animal grease can be waste oil from restaurant.
The rocket engine fuel prepared according to preceding method of the present invention all can meet the standard as No. 3 rocket engine fuels except density.And in embody rule process, in order to the standard making rocket engine fuel density of the present invention also can meet existing No. 3 rocket engine fuels, can the rocket engine fuel that rocket engine fuel of the present invention and existing employing refining of petroleum method obtain be carried out used in combination, in process used in combination, the weight concentration of rocket engine fuel of the present invention is 10-70 % by weight, is preferably 30-50 % by weight.
The method of fractionation in the present invention is conventional fractionating method, is generally fractionation by distillation.
Below will be described the present invention by embodiment.
Hydrogenation deoxidation catalyst adopts RN-10 catalyzer (China Petrochemical Industry's catalyst Co. Chang Ling catalyzer branch office, mainly consist of alumina catalyst support and metal active constituent nickel and tungsten, wherein nickel is 2.3 % by weight with the content of oxide basis, and tungsten is 25.3 % by weight with the content of oxide basis).Hydrobon catalyst adopts RLF-10W catalyzer (China Petrochemical Industry's catalyst Co. Chang Ling catalyzer branch office, mainly consists of alumina catalyst support and metal active constituent platinum, and wherein metal active constituent platinum is 0.5 % by weight in the content of element).
In following examples, the color of rocket engine fuel, freezing point, flash-point record according to the method for GB/T3555, GB/T2430 and GB/T261 respectively, and in rocket engine fuel, olefin(e) centent, aromaticity content record according to the method for GB/T11132.The quality that mass yield refers to the rocket engine fuel prepared and the mass percent of stock oil added.
Describe in embodiment be preparation process after steady running instead of react initial time state, such as, when preparation process just starts, there is no adding of last running in step (2), and in a stable operation state because step (3) has obtained last running, therefore, under steady operational status, step (2) is carried out under last running exists.Those skilled in the art are readily appreciated that this according to the specifically described technical scheme of the present invention.
Preparation embodiment 1
Hydroisomerisation catalysts is prepared: (alumina content is 60 % by weight to take catalyzer C1 prepared by embodiment 1 in 40g CN1382526A and 22g solid oxide Alumina gel according to the method for embodiment in CN1382526A 6 Kaolinite Preparation of Catalyst, Inst., of Alunite Comprehensive Utilization, Zhejiang Prov. produces) mix, be extruded into the trilobal bar that circumscribed circle diameter is 1.8 millimeters, 120 DEG C of oven dry, then 550 DEG C of roastings 4 hours are the Pt (NH of 0.3 % by weight with platinum constituent content
3)
4cl
2h
2o aqueous solution 53.2g floods, 120 DEG C of oven dry, be the hydrogen reducing 4 hours of 800 ml/min at 450 DEG C with flow, obtaining catalyst A (is the SAPO-11 molecular sieve 75 % by weight of 77% containing degree of crystallinity in A, in element platinum content 0.3 % by weight, all the other are aluminum oxide).
Preparation embodiment 2
According to the method Kaolinite Preparation of Catalyst of embodiment in CN1382526A 6, just replacing the reference agent C1 of embodiment 1 preparation in CN1382526A to obtain catalyst B with the reference agent B1 of preparation in CN1382526A comparative example 1 (is the SAPO-11 molecular sieve 75 % by weight of 67% containing degree of crystallinity in B, in element platinum content 0.3 % by weight, all the other are aluminum oxide).
Embodiment 1
(1) under hydrodeoxygenation conditions, plam oil (vulcanizing agent Methyl disulfide ether content is 0.02 % by weight), hydrogen are contacted with hydrogenation deoxidation catalyst RN-10, hydrodeoxygenation conditions comprises: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 1000: 1 (Nm
3/ m
3);
(2) under hydroisomerization condition, the last running of the normal paraffin of the C13-C20 obtained after the product dehydrate after aforementioned hydrogenation deoxidation and step (3) are obtained 90 % by weight, H
2contact with hydroisomerisation catalysts A, wherein, comprise under hydroisomerization condition: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3);
(3) under Hydrofinishing conditions, by the product after aforementioned hydrogenation isomerization, H
2contact with Hydrobon catalyst RLF-10W, Hydrofinishing conditions comprises: temperature is 150 DEG C, and pressure is 5.0MPa, and volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3); Product fractionation after hydrofining is obtained the jet fuel fraction of 150-260 DEG C and the last running of more than 260 DEG C, wherein the character of gained rocket engine fuel is as shown in table 1.
Embodiment 2
(1) under hydrodeoxygenation conditions, by the mixture of plam oil and lard, (wherein the weight ratio of plam oil and lard is 4: 1, vulcanizing agent Methyl disulfide ether content is 0.02 % by weight), hydrogen contacts with hydrogenation deoxidation catalyst RN-10, hydrodeoxygenation conditions comprises: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 1000: 1 (Nm
3/ m
3);
(2) under hydroisomerization condition, the last running of the normal paraffin of the C13-C20 obtained after the product dehydrate after aforementioned hydrogenation deoxidation and step (3) are obtained 75 % by weight, H
2contact with hydroisomerisation catalysts A, wherein, comprise under hydroisomerization condition: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3);
(3) under Hydrofinishing conditions, by the product after aforementioned hydrogenation isomerization, H
2contact with Hydrobon catalyst RLF-10W, Hydrofinishing conditions comprises: temperature is 150 DEG C, and pressure is 5.0MPa, and volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3); Product fractionation after hydrofining is obtained the jet fuel fraction of 150-260 DEG C and the last running of more than 260 DEG C, wherein the character of gained rocket engine fuel is as shown in table 1.
Comparative example 1
(1) under hydrodeoxygenation conditions, plam oil, hydrogen are contacted with hydrogenation deoxidation catalyst RN-10, hydrodeoxygenation conditions comprises: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 1000: 1 (Nm
3/ m
3);
(2) under hydroisomerization condition, by normal paraffin, the H of C13-C20 that obtain after the product dehydrate after aforementioned hydrogenation deoxidation
2contact with hydroisomerisation catalysts A, wherein, comprise under hydroisomerization condition: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3);
(3) under Hydrofinishing conditions, by the product after aforementioned hydrogenation isomerization, H
2contact with Hydrobon catalyst RLF-10W, Hydrofinishing conditions comprises: temperature is 150 DEG C, and pressure is 5.0MPa, and volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3); Obtain the product fractionation after hydrofining being less than the lighting end of 150 DEG C, the jet fuel fraction of 150-260 DEG C and the last running of more than 260 DEG C, wherein the character of gained rocket engine fuel is as shown in table 1.
Comparative example 2
Rocket engine fuel is prepared according to the method for comparative example 1, unlike, reaction raw materials is the mixture of plam oil and lard, and wherein the weight ratio of plam oil and lard is 4: 1, and the character of gained rocket engine fuel is as shown in table 1.
Embodiment 3
(1) under hydrodeoxygenation conditions, plam oil (vulcanizing agent Methyl disulfide ether content is 0.02 % by weight), hydrogen are contacted with hydrogenation deoxidation catalyst RN-10, hydrodeoxygenation conditions comprises: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 1000: 1 (Nm
3/ m
3);
(2) under hydroisomerization condition, the last running of the normal paraffin of the C13-C20 obtained after the product dehydrate after aforementioned hydrogenation deoxidation and step (3) are obtained 30 % by weight, H
2contact with hydroisomerisation catalysts B, wherein, comprise under hydroisomerization condition: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3);
(3) under Hydrofinishing conditions, by the product after aforementioned hydrogenation isomerization, H
2contact with Hydrobon catalyst RLF-10W, Hydrofinishing conditions comprises: temperature is 150 DEG C, and pressure is 5.0MPa, and volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3); Product fractionation after hydrofining is obtained the jet fuel fraction of 150-260 DEG C and the last running of more than 260 DEG C, the character of gained rocket engine fuel is as shown in table 1.
Comparative example 3
(1) under hydrodeoxygenation conditions, plam oil, hydrogen are contacted with hydrogenation deoxidation catalyst RN-10, hydrodeoxygenation conditions comprises: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 1.0h
-1, hydrogen to oil volume ratio is 1000: 1 (Nm
3/ m
3);
(2) under hydroisomerization condition, by normal paraffin, the H of C13-C20 that obtain after the product dehydrate after aforementioned hydrogenation deoxidation
2contact with hydroisomerisation catalysts B, wherein, comprise under hydroisomerization condition: pressure is 5.0MPa, temperature is 320 DEG C, volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3);
(3) under Hydrofinishing conditions, by the product after aforementioned hydrogenation isomerization, H
2contact with Hydrobon catalyst RLF-10W, Hydrofinishing conditions comprises: temperature is 150 DEG C, and pressure is 5.0MPa, and volume space velocity is 2.0h
-1, hydrogen to oil volume ratio is 500: 1 (Nm
3/ m
3); Obtain the product fractionation after hydrofining being less than the lighting end of 150 DEG C, the jet fuel fraction of 150-260 DEG C and the last running of more than 260 DEG C, the character of gained rocket engine fuel is as shown in table 1.
Table 1
As can be seen from the result of table 1, the rocket engine fuel adopting method of the present invention to prepare can meet the requirement of No. 3 rocket engine fuels except density, can used as No. 3 rocket engine fuels.
Claims (10)
1. prepare a method for rocket engine fuel, the method comprises:
(1) be obtain mixture after the last running of more than 260 DEG C mixes with the normal paraffin of C8-C24 by boiling point; Under hydroisomerization condition, described mixture, hydrogen are contacted the product after obtaining isomery with hydroisomerisation catalysts;
(2) under Hydrofinishing conditions, the product after described isomery, hydrogen are contacted aftercut with Hydrobon catalyst and obtain the last running that rocket engine fuel and described boiling point are more than 260 DEG C;
Wherein, described in step (1), last running accounts for the 50-90 % by weight of last running described in step (2);
Described hydroisomerisation catalysts contains carrier and metal active constituent, and described carrier contains aluminium silicophosphate molecular sieve, described metal active constituent contain in group VIII metal element one or more;
Described aluminium silicophosphate molecular sieve is one or more in SAPO-11, SAPO-31 and SAPO-41 molecular sieve, and the degree of crystallinity of described aluminium silicophosphate molecular sieve is at least 70%.
2. method according to claim 1, wherein, described metal active constituent is one or more in Fe, Co, Ni, Ru, Rh, Pb, Os, Ir, Pt.
3. method according to claim 2, wherein, described metal active constituent is Pt.
4. method according to claim 1, wherein, with total restatement of hydroisomerisation catalysts, described metal active constituent is in the content of element for 0.1-10 % by weight, and the content of described carrier is 90-99.9 % by weight; Wherein, in carrier, the content of aluminium silicophosphate molecular sieve is 5-100 % by weight.
5. method according to claim 1, wherein, described hydroisomerization condition comprises: temperature is 250-450 DEG C, and pressure is 1-7MPa, and volume space velocity is 0.1-5h
-1, hydrogen to oil volume ratio is 100-800:1Nm
3/ m
3.
6. method according to claim 1, wherein, described Hydrofinishing conditions comprises: temperature is 100-250 DEG C, and pressure is 1-7MPa, and volume space velocity is 0.5-5h
-1, hydrogen to oil volume ratio is 100-500:1Nm
3/ m
3.
7. method according to claim 1, wherein, described normal paraffin by vegetables oil and/or animal grease and hydrogen, is contacted with hydrogenation deoxidation catalyst and obtains under hydrodeoxygenation conditions.
8. method according to claim 7, wherein, described hydrodeoxygenation conditions comprises: temperature is 200-400 DEG C, and pressure is 1.0-7.0MPa, and volume space velocity is 0.5-5.0h
-1, hydrogen to oil volume ratio is 300-1500:1Nm
3/ m
3.
9. method according to claim 7, wherein, described vegetables oil is one or more in soybean oil, rapeseed oil, Oleum Gossypii semen, Semen Maydis oil, Rice pollard oil, sunflower oil, peanut oil, Viscotrol C, sesame oil, Fructus Zanthoxyli oil, tea oil, Oleum Cocois, sweet oil, coptis wood oil, plam oil, tung oil, rosin oil and Chinese vegetable tallow, and described animal grease is one or more in lard, butter, sheep oil and fish oil.
10. method according to claim 7, wherein, described vegetables oil and/or animal grease are waste oil from restaurant.
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| CN103801295B (en) * | 2014-03-07 | 2016-04-13 | 南开大学 | The Catalysts and its preparation method of aviation kerosine prepared by castor oil |
| CN106256880B (en) * | 2015-06-18 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method that jet fuel is prepared by animal and plant fat |
| CN106281402B (en) * | 2015-06-23 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method that jet fuel is prepared by renewable raw materials |
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| CN101952392A (en) * | 2007-12-21 | 2011-01-19 | 环球油品公司 | Prepare aviation fuel from biological renewable raw materials |
| CN102124080A (en) * | 2008-07-01 | 2011-07-13 | 耐思特石油公司 | Process for the manufacture of hydrocarbons of biological origin |
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| JP5339863B2 (en) * | 2008-11-20 | 2013-11-13 | Ｊｘ日鉱日石エネルギー株式会社 | Method for producing aviation fuel oil composition |
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| CN101952392A (en) * | 2007-12-21 | 2011-01-19 | 环球油品公司 | Prepare aviation fuel from biological renewable raw materials |
| CN102124080A (en) * | 2008-07-01 | 2011-07-13 | 耐思特石油公司 | Process for the manufacture of hydrocarbons of biological origin |
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