CN111647449A - High-performance aviation alternative fuel and preparation method thereof - Google Patents
High-performance aviation alternative fuel and preparation method thereof Download PDFInfo
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- CN111647449A CN111647449A CN202010554841.2A CN202010554841A CN111647449A CN 111647449 A CN111647449 A CN 111647449A CN 202010554841 A CN202010554841 A CN 202010554841A CN 111647449 A CN111647449 A CN 111647449A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2270/00—Specifically adapted fuels
- C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
- C10L2290/12—Regeneration of a solvent, catalyst, adsorbent or any other component used to treat or prepare a fuel
Abstract
The invention relates to a high-performance aviation alternative fuel and a preparation method thereof. The method takes mixed liquor or fermentation liquor which is obtained by fermenting biomass and contains water, acetone and optional butanol and ethanol as raw materials, and can prepare the high-performance aviation alternative fuel after condensation reaction, trimerization condensation reaction and hydrodeoxygenation reaction. The aviation alternative fuel is C with branched chain21Or C15The cycloparaffin mixture of (1) has two isomers, and the freezing point and the energy density of the cycloparaffin mixture meet the standards of aviation fuel. The bio-based aviation alternative fuel is used as an aircraft engine fuel, so that the demand on petroleum-based aviation fuel can be greatly reduced. The preparation method of the high-performance aviation alternative fuel provided by the invention has the advantages of simple production process flow, low energy consumption, high product performance, high yield, low raw material cost, environmental friendliness and potential for realizing large-scale production.
Description
Technical Field
The invention belongs to the technical field of new energy, and relates to a high-performance aviation alternative fuel and a preparation method thereof.
Background
Aviation fuel is a fuel used by aircraft engines, which is mainly a saturated hydrocarbon compound, and the carbon number range of civil aviation fuel is generally 8-16, and the carbon number range of military aviation fuel is even 21-33. Aviation fuel, unlike automotive fuel, requires a low freezing point to prevent icing and a high energy density (volumetric heating value) to provide a powerful energy source. At present, with the continuous consumption and increasing supply pressure of traditional fossil energy such as natural gas and petroleum in the world, the development and utilization of biomass energy are receiving more and more attention, wherein one typical biomass raw material is ABE fermentation liquor. The ABE fermentation liquor is short for acetone/butanol/ethanol fermentation liquor as a main component, and can be prepared into a long-chain compound by utilizing a chemical catalysis integration mode. The ABE fermentation liquor often contains a large amount of water, and if the water in the ABE fermentation liquor is completely removed, a complicated process is needed and huge energy is consumed, so that the promotion of the water-containing ABE mixed liquor into a long-chain product is catalyzed, and the research is hot.
However, there are still two serious problems with the current preparation of aviation alternative fuels by catalyzing aqueous ABE mixed liquor. On the one hand, poor water tolerance of the catalyst results in poor catalytic activity in catalyzing the alkylation reaction of the high aqueous ABE mixture. For example, Gong, Y.H. has previously described the article "Improved selection of long-chain products from organic query of acetic on-ebutanol-ethanol mixture over high water resistance catalyzed on hydrolytic SBA-16" (ACS Sustainable Chemistry)&Engineering,2019,7,10323-10331.), and C which can be used as a precursor of aviation alternative fuels when the water content in the ABE mixed liquid is increased from 0 wt% to 11 wt%8–C16The yield of ketone or alcohol was reduced from 44.5% to 7.4%. On the other hand, the performance problems of the product, i.e., the freezing point and energy density of the product, are difficult to meet with the stringent performance requirements of aviation fuels. Currently, long chain products prepared from ABE mixtures have difficulty meeting this requirement, for example. Chinese patent CN106047425A discloses a method for preparing aviation fuel additive by using ABE mixed liquor, and the prepared C8–C16The hydrocarbons of (a) although meeting the aviation fuel carbon number range, the linear nature of their products limits their performance; chinese patent CN109422638A discloses a method for preparing ketone compounds by converting ABE fermentation liquor containing 20 wt% of water, but the prepared 4-heptanone can not be used as an aviation fuel precursor.
Therefore, there is an urgent need for a new process for catalytically converting aqueous ABE mixed liquor into high performance aviation alternative fuels.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-performance aviation alternative fuel aiming at the defects of the prior art, wherein the aviation alternative fuel is prepared based on aqueous ABE raw material liquid, and has the advantages of low freezing point, high energy density (volume heat value) and wide raw material source. The invention also provides a preparation method of the high-performance aviation alternative fuel. The method takes water-containing ABE mixed liquid as a raw material, and prepares the annular high-performance aviation alternative fuel through three steps of catalytic processes.
To this end, the invention provides, in a first aspect, a high-performance aviation alternative fuel, which is prepared on the basis of an aqueous ABE mixed liquor and comprises a branched C as a main component21Or C15Cycloalkane of (a); wherein the ABE mixed solution is a feed solution containing water, acetone, butanol and ethanol; preferably, the ABE feedstock is a fermentation broth comprising water, acetone, butanol and ethanol.
According to the invention, the high-performance aviation alternative fuel has the freezing point of less than 123-3The above.
In some embodiments of the invention, of the high performance aviation alternative fuels, C15The freeze point and energy density (volumetric heating value) of the cycloparaffins meet the requirements of JP-5 for military aviation fuel.
In other embodiments of the present invention, C21The freeze point and energy density of the cycloparaffins meet the requirements of JP-5 and JP-10 for military aviation fuels.
In a second aspect, the present invention provides a method for preparing a high performance aviation alternative fuel according to the first aspect of the present invention, which comprises:
step L, carrying out condensation reaction on the aqueous ABE mixed solution to prepare a liquid mixture with a main component of 2-heptanone or 2-pentanone;
step M, carrying out trimeric condensation reaction on the liquid mixture mainly containing 2-heptanone or 2-pentanone to obtain the liquid mixture mainly containing C15Or C21Mixtures of cyclic ketones of (a);
step N, the main component is C15Or C21The cyclic ketone mixture is subjected to hydrodeoxygenation treatment to prepare the high-performance aviation alternative fuel.
Wherein the main component of the high-performance aviation alternative fuel is C with branched chain15Or C21Cycloalkane of (a); the ABE mixed solution is a feed liquid containing water, acetone, butanol and ethanol; preferably, the ABE feedstock is a fermentation broth comprising water, acetone, butanol and ethanol.
In some embodiments of the invention, the ABE feedstock solution comprises, based on the total weight of the ABE feedstock solution, 9.8 wt% to 12.1 wt% water, 32.4 wt% to 49.0 wt% acetone, 0 wt% to 53.7 wt% butanol, and 2.2 wt% to 42.9 wt% ethanol.
According to some embodiments of the invention, in step L, the condensation reaction is carried out in the presence of catalyst a, which is a Ni-MgO-SBA-16 catalyst; preferably, the molar ratio of Ni, MgO and SBA-1 in the Ni-MgO-SBA-16 catalyst is (1.7-8.5) 50:50, more preferably 4.26:50: 50; further preferably, the catalyst a is used in an amount of 10 wt% based on the total weight of the ABE feedstock solution.
In some preferred embodiments of the present invention, the condensation reaction temperature is 240 ℃ and the condensation reaction time is 24 hours.
According to other embodiments of the present invention, in step M, the trimerization condensation reaction is carried out in the presence of a catalyst B comprising MgAl-MMO catalyst, gamma-Al, and a solvent C2O3One or more of a catalyst and a MgO catalyst; preferably, the catalyst B is used in an amount of 10 wt% to 133 wt%, based on the total weight of the liquid mixture of 2-heptanone or 2-pentanone.
In some embodiments of the present invention, the solvent C comprises one or more of 2-heptanol, n-undecane, decalin, toluene, and n-heptane, preferably the solvent C is n-heptane or toluene; preferably, the solvent C is used in an amount of 40 wt% to 1000 wt%, based on the total weight of the liquid mixture of 2-heptanone or 2-pentanone.
In some preferred embodiments of the present invention, in step M, the trimerization condensation reaction is further carried out in the presence of a dehydrating agent, which is anhydrous CaCl2(ii) a Preferably, the dehydrating agent is used in an amount of 50 wt% to 100 wt% based on the total mass of the catalyst.
In some preferred embodiments of the present invention, in step M, the trimerization condensation reaction temperature is 160-180 ℃, and the trimerization condensation reaction time is 6 h.
According to still further embodiments of the present invention, in step N, the hydrodeoxygenation reaction is performed in the presence of a catalyst D and a solvent E, wherein the catalyst D is Ni/MgSiO3(ii) a Preferably based on Ni/MgSiO in the catalyst3Based on the total moles of (A), the Ni/MgSiO3The mole fraction of Ni in the catalyst is 10.8%; further preferably, the catalyst D is used in an amount based on C15Or C21Based on the total weight of the cyclic ketone mixture (2), is 100 wt%.
In some embodiments of the invention, the solvent E is cyclohexane; preferably, the solvent E is used in an amount based on C15Or C21The total weight of the cyclic ketone mixture (b) was 3250 wt%.
In some preferred embodiments of the present invention, in step N, the hydrodeoxygenation reaction is carried out at a pure hydrogen atmosphere pressure of 2.5 MPa; preferably, the hydrodeoxygenation reaction temperature is 180 ℃, and the hydrodeoxygenation reaction time is 12 h.
The invention provides a three-step catalytic process flow for preparing high-performance aviation alternative fuel by using high-water-content ABE mixed liquid. Compared with the reported preparation method, the method has the following advantages: 1) the water content of the raw material of the catalyzed ABE mixed liquid is high and reaches 12.1 wt%, so that the cost consumed by separating water in the ABE fermentation liquid is reduced; 2) the product has low freezing point and high energy density, and meets the requirements of military aviation fuels JP-5 and JP-10; 3) the whole process flow is simple to operate, the product can be automatically separated from oil and water, and the energy consumption of separation is reduced; 4) the used catalyst is a non-noble metal catalyst, is energy-saving and environment-friendly, and meets the green chemical standard. The method has the advantages of simple production process, low energy consumption, good product quality, wide raw material source and low production cost, and provides a new way for producing high-performance aviation fuel by using the aqueous ABE fermentation liquor.
Drawings
The invention is described in further detail below with reference to the attached drawing figures:
FIG. 1 shows the preparation of branched cyclic C from aqueous ABE mixtures by a three-step process15Or C21And (3) reaction process of alkane.
Detailed Description
In order that the invention may be readily understood, a detailed description of the invention is provided below. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Where a range of values is provided, it is understood that each intervening value, to the extent that there is no stated or intervening value in that stated range, to the extent that there is no such intervening value, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and are also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where a specified range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the invention.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
Term of
The term "total number of moles of ABE carbon" as used herein refers to the total number of moles of acetone, butanol, and ethanol.
The invention relates to a mesoporous silica molecular sieve which is hydrothermally synthesized with SBA-16 of 220 ℃, and the preparation method is shown in Zhang, P.L. and other articles 'Ordered cubic mesoporous silica with large pore size synthesized via high-temperature route, Langmuir,2009,25(22), 13169-13175'.
The term "C" according to the invention8-C16The "ketone" in (A) means a ketone having 8 to 16 carbon atoms.
The term "C" according to the invention8-C16The "alcohol(s)" refers to an alcohol having 8 to 16 carbon atoms.
The term "C" to which the present invention pertains21The cyclic ketone "refers to a cyclic ketone containing two isomers and having a carbon number of 21, and the specific structure is shown in fig. 1.
The term "C" to which the present invention pertains15The cyclic ketone "refers to a cyclic ketone containing two isomers and having a carbon number of 15, and the specific structure is shown in fig. 1.
The term "high-performance aviation alternative fuel" refers to a fuel with a freezing point of < 123-3The above aviation replaces fuels.
The term aviation alternative fuel as used herein refers to non-petroleum based aviation fuels.
As used herein, the term "density" is a measure of the mass of liquid fuel in a particular volume, and is equal to the mass of the fuel divided by the volume in g/mL.
The term "energy density" as used herein is a measure of the heating value of a liquid fuel in a particular volume, equal to the heating value of the fuel divided by the volume, in btu/gal, also referred to herein as the volumetric heating value.
II, embodiments
As mentioned above, the method for producing biological aviation fuel from ABE mixed liquor in the prior art has a long distance away from the actual practical application, and the main problem is that the product properties (freezing point and energy density) can not meet the requirements of aviation fuel. Based on this, the present inventors have conducted a great deal of experimental studies on the technique of upgrading ABE mixed liquor and the corresponding aqueous ABE mixed liquor to a long chain product. The inventor finds that 2-pentanone or 2-heptanone can be selectively produced by using high-water-content ABE mixed liquor as a raw material through a first-step catalytic reaction; and 2-pentanone or 2-heptanone can produce the cyclic branched alkane with low freezing point and high energy density after undergoing the second trimerization condensation reaction and the third hydrodeoxygenation reaction. The present invention has been made based on this finding.
Therefore, the high-performance aviation alternative fuel related to the first aspect of the invention is prepared based on an aqueous ABE mixed liquid, and the main component of the high-performance aviation alternative fuel is C with branched chains21Or C15Cycloalkane of (a); wherein the ABE mixed solution is a feed solution containing water, acetone, butanol and ethanol; preferably, the ABE feedstock is a fermentation broth comprising water, acetone, butanol and ethanol.
The results of comparing the freezing point, density and volumetric heat value of the annular high-performance aviation alternative fuel provided by the invention with other aviation fuels are shown in Table 1, wherein C15And C21The data for naphthenes were determined experimentally and the remaining parameters were obtained with reference to the Meylens, H.A et al article "efficiency conversion of pure and mixed depends on fuels to high reliability fuels" (Fuel,2012,97, 560-568).
TABLE 1
As can be seen from Table 1, the annular high-performance aviation alternative fuel provided by the invention has the freezing point of less than 123-3The above. In comparison with the properties of other fuels, in terms of freezing point, C15And C21The cycloparaffins meet the requirements of JP-5 and JP-10 for military aviation fuel; in terms of energy density, C15Cycloalkanes corresponding to JP-5, C21Cycloalkanes are equivalent to JP-10. In particular, among the high-performance aviation alternative fuels, C15The freezing point and energy density of the cycloalkane are satisfied by JP-5 for military aviation fuelRequiring; c21The freeze point and energy density of the cycloparaffins meet the requirements of JP-5 and JP-10 for military aviation fuels.
In order that the present disclosure may be more readily understood, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.
FIG. 1 shows the reaction path for the conversion of highly aqueous (12.1 wt%) ABE mixtures to branched cycloalkanes. The main reaction of the whole process comprises three steps: first, the ABE mixture is converted to methyl ketone (2-pentanone (2-C)5(＝O)) Or 2-heptanone (2-C)7(＝O)) ); in the second step, the methyl ketone obtained is subjected to a trimerization reaction [ dimerization reaction and Ronbinson annulation (Robinson cyclization reaction) ] in series]Formation of cyclic ketones (3a and 3 b); and thirdly, performing Hydrodeoxygenation (HDO) on the product obtained in the second step to obtain branched cycloparaffin. In the first step, except that 2-pentanone (2-C) is formed as the target product5(＝O)) And 2-heptanone (2-C)7(＝O)) In addition, 4-nonanone ((4-C) is a by-product9(＝O)) 6-undecenone (6-C)11(＝O)) 5-ethyl-4-undecanone (C)13(＝O)) 9-Ethyl-6-tridecanone (C)15(＝O)) 2-ethylhexanol (C)8(-OH)) Can likewise be produced by further bilateral alkylation reactions or Guerbet reactions (Guerbet reactions). In the second step, for example 2-heptanone, a dimerization product C of one molecule14-1a is formed from two molecules of 2-heptanone by aldol condensation; then C14Michael addition of-1 a to 2-heptanone to form C21-2 a; and finally C21-2a intramolecular aldol condensation to form a cyclic ketone C21-3a。
Therefore, the preparation method of the high-performance aviation alternative fuel according to the second aspect of the invention is a high-performance aviation alternative fuel prepared by using a feed liquid containing water, acetone, butanol and ethanol as a raw material and sequentially carrying out three steps of treatment, namely condensation reaction, trimerization condensation reaction and hydrodeoxygenation. According to some embodiments of the invention, the method of producing an aviation alternative fuel comprises:
step L, carrying out condensation reaction on the aqueous ABE mixed solution to prepare a liquid mixture with a main component of 2-heptanone or 2-pentanone;
step M, carrying out trimeric condensation reaction on the liquid mixture mainly containing 2-heptanone or 2-pentanone to obtain the liquid mixture mainly containing C15Or C21Mixtures of cyclic ketones of (a);
step N, the main component is C15Or C21The cyclic ketone mixture is subjected to hydrodeoxygenation treatment to prepare the high-performance aviation alternative fuel.
Wherein the main component of the high-performance aviation alternative fuel is C with branched chain15Or C21Wherein said branched C15Or C21The cyclic alkane of (A) comprises two isomers, and the specific structure is shown in figure I.
In the invention, the ABE raw material liquid is a mixed liquid containing water, acetone, ethanol and butanol, which can be a prepared feed liquid and also can be a fermentation liquid containing water, acetone, ethanol and butanol obtained by biomass fermentation; preferably, the ABE feedstock is a fermentation broth comprising water, acetone, ethanol and butanol.
In some embodiments of the invention, in the aqueous ABE mixture, based on the total weight of the aqueous ABE mixture, the water content is 9.8 wt% to 12.1 wt%, the acetone content is 32.4 wt% to 49.0 wt%, the butanol content is 0 wt% to 53.7 wt%, and the ethanol content is 2.2 wt% to 42.9 wt%; preferably, in the aqueous ABE mixture, based on the total weight of the aqueous ABE mixture, the water content is 12.1 wt%, the acetone content is 32.4 wt%, the butanol content is 53.4 wt%, and the ethanol content is 2.2 wt% or the water content is 12.1 wt%, the acetone content is 45.0 wt%, the butanol content is 0 wt%, and the ethanol content is 42.9 wt%.
In some embodiments of the invention, the method further comprises a step K, prior to step L, of fermenting the biomass to produce a fermentation broth comprising water, acetone, ethanol, and butanol. Wherein the biomass is non-grain biomass, including but not limited to corn stover and the like.
According to some embodiments of the invention, in step L, the condensation reaction is carried out in the presence of catalyst a in an amount of 10 wt% based on the total weight of the aqueous ABE mixture.
In the invention, the catalyst A is a solid-phase catalyst which is a Ni-MgO-SBA-16 catalyst.
In some embodiments of the invention, the molar ratio of Ni, MgO, and SBA-1 in the Ni-MgO-SBA-16 catalyst is (1.7-8.5):50:50, more preferably 4.26:50: 50. In some instances, for example, a Ni-MgO-SBA-16 catalyst of this composition may be represented as 4.26Ni-50MgO-50 SBA-16.
The catalyst provided by the invention has good catalytic activity and selectivity for ABE mixed liquor containing 12.1 wt% of water, namely good selectivity for a target product 2-pentanone or 2-heptanone, and after a condensation reaction occurs, the reaction liquid can automatically phase separate, so that a water phase can be easily removed, and the energy consumption cost of separation is greatly reduced. In addition, the reaction solution is subjected to simple distillation, so that the concentration of the target product in the reaction solution is higher, and the unreacted ABE can be recovered.
The reactor for the condensation reaction is not particularly limited, and in some embodiments of the present invention, for example, a tank reactor may be used for the condensation reaction. In some embodiments of the invention, the temperature of the condensation reaction is 240 ℃ and the time of the condensation reaction is 24 hours.
According to the process of the invention, in step M, the trimeric condensation reaction is carried out in the presence of a catalyst B and a solvent C.
In the invention, the catalyst B is a solid-phase catalyst and comprises MgAl-MMO catalyst and gamma-Al2O3Catalyst and MgO catalyst, wherein the MgAl-MMO catalyst refers to mixed oxide catalyst obtained after MgAl hydrotalcite is calcined, gamma-Al2O3The catalyst refers to gamma-phase nano Al2O3Catalyst powder, MgO catalyst refers to MgO powder catalyst, preferably the catalyst B is gamma-Al2O3A catalyst.
According to some embodiments of the present invention, the catalyst B is used in an amount of 10 wt% to 133 wt% based on the total weight of the liquid mixture of 2-pentanone or 2-heptanone, preferably the catalyst is used in an amount of 133 wt% based on the total weight of the liquid mixture of 2-pentanone or 2-heptanone.
According to further embodiments of the present invention, solvent C is an organic solvent comprising one or more of 2-heptanol, n-undecane, decalin, toluene and n-heptane, preferably said solvent C is n-heptane or toluene, the amount of solvent is 40 wt% to 1000 wt% based on the total weight of the liquid mixture of 2-pentanone or 2-heptanone, preferably the amount of solvent is 1000 wt% based on the total weight of the liquid mixture of 2-pentanone or 2-heptanone.
The reaction apparatus in the present invention is not particularly limited as long as the reaction requirements of the present invention can be satisfied, and for example, the reaction apparatus may be a tank reactor or a Dean-Stark apparatus.
In the present invention, anhydrous CaCl2Can be used as dehydrating agent to promote the trimeric condensation reaction, CaCl2The addition amount of (B) is 50 wt% -100 wt% based on the total mass of the catalyst. Anhydrous CaCl2Has a certain positive promoting effect on the reaction, but is not necessarily added, and does not participate in the trimerization condensation reaction.
The trimerization condensation reaction of the present invention may be carried out using a reactor conventional in the art, and in some embodiments of the present invention, the trimerization condensation reaction may be carried out using, for example, a Dean-Stark apparatus, at a reaction temperature of 160 ℃ to 180 ℃ for a reaction time of 6 hours. In other embodiments of the invention, a tank reactor may also be used, preferably at a reaction temperature of 180 ℃.
According to the process of the invention, in step N, the hydrodeoxygenation reaction is carried out in the presence of a catalyst D and of a solvent E.
In the invention, the catalyst D is a solid-phase catalyst Ni/MgSiO3Based on Ni/MgSiO in the catalyst3Based on the total moles of (A), the Ni/MgSiO3In the catalyst, the molar fraction of Ni was 10.8%.
In the present invention, the solvent E is cyclohexane.
In some embodiments of the invention, the amount of catalyst D is based on C15Or C21Based on the total weight of the cyclic ketone mixture (2), is 100 wt%.
In some embodiments of the invention, the amount of solvent E is based on C15Or C21The total weight of the cyclic ketone mixture (b) was 3250 wt%.
The hydrodeoxygenation reactor can be a kettle type reactor, and before reaction, the air in the reaction kettle can be exhausted by nitrogen, and H with the molar fraction of 99.9 percent and the pressure of 2.5Mpa is filled2The hydrodeoxygenation reaction time is 12 hours, and the hydrodeoxygenation reaction temperature is 180 ℃.
The high-performance aviation alternative fuel with high energy density and low freezing point is prepared by using a high-water-content ABE mixed liquid level raw material through a three-step catalytic process. The aviation alternative fuel is branched cycloparaffin with carbon number of 15 or 21. When the bio-based aviation alternative fuel is used as the main component of the aviation fuel, the consumption of petroleum-based aviation fuel can be greatly reduced while the aviation fuel standard is met.
The aviation alternative fuel prepared by the method has the following advantages:
(1) the method can produce the high-performance aviation alternative fuel by using feed liquid or fermentation liquid containing water, acetone and optional butanol and ethanol obtained by fermenting non-grain biomass as raw materials, and the ABE fermentation liquid has mature process and wide source and is beneficial to sustainable development of energy sources.
(2) The water content of the ABE mixed liquor used by the invention is high and reaches 12.1 wt%, so that the cost consumed by separating water in the ABE fermentation liquor is greatly reduced, and the large-scale production is favorably realized.
(3) In the process of preparing the high-performance aviation alternative fuel, Ni-MgO-SBA-16 catalyst is respectively adopted as a condensation reaction catalyst, and gamma-Al is adopted2O3Catalyst and/or MgAl-MMO catalyst as trimerization condensation catalyst, Ni/MgSiO3The catalyst is a hydrodeoxygenation catalyst, the high-selectivity preparation of the branched annular aviation alternative fuel with the carbon number range of 15 or 21 is realized, and the catalyst is good in stability and long in service life. And the final product has low freezing point, high energy density and even performanceIs equivalent to JP-5 and JP-10 of military aviation fuel.
(4) The process flow is simple to operate, the 2-pentanone or 2-heptanone can be selectively prepared in the step L, the product can be automatically subjected to oil-water separation, and the energy consumption required by the whole process flow is further reduced.
(5) The catalysts used in the steps of the method are non-noble metal catalysts, so that the method is energy-saving and environment-friendly and meets the environment-friendly standard.
In conclusion, the method has the advantages of simple production process, high product performance, wide raw material source and low production cost, and has the potential of realizing large-scale production.
Examples
In order that the present invention may be more readily understood, the following detailed description of the present invention is given by way of example only, and is not intended to limit the scope of the present invention.
In the invention, the volume heat value is measured by an XRY1 type oxygen bomb calorimeter (Shanghai Shuo photoelectron technology Co., Ltd.) by adopting a standard bomb calorimeter method (refer to the national standard GB/T30991-; the density was measured by a densitometer of BSY-110 type (shanghai sinno instruments ltd) using a pycnometer method [ refer to the national standard GB/T2540, petroleum products densitometry (pycnometer method) ]; the freezing point is measured by a DSC 214 type Polyma differential scanning calorimeter (German Schrad group) by differential scanning calorimetry (reference standard ASTM E794-2001, test methods for melting point temperature and crystallization temperature for thermal analysis).
The reaction liquid of the invention is quantitatively tested by gas chromatography, and an internal standard method is adopted for calculation, and the internal standard substance is n-dodecane. The conversion of the reactants and the selectivity or yield of the corresponding target products in the following examples were calculated as shown in the formulas (I) to (VI), respectively.
Step L:
conversion of ABE [ [ (P)ABE1-PABE2)/PABE1]×100％ (Ⅰ)
In formula (I):
PABE1: the total mole number of ABE carbon in the ABE raw material solution;
PABE2: total moles of unreacted ABE carbon in the liquid mixture after reaction.
Selectivity of 2-pentanone or 2-heptanone ═ PKetone 1/(PABE1-PABE2)]×100％； (Ⅱ)
In formula (II):
Pketone 1: the total moles of 2-pentanone or 2-heptanone in the 2-pentanone or 2-heptanone liquid mixture;
PABE1: the total mole number of ABE carbon in the ABE raw material solution;
PABE2: total moles of unreacted ABE carbon in the liquid mixture after the condensation reaction.
Step M:
conversion of 2-pentanone or 2-heptanone ═ PKetone 1-PKetone 2)/PKetone 1]×100％； (Ⅲ)
In the formula (III):
Pketone 1: the moles of 2-pentanone or 2-heptanone in the 2-pentanone or 2-heptanone liquid mixture;
Pketone 2: moles of unreacted 2-pentanone or 2-heptanone after trimeric condensation reaction.
C15Or C21Yield of cyclic ketones of (1) ([ P ]Cyclic ketones 1/PKetone 1× coefficient of stoichiometry]×100％； (Ⅳ)
In the formula (III):
Pcyclic ketones 1: c in trimeric condensation products15Or C21The total molar number of cyclic ketones of (a);
Pketone 1: moles of 2-pentanone or 2-heptanone in the 2-pentanone or 2-heptanone liquid mixture.
And step N:
C15or C21The conversion of cyclic ketones of (2) [ (P)Cyclic ketones 1-PCyclic ketones 2)/PCyclic ketones 1]×100％； (Ⅴ)
In formula (V):
Pcyclic ketones 1: c in trimeric condensation products15Or C21Total number of moles of cyclic ketones
PCyclic ketones 2: c in hydrodeoxygenation product15Or C21Total number of moles of cyclic ketones
C15Or C21Yield of cycloalkane of (1) [ (P)Cycloalkanes)/PCyclic ketones 1]×100％； (Ⅵ)
In formula (VI):
Pcycloalkanes: c in hydrodeoxygenation product15Or C21The total number of moles of cycloalkanes;
Pcyclic ketones 1: c in trimeric condensation products15Or C21Total number of moles of cyclic ketones (a).
Example 1:
(1) 10g of a mixed solution of ABE (molar ratio, acetone: butanol: ethanol ═ 7.9:9.9:0.8) having a water content of 12.1 wt% was placed in an 80mL tank reactor, and subjected to condensation reaction at 240 ℃ for 24 hours in the presence of 1g of a solid catalyst composed of 4.26Ni-50MgO-50SBA-16, followed by solid-liquid separation to obtain a liquid mixture containing 2-heptanone as a main component. The detection and calculation result shows that the conversion rate of ABE is 55.0%, the selectivity of 2-heptanone is 62.8%, and the selectivity of 2-pentanone is 5.2%.
(2) After the unreacted ABE was removed by simple distillation of the 2-heptanone liquid mixture, the 2-heptanone content in the mixed liquid was 76.8% by weight. 2g of the distilled 2-heptanone liquid mixture was placed in an 80mL tank reactor in 2g of γ -Al2O3Catalyst, 1g anhydrous CaCl2Dehydrating agent, 20g of n-heptane solvent, trimerization condensation reaction at 180 deg.C for 6h, and solid-liquid separation to obtain C as main component21Mixtures of cyclic ketones of (a). The conversion rate of the 2-heptanone is 92.3 percent through detection and calculation, and C21The total yield of cyclic ketones of (4) was 87.2%.
(3) 0.4g C21The cyclic ketone mixed solution is put into an 80mL kettle reactor, and then the mixed solution is added into a reactor containing 0.4g of Ni and Ni/MgSiO with the mole fraction of 10.8 percent3Catalyst of (2)In the presence of 8g of cyclohexane solvent, carrying out hydrodeoxygenation reaction for 12 hours at 180 ℃ in the atmosphere of pure hydrogen pressure of 2.5MPa to obtain high-performance aviation alternative fuel (C with branched chain)21Cycloalkane of (a). Through detection and calculation, C21Conversion of cyclic ketones of (2) is 100%, C21The total yield of cycloalkanes (C) was 99.0%.
Example 2:
this example is different from example 1 in that the proportion of ABE in the ABE mixture solution having a water content of 12.1 wt% used in the condensation reaction in step (1) was acetone/butanol/ethanol (molar ratio) of 7.1:0:8.5 [ that is, butanol/acetone/ethanol (molar ratio) of 0:7.1:8.5 ], and the reaction conditions were the same as in example 1. According to detection and calculation, the conversion rate of ABE is 60.8%, the selectivity of 2-pentanone is 60.8%, and the selectivity of 2-heptanone is 4.5%. After simple distillation, 89.3 wt% of 2-pentanone mixed solution is obtained.
The reaction solution of the trimerization condensation reaction of the step (2) was 89.3 wt% of 2-pentanone, and the remaining reaction conditions were the same as in example 1. Through detection and calculation, the conversion rate of 2-pentanone is 91.7 percent, and C is15The total yield of cyclic ketones (2) was 85.0%.
The reaction liquid of the hydrodeoxygenation reaction in the step (3) is C15The reaction conditions of the cyclic ketone mixture (2) were the same as in example 1. Through detection and calculation, C15Conversion of cyclic ketones of (2) is 100%, C15The total yield of cycloalkanes (C) was 98.9%.
Example 3:
this example is different from example 1 in that, in the trimerization condensation reaction in the step (2), the reaction solution was a commercially available analytically pure 2-heptanone solution, the mass of the reaction solution was 10g, the solvent was toluene, the mass of the solvent was 4g, the catalyst was MgAl-MMO, the mass was 1g, the reaction apparatus was a Dean-Stark apparatus, the reaction temperature was 160 ℃, and the remaining reaction conditions were the same as in example 1. The conversion rate of the 2-heptanone is 99.2 percent through detection and calculation, and C21The total yield of cyclic ketones of (3) was 96.2%.
Example 4:
this embodiment andexample 1 is different in that, in the trimerization condensation reaction in the step (2), the reaction solution was a commercially available analytically pure 2-heptanone solution, the mass of the reaction solution was 10g, the mass of the solvent was 4g, the mass of the catalyst was MgAl-MMO was 1g, the reaction apparatus was a Dean-Stark apparatus, the reaction temperature was 160 ℃, and the other reaction conditions were the same as in example 1. The conversion rate of the 2-heptanone is 98.1 percent through detection and calculation, and C21The total yield of cyclic ketones of (4) was 95.1%.
Example 5:
this example is different from example 1 in that, in the trimerization condensation reaction in the step (2), the reaction solution was a commercially available analytically pure 2-heptanone solution, the mass of the reaction solution was 1.5g, the catalyst was MgAl-MMO, and the other reaction conditions were the same as in example 1. The conversion rate of the 2-heptanone is 97.3 percent through detection and calculation, and C21The total yield of cyclic ketones (2) was 94.6%.
Example 6:
this example is different from example 1 in that, in the trimerization condensation reaction in the step (2), the reaction solution was a commercially available analytically pure 2-heptanone solution, the mass of the reaction solution was 1.5g, the catalyst was MgAl-MMO, the reaction temperature was 160 ℃ and the other reaction conditions were the same as in example 1. The conversion rate of the 2-heptanone is 91.7 percent through detection and calculation, and C21The total yield of cyclic ketones of (4) was 89.1%.
Example 7:
this example is different from example 1 in that, in the trimerization condensation reaction in the step (2), the reaction solution was a commercially available analytically pure 2-heptanone solution, the mass of the reaction solution was 1.5g, the catalyst was MgAl-MMO, the reaction temperature was 160 ℃ and anhydrous CaCl without a dehydrating agent was added2The remaining reaction conditions were the same as in example 1. The conversion rate of the 2-heptanone is 86.2 percent through detection and calculation, and C21The total yield of cyclic ketones of (3) was 81.4%.
For the above embodiment C21Cycloalkane of (2)15The cycloparaffin is detected, and the result shows that the invention C21The volume calorific value of the cycloalkane is 143btu/gal/103The density is 0.91g/mL, and the freezing point is less than 123K; c15The volume calorific value of the cycloalkane is 126btu/gal/103The density is 0.89g/mL, and the freezing point is 183K.
As can be seen from the above examples, the process of the present invention for converting aqueous ABE mixtures into high performance aviation alternative fuels is accomplished by a well-defined three-step series reaction. The method has many advantages, such as high catalytic efficiency, simple process and environmental protection, and is a novel process for preparing the bio-based high-performance aviation alternative fuel.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A high-performance aviation alternative fuel is prepared based on aqueous ABE mixed liquid, and comprises branched C as main component21Or C15Cycloalkane of (a); wherein the ABE mixed solution is a feed solution containing water, acetone, butanol and ethanol; preferably, the ABE feedstock is a fermentation broth comprising water, acetone, butanol and ethanol.
2. The high-performance aviation alternative fuel as claimed in claim 1, wherein the high-performance aviation alternative fuel has a freezing point of < 123- > 183K, a density of 0.89-0.91g/mL or more, and a volumetric heat value of 126- > 143btu/gal/103The above; preferably, among said high performance aviation alternative fuels, C15The freezing point and the energy density of the cyclane meet the requirements of JP-5 for military aviation alternative fuel, C21The freezing point and energy density of the cyclanes meet the requirements of JP-5 and JP-10 for military aviation alternative fuelsAnd (6) obtaining.
3. A method of producing an aviation alternative fuel as claimed in claim 1 or claim 2, which comprises:
step L, carrying out condensation reaction on the aqueous ABE mixed solution to prepare a liquid mixture with a main component of 2-heptanone or 2-pentanone;
step M, carrying out trimeric condensation reaction on the liquid mixture mainly containing 2-heptanone or 2-pentanone to obtain the liquid mixture mainly containing C15Or C21Mixtures of cyclic ketones of (a);
step N, the main component is C15Or C21The cyclic ketone mixture is subjected to hydrodeoxygenation treatment to prepare high-performance aviation alternative fuel;
wherein the main component of the high-performance aviation alternative fuel is C with branched chain15Or C21Cycloalkane of (a); the ABE mixed solution is a feed liquid containing water, acetone, butanol and ethanol; preferably, the ABE feedstock is a fermentation broth comprising water, acetone, butanol and ethanol.
4. The method according to claim 3, wherein the ABE feed solution contains 9.8 wt% to 12.1 wt% of water, 32.4 wt% to 49.0 wt% of acetone, 0 wt% to 53.7 wt% of butanol, and 2.2 wt% to 42.9 wt% of ethanol, based on the total weight of the ABE feed solution.
5. The process according to claim 3 or 4, wherein, in step L, the condensation reaction is carried out in the presence of a catalyst A which is a Ni-MgO-SBA-16 catalyst; preferably, the molar ratio of Ni, MgO and SBA-1 in the Ni-MgO-SBA-16 catalyst is (1.7-8.5) 50:50, more preferably 4.26:50: 50; further preferably, the catalyst a is used in an amount of 10 wt% based on the total weight of the ABE feedstock solution.
6. The method according to any one of claims 3 to 5, wherein, in the step M, the stepThe trimerization condensation reaction is carried out in the presence of a catalyst B and a solvent C, wherein the catalyst B comprises MgAl-MMO catalyst and gamma-Al2O3One or more of a catalyst and a MgO catalyst; preferably, the catalyst B is used in an amount of 10 wt% to 133 wt%, based on the total weight of the liquid mixture of 2-heptanone or 2-pentanone; and/or the solvent C comprises one or more of 2-heptanol, n-undecane, decalin, toluene and n-heptane, preferably the solvent C is n-heptane or toluene; preferably, the solvent C is used in an amount of 40 wt% to 1000 wt%, based on the total weight of the liquid mixture of 2-heptanone or 2-pentanone.
7. The process according to claim 6, wherein in step M, the trimeric condensation reaction is also carried out in the presence of a dehydrating agent, which is anhydrous CaCl2(ii) a Preferably, the dehydrating agent is used in an amount of 50 wt% to 100 wt% based on the total mass of the catalyst.
8. The method according to any one of claims 3 to 7, wherein in step N, the hydrodeoxygenation reaction is carried out in the presence of a catalyst D and a solvent E, wherein the catalyst D is Ni/MgSiO3(ii) a Preferably based on Ni/MgSiO in the catalyst3Based on the total moles of (A), the Ni/MgSiO3The mole fraction of Ni in the catalyst is 10.8%; further preferably, the catalyst D is used in an amount based on C15Or C21Based on the total weight of the cyclic ketone mixture (2), is 100 wt%.
9. The method according to claim 8, wherein the solvent E is cyclohexane; preferably, the solvent E is used in an amount based on C15Or C21The total weight of the cyclic ketone mixture (b) was 3250 wt%.
10. The production method according to any one of claims 3 to 9,
in the step L, the temperature of the condensation reaction is 240 ℃, and the time of the condensation reaction is 24 hours;
and/or, in the step M, the trimerization condensation reaction temperature is 160-180 ℃, and the trimerization condensation reaction time is 6 h;
and/or, in the step N, the hydrodeoxygenation reaction is carried out under the pure hydrogen atmosphere pressure of 2.5 Mpa; preferably, the hydrodeoxygenation reaction temperature is 180 ℃, and the hydrodeoxygenation reaction time is 12 h.
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