CN105754633A - Method for producing biological aviation kerosene from biomass - Google Patents
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Abstract
The invention relates to a method for producing biological aviation kerosene by taking biomass as a raw material. According to the method, a middle fraction, having a distillation range of 130-290 DEC, of Fischer-Tropsch synthesized wax is mixed with grease to form a raw material, which reacts with hydrogen to produce a liquid hydrocarbon product, water, and a gas product. According to the method, Fischer-Tropsch synthesized wax is converted from synthesized gas produced from vaporization of biomass, and the liquid hydrocarbon product mainly is isoparaffin. In the method, biomass is taken as a raw material for producing isoparaffin, which has characteristics of high energy density, good stability, and low freezing point, and can be used as biological aviation kerosene. In the method, Fischer-Tropsch synthesized wax is mixed with grease for feeding, thereby decreasing heat release of a hydrogenation reaction of grease and reducing the reaction heat effect on a catalyst, so that the raw material can be stably converted into biological aviation kerosene.
Description
Technical field
The present invention relates to the conversion process of biomass, more particularly to the process with biomass for raw material production hydrocarbon compound.The hydro carbons produced in the present invention is mainly isoparaffin, has the feature of high-energy-density, high stability and low freezing point, can use as biological aerial kerosene.
Background technology
Along with economic, social development, the minimizing day by day of the disposable energy such as oil and coal, the price bringing energy scarcity problem, crude oil and coal constantly rises in recent years, and the price of automotive fuel is also caused impact by this.Additionally, due to oil and coal broadly fall into containing carbon resource and containing the element such as nitrogen, sulfur, the inevitable toxic gas producing carbon dioxide and environment being had harm in its conversion and products thereof use procedure.Based on this, simultaneously also for politics and economic factor, some countries have put into effect relevant policy for the restriction that utilizes of fossil energy product.Such as, European Union once released carbon tax in the early 1990s and imposed policy, was proposed again aviation carbon tax in 2008 and imposes bill.Factors above promotes researcher to be sought for the novel energy of alternative fossil energy.Biomass energy is the unique carbon containing regenerative resource of nature, and it utilizes the carbon dioxide produced in process can pass through the photosynthesis consumption of plant, and environment is impacted hardly.From this angle, develop from the production technology of the liquid fuels such as biomass biodiesel, biological aerial kerosene protecting environment, adapting to current energy consumption structure and safeguard that national energy security is significant.
The biomass containing fatty glyceride, fatty acid ester and fatty acid such as animal and plant fat are directly over hydrogenation, deoxidation can be converted into hydrocarbon compound.Fatty acid carbon chain carbon number contained by animal and plant fat is 12-24 (wherein in the majority with 16 and 18), it is after hydrogenation, deoxidation convert completely, mainly generate the alkane that carbochain carbon number is 11-24, owing to its carbochain is similar with the carbochain that petrochemical industry boat coal, diesel oil hydro carbons have, it is possible to use as biodiesel or aerial kerosene.
Above-mentioned biodiesel or aerial kerosene group to consist of isoparaffin.At present its preparation process relies primarily on two-step method and realizes, and the first step of two-step process is that oils and fats is hydrogenated, deoxidation produces n-alkane, water and some other by-product；The n-alkane that second step is after isolation of purified produces isoparaffin and short-chain branch alkane by hygrogenating isomerization reaction or cracking reaction.Concretely comprise the following steps: the first step, hydrogenation reaction is there is in animal and plant fat in hydrogenation reactor, make the carbon-carbon double bond in oils and fats be able to saturated, oxygen to be removed, thus being converted into long-chain normal paraffin and by-product propane, water, carbon dioxide, carbon monoxide etc., the technique that patent US20080308457, US5705722, US20060186020, WO2006075057 etc. disclose this process；Second step, hysomer/cracking reaction is there is in the long-chain normal paraffin after separated purification in isomerization reactor, thus producing the isoparaffin obtaining low condensation point, the technique that patent WO2010028717, WO2009156452, WO2008113492, US2010000908 etc. disclose this process.
Owing to two-step method process is that multistep is integrated, oil hydrogenation, deoxidation process and alkane isomerization process carry out respectively in different reactor and different catalysts, therefore, whole process needs multiple reactors, many more manipulations operation, complex process, hydrogen consumption and energy consumption are high, and the investment of the equipment of production is big.If making the process that the raw materials such as animal and plant fat are converted into low condensation point isoparaffin only realize through single step reaction, just can reduce operation sequence, reducing hydrogen consumption and energy consumption.And want to make animal and plant fat be converted into isoparaffin through single step reaction, it is necessary to make the hydrogenation of unsaturated double-bond in oils and fats, the deoxidation of ester group and the alkane isomerization reaction can in fixed bed reactors, one section of catalyst carries out simultaneously.
And each reaction involved from oil hydrogenation conversion process to carry out thermodynamic analysis results known, for soybean oil, soybean oil generates the total enthalpy change of isoparaffin and is respectively as follows :-1562kJ/mol (hydrogenation deoxidation mode) ,-1150kJ/mol (hydrogenation decarbonylation mode) and-1247kJ/mol (hydrogenation decarboxylation mode), for strong exothermal reaction.When reaction occurs, if heat can not be pulled away in time, it would be possible to make the active metal component on the load type metal catalyst used by oils and fats one step Hydrogenation isoparaffin sinter.If using hydrocarbon raw material as the co-fed oils and fats that dilutes, reducing oil hydrogenation exothermic heat of reaction amount, and making heat of reaction immediately be pulled away, thus alleviating the heat effect impact on catalyst, making process stabilization produce isoparaffin.
Fischer Tropsch waxes is that synthesis gas (carbon monoxide and hydrogen) reacts, through F-T synthesis (Fischer-TropschSynthesis is called for short FT synthesis), the hydro carbons that the molecular weight distribution generated is very wide on transition metal (such as cobalt-based, iron-based etc.) catalyst.Wherein, the synthesis gas as raw material can be converted by the fossil energy such as coal, natural gas and obtain, and also can be vaporized by biomass and obtain.Fischer Tropsch waxes mainly comprise as n-alkane, its light ends octane number is low, it is impossible to use as gasoline；Its midbarrel (boiling range is 130-290 DEG C) freezing point is high, it is impossible to use as aerial kerosene.Accordingly, it would be desirable to it is carried out upgrading by isomerization reaction, n-alkane is made to be converted into isoparaffin.
Summary of the invention
The present invention provides a kind of process being produced biological aerial kerosene by biomass.
The present invention is achieved by the following technical solutions:
In fixed bed reactors, in Fischer Tropsch waxes midbarrel, boiling range is fraction and the oils and fats mixing of 130-290 DEG C, react with hydrogen generation hydrogenation catalyst under the effect of catalyst, product includes liquid hydrocarbon component, gas component and water, described liquid hydrocarbon component is mainly isoparaffin, separates gaseous product and product liquid, removes the water in product liquid, remove the boiling point fraction less than 130 DEG C and the fraction more than 290 DEG C through distillation, obtain target product biology aerial kerosene.
Described process, wherein, the Fischer Tropsch waxes in raw material is the n-alkane that synthesis gas (carbon monoxide and hydrogen) generates through Fischer-Tropsch synthesis.
Described process, wherein, the Fischer Tropsch waxes midbarrel in raw material is that in the n-alkane that Fischer-Tropsch synthesis generates, boiling range is the fraction of 130-290 DEG C.
Described process, wherein, the oils and fats in raw material is one or two or more kinds in fatty acid, derivative of fatty acid, triglyceride, diglyceride, monoglyceride, phospholipid, fatty acid ester.
Described process, wherein, in raw material, Fischer Tropsch waxes midbarrel is 1:10 to 100:1 with the volume ratio of oils and fats.It is preferably 1:1 to 10:1.The synthesis gas that described Fischer Tropsch waxes is generated by biomass vaporization prepares through Fischer-Tropsch synthesis.
Described process, wherein, oil hydrogenation, deoxidation and alkane isomerization, cracking are had catalysis activity by described catalyst simultaneously.
Described process, wherein, described catalyst is with a kind of in Si-Al molecular sieve, aluminium silicophosphate molecular sieve or hetero-atom molecular-sieve or two kinds or three kinds for one or two or more kinds in the load type metal catalyst of carrier.Such as Pt/SAPO-5, Pt/SAPO-11, Pt/SAPO-31, Pt/SAPO-41, Pt//ZSM-5, Pt/ZSM-22, Pt/ZSM-23 etc..
Described process, wherein, product liquid and gaseous product separate in knockout drum.
Described process, wherein, product liquid includes liquid hydrocarbon product and water.
Described process, wherein, the process removing the water in product liquid is that liquid hydrocarbon product separates through separatory with water.
Described process, wherein, adopts air-distillation to isolate the liquid hydrocarbon product mid-boiling point fraction less than 130 DEG C, then the boiling point fraction more than 130 DEG C is carried out decompression distillation, obtains the hydrocarbon product that boiling range is 130-290 DEG C, i.e. target product biology aerial kerosene.
Described hydrogenation catalyst reaction carries out in one or more fixed bed reactors；The temperature of described hydrogenation catalyst reaction is 250-450 DEG C, it is preferable that reaction temperature is 280-400 DEG C；Pressure is 1000-15000kPa, it is preferable that reaction pressure is 1000-12000kPa；Liquid hourly space velocity (LHSV) (in the unit interval ratio of feedstock volume and the catalyst volume of filling) is 0.1-5h-1, it is preferred to 0.2-2h-1；The volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 300-5000NL/NL, it is preferred to 300-3000NL/NL.
Final products obtained therefrom boiling point is between 130-290 DEG C, and freezing point is not higher than-40 DEG C
Ebulliometry method is GB/T616-2006, and kryoscopy method is that petroleum products questionable points bioassay standard method GB/T510 surveys method.
Described process, wherein, the hydrogenation reaction from oils and fats to biological aerial kerosene mainly experiences following reaction: oils and fats occurs hydrogenation saturated reaction to generate saturated fatty acid glyceride；Generating carbon number after saturated fat acid glyceride generation deoxygenation is the linear paraffin of 11 to 24；Linear paraffin generation isomerization is largely converted into isoparaffin, and has partial hydrogenation cracking.
Described process, wherein, from Fischer Tropsch waxes to biological aerial kerosene experience alkane isomerization and cracking reaction, makes the Fischer Tropsch waxes mainly comprised as n-alkane be converted into isoparaffin.
Described process, wherein, the hydrogenation of oils and fats, deoxidation and alkane isomerization, cracking simultaneously complete through a step hydrogenation reaction.
Described process, wherein, the product liquid that the hydrogenated reaction of oils and fats generates includes hydrocarbon mixture and water；Gaseous product includes CO, CO of generating through deoxygenation2And C3H8, through the CH that methanation reaction generates4CH with cracked reaction generation4、C2H6、C3H8And C4H10Deng.
Described process, wherein, liquid hydrocarbon product includes oil hydrogenation product and Fischer Tropsch waxes hydrogenation products.
Described process, wherein, the liquid hydrocarbon product that the hydrogenated reaction of oils and fats generates is mainly: the C11-C24 n-alkane that oil hydrogenation, deoxidation generate is after further isomerization and cracking reaction, the boiling range generated is at the C8-C16 isoparaffin of 130-290 DEG C, and the C11-C24 n-alkane of the short chain alkanes that generates of a small amount of cracked reaction and conversion further.
Described process, wherein, the liquid hydrocarbon product that Fischer Tropsch waxes hydrogenation reaction generates is mainly: the boiling range generated through isomerization reaction is at the C8-C16 isoparaffin of 130-290 DEG C, and the short chain alkanes that generates of a small amount of cracked reaction and unconverted boiling range are at the n-alkane of 130-290 DEG C.
Process involved in the present invention, by making Fischer Tropsch waxes and oils and fats mixed feeding, alleviates oil hydrogenation exothermic heat of reaction, reduces the reaction heat effect impact on catalyst, makes raw material can stably be converted into biological aerial kerosene.
Process involved in the present invention is by making Fischer Tropsch waxes and oils and fats mixed feeding, moreover it is possible to makes Fischer Tropsch waxes be further converted to isoparaffin, improves its cryogenic property.
In embodiment involved in the present invention, its target product is biological aerial kerosene.It is therefore preferred that the mainly comprising as boiling point fraction between 130-290 DEG C of product.In some currently preferred embodiments of the present invention, the yield of biological aerial kerosene is more than 50wt.% (calculating according to the weight * 100% of the weight/raw material of fraction between 130-290 DEG C generated)；Wherein, isoparaffin selectivity is more than 80wt.% (calculating according to the alkane gross weight * 100% of the weight/generation of the isoparaffin generated).The product liquid that this process generates GC (gas chromatogram) and/or GC-MS (gas chromatography-mass spectrography) analyzes.
In embodiment involved in the present invention, its target product is biological aerial kerosene.Therefore, its freezing point is not higher than-40 DEG C (RP-4 and JetA standards), or not higher than-47 DEG C (RP-3 and JetA-1 standards).
Oils and fats involved in the present invention is made up of one or several in vegetable oil, Animal fat and waste cooking oil.Wherein, vegetable oil includes one or several in Oleum Brassicae campestris, Oleum Arachidis hypogaeae semen, soybean oil, Semen Maydis oil, Rice oil, safflower oil, Petiolus Trachycarpi oil, curcas oil, Testa oryzae oil, Oleum Ricini, Oleum Cocois, tall oil, Fructus Canarii albi wet goods.Animal oil includes one or several in Adeps Sus domestica, Adeps Bovis seu Bubali, Adeps Caprae seu ovis, chicken oil, fish oil, whale oil etc..Oils and fats as raw material is not limited to polished fat, it is also possible to for the oils and fats of waste cooking oil He other course of processing by-products, the by-product high-load free fatty acid oils and fats that such as processing vegetable oil generates.
Oils and fats involved in the present invention can obtain from any suitable resource, it is preferable that from living resources, obtains in plant or animal.Such as, oils and fats can be made up of one or several in vegetable oil, Animal fat and waste cooking oil.Raw material can allow containing other non-oil components of trace.
Fischer Tropsch waxes involved in the present invention derives from biomass and converts.
The synthesis gas that Fischer Tropsch waxes involved in the present invention is generated by biomass vaporization prepares through Fischer-Tropsch synthesis.
Fischer Tropsch waxes involved in the present invention and oils and fats, on solid catalyst, react with hydrogen.
Catalytic reaction involved in this process can carry out at suitable temperature and pressure.The preferable reaction temperature of the present invention is 250-450 DEG C, such as 280-400 DEG C.The change of reaction temperature is relevant with the catalyst used, but all within described constant interval.
Catalytic reaction pressure involved in this process is 1000-15000kPa, such as 1000-8000kPa, such as 2000-12000kPa.
The volume of hydrogen of catalytic reaction involved in this process and the volume of Fischer Tropsch waxes midbarrel and oils and fats and ratio be 300-5000NL/NL, such as 300-3000NL/NL.
The LHSV (liquid hourly space velocity (LHSV), feedstock volume is divided by the catalyst volume of filling per hour) of the catalytic reaction involved by this process is 0.1-5.0h-1, such as 0.2-2h-1。
In the present invention, the design of the reactor in different embodiments can be different.In certain embodiments, reactor can be only made up of a fixed bed reactors unit；In further embodiments, reactor can be a reactor system, and this reactor system can be made up of multiple reactor units.
In an embodiment of the present invention, one or more catalyst can be loaded in a reactor or reactor unit；Different reactor or reactor unit can be loaded of the same race or multiple catalysts.
Therefore, in reactor system involved in the present invention, in one or more beds, it is possible to load different several catalyst.When reactor system contains multiple beds, identical or different catalyst can be seated in these beds in the way of appropriately combined.An involved step catalytic reaction is referred to following manner and carries out: in a reactor or a reactor unit, a step catalytic reaction occurs；Two or more reactor/reactor units occur a step catalytic reaction.In certain embodiments, an involved step catalytic reaction can carry out on the same catalyst；In further embodiments, an involved step catalytic reaction can carry out in the different catalysts combined with certain forms.
In an embodiment of the present invention, reaction condition such as temperature, pressure, air speed etc. is likely to change in hydrogenation catalyst course of reaction.In certain embodiments, the reaction condition of hydrogenation catalyst course of reaction is likely to always constant, is also likely to fixing routine change.Such as, temperature, pressure, air speed are always maintained at constant, or temperature, pressure, air speed are with fixing routine change.
Method provided by the present invention, product composition and/or device flow process are listed in the accompanying drawing of this patent.
Some features in the idiographic flow of the present invention and preferred embodiment display with the form of the following drawings:
Device flow process in figure includes A, B, five primary operational unit of C, D and E.It is pointed out that each operating unit in actual production process is likely to be made up of multiple devices, it is not limited to single or single reactor/separator.Operating unit A is the fixed bed reactors of loading catalyst, raw material (includes 1 oils and fats and 2 Fischer Tropsch waxes midbarrels) and 3 hydrogen (include from reaction end gas processor E recycle hydrogen) are loaded into reactor A together, and be hydrogenated with on a catalyst simultaneously, deoxidation and hygrogenating isomerization reaction.The product 4 generated mainly contains isoparaffin, n-alkane, water, propane, carbon monoxide, carbon dioxide etc..Product is flowed into oil water separator B from reactor A, and 6 gases therein (include hydrogen and the gas of 10 carbon less than 4), 5 liquid hydrocarbon products and 7 water are separated in B.Liquid hydrocarbon product moves to and makes 8 light components (less than 130 DEG C of fractions) separate in atmospheric distillation plant C, remaining in 9 liquid hydrocarbon products entrance vacuum distillation apparatus D makes 11 aerial kerosene components (130-290 DEG C of fraction) and 12 heavy constituents (more than 290 DEG C of fractions) be separated, and obtains biological aerial kerosene product (130-290 DEG C of fraction).
Process from oils and fats biology aerial kerosene provided by the invention has the advantage that
1. the hydrogenation of oils and fats, deoxidation and alkane isomerization can realize simultaneously；
2., compared to existing oils and fats two step hydrogenation method technique, which simplify flow process, and reduce hydrogen consumption and energy consumption；
3., compared to existing oils and fats two step hydrogenation method technique, it reduces in the equipment of production and operational expense；
4. Fischer Tropsch waxes is as common raw material, dilutes the content of oils and fats in raw material, decreases the heat release because oil hydrogenation reaction produces, and makes heat of reaction be diluted material in time to take away, make catalyst stability strengthen；The Fischer Tropsch waxes simultaneously deriving from biomass also can occur isomerization reaction to be further converted to isoparaffin, i.e. biological aerial kerosene, and then makes whole process can produce biological aerial kerosene steadily in the long term.
5. the biological aerial kerosene produced has the advantages such as energy density height, stability height and freezing point are low；
6. provide a new way preparing alternative energy source from biomass.
Accompanying drawing explanation
Fig. 1 device flow chart.
Wherein A is the fixed bed reactors of loading catalyst, B is oil water separator, C atmospheric distillation plant is, D is vacuum distillation apparatus, E is reaction end gas processor, 1 is oils and fats, 2 is Fischer Tropsch waxes midbarrel, 3 is hydrogen (including the hydrogen recycled from reaction end gas processor E), 4 is product, 5 is the liquid hydrocarbon product in product, 6 is the gas in product, 7 is the water in product, 8 is the light component in liquid hydrocarbon product in product (less than 130 DEG C of fractions), 9 liquid hydrocarbon products remove the remaining ingredient less than 130 DEG C of fractions, 10 is the gas of the carbon less than 4 in product in gas, 11 is aerial kerosene component (130-290 DEG C of fraction), 12 heavy constituents (more than 290 DEG C of fractions).
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated, it is to be noted that present invention is not limited thereto.Embodiment all carries out in Fig. 1 shown device.
Embodiment 1
The volume ratio of soybean oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 2:1, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 370 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 5.4wt.%, and in liquid product, the ratio of organic facies is 94.6wt.%, and in organic facies, isoparaffin content is 88.5wt.%, and normal paraffin content is 11.5wt.%.Light component (fractions less than 130 DEG C) yield is 4.7wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 51.7wt.%.Biological aerial kerosene freezing point is-47 DEG C.Reaction result is listed in table 1.
Embodiment 2
The volume ratio of soybean oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:1, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 370 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 3.8wt.%, and in liquid product, the ratio of organic facies is 96.2wt.%, and in organic facies, isoparaffin content is 89.2wt.%, and normal paraffin content is 10.8wt.%.Light component (fractions less than 130 DEG C) yield is 4.9wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 58.6wt.%.Biological aerial kerosene freezing point is-48 DEG C.Reaction result is listed in table 1.
Embodiment 3
The volume ratio of soybean oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:2, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 370 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 2.7wt.%, and in liquid product, the ratio of organic facies is 97.3wt.%, and in organic facies, isoparaffin content is 89.8wt.%, and normal paraffin content is 10.2wt.%.Light component (fractions less than 130 DEG C) yield is 5.1wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 70.2wt.%.Biological aerial kerosene freezing point is-49 DEG C.Reaction result is listed in table 1.
Embodiment 4
The volume ratio of soybean oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:3, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 370 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 2.1wt.%, and in liquid product, the ratio of organic facies is 97.9wt.%, and in organic facies, isoparaffin content is 90.0wt.%, and normal paraffin content is 10.0wt.%.Light component (fractions less than 130 DEG C) yield is 5.2wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 76.9wt.%.Biological aerial kerosene freezing point is-49 DEG C.Reaction result is listed in table 1.
Embodiment 5
The volume ratio of soybean oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:4, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 380 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 1.7wt.%, and in liquid product, the ratio of organic facies is 98.3wt.%, and in organic facies, isoparaffin content is 90.9wt.%, and normal paraffin content is 9.1wt.%.Light component (fractions less than 130 DEG C) yield is 5.6wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 79.7wt.%.Biological aerial kerosene freezing point is-51 DEG C.Reaction result is listed in table 1.
Embodiment 6
The volume ratio of soybean oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:9, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 380 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 1.0wt.%, and in liquid product, the ratio of organic facies is 98.3wt.%, and in organic facies, isoparaffin content is 91.5wt.%, and normal paraffin content is 8.5wt.%.Light component (fractions less than 130 DEG C) yield is 6.2wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 86.5wt.%.Biological aerial kerosene freezing point is-52 DEG C.Reaction result is listed in table 1.
Embodiment 7
The volume ratio of Testa oryzae oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:9, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 360 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 1.1wt.%, and in liquid product, the ratio of organic facies is 98.3wt.%, and in organic facies, isoparaffin content is 86.2wt.%, and normal paraffin content is 13.8wt.%.Light component (fractions less than 130 DEG C) yield is 3.4wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 89.7wt.%.Biological aerial kerosene freezing point is-45 DEG C.Reaction result is listed in table 1.
Embodiment 8
The volume ratio of Testa oryzae oil and Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) is 1:3, and both are made into raw material by mix homogeneously.Weighing the Pt/SAPO-11 catalyst (100mL, granular size is 10-20 order) that 90gPt loading is 1wt.%, be loaded on internal diameter to be 25mm, pipe range be in the rustless steel fixed bed reactors of 1.5m, reactor two ends 20-40 order quartz sand is filled.Reaction condition is: 360 DEG C, 6.0MPa, and LHSV is 1h-1, the volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 3000NL/NL.Sampling after reaction 24h.Liquid hydrocarbon product separates through separatory with water, and liquid hydrocarbon product is carried out air-distillation, makes light component (fractions less than 130 DEG C) separate, obtains the fraction more than 130 DEG C；Carry out decompression distillation again, make heavy constituent (fractions more than 290 DEG C) separate, obtain biological aerial kerosene product (130-290 DEG C of fraction).Liquid hydrocarbon product GC, GC-MS analyze, and adopt automatic freezing point analyzer to analyze biological aerial kerosene product freezing point.
Reaction result in table 1. embodiment
Reaction result is: soybean oil conversion ratio is 100%, and in liquid product, the ratio of water is 2.3wt.%, and in liquid product, the ratio of organic facies is 97.7wt.%, and in organic facies, isoparaffin content is 84.5wt.%, and normal paraffin content is 15.5wt.%.Light component (fractions less than 130 DEG C) yield is 3.1wt.%, and biological aerial kerosene (130-290 DEG C of fraction) yield is 78.4wt.%.Biological aerial kerosene freezing point is-45 DEG C.Reaction result is listed in table 1.
Claims (10)
1. the method being produced biological aerial kerosene by biomass, it is characterised in that: comprise the following steps:
In fixed bed reactors, Fischer Tropsch waxes midbarrel (boiling range is 130-290 DEG C) and oils and fats mixing, react with hydrogen generation hydrogenation catalyst under the effect of catalyst, separate gaseous product and product liquid, removing the water in product liquid, in gained product liquid, boiling range is the hydrocarbon product of 130-290 DEG C is target product biology aerial kerosene.
2. the method for claim 1, it is characterised in that: in described raw material, the volume ratio of Fischer Tropsch waxes midbarrel and oils and fats is 1:10 to 100:1, it is preferable that volume ratio is 1:1 to 10:1.
3. the method for claim 1, it is characterised in that: described hydrogenation catalyst reaction carries out in one or more fixed bed reactors；The temperature of described hydrogenation catalyst reaction is 250-450 DEG C, it is preferable that reaction temperature is 280-400 DEG C；Pressure is 1000-15000kPa, it is preferable that reaction pressure is 1000-12000kPa；Liquid hourly space velocity (LHSV) (in the unit interval ratio of feedstock volume and the catalyst volume of filling) is 0.1-5h-1, it is preferred to 0.2-2h-1；The volume of the volume of hydrogen and Fischer Tropsch waxes midbarrel and oils and fats and ratio be 300-5000NL/NL, it is preferred to 300-3000NL/NL.
4. the method for claim 1, it is characterised in that: oil hydrogenation, deoxidation and alkane isomerization, cracking are had catalysis activity by described catalyst simultaneously.
5. the method as described in claim 1 or 4, it is characterised in that: described catalyst is with a kind of in Si-Al molecular sieve, aluminium silicophosphate molecular sieve or hetero-atom molecular-sieve or two kinds or three kinds for one or two or more kinds in the load type metal catalyst of carrier.
6. the method for claim 1, it is characterized in that: described oils and fats is one or two or more kinds in vegetable oil, Animal fat or waste cooking oil, synthesis gas boiling range in the n-alkane that Fischer-Tropsch synthesis generates that described Fischer Tropsch waxes is generated by biomass vaporization is the fraction of 130-290 DEG C.
7. the method as described in claim 1 or 6, it is characterised in that: described oils and fats is one or two or more kinds in fatty acid, derivative of fatty acid, triglyceride, diglyceride, monoglyceride, phospholipid, fatty acid ester.
8. the method for claim 1, it is characterised in that: described separation gaseous product and product liquid carry out in knockout drum；The method removing the water in product liquid is that separatory separates.
9. the method for claim 1, it is characterised in that: described liquid hydrocarbon product removes the boiling point fraction less than 130 DEG C and the fraction more than 290 DEG C through distillation, obtains target product biology aerial kerosene.
10. method as claimed in claim 9, it is characterised in that: described biological aerial kerosene boiling point is between 130-290 DEG C, and freezing point, not higher than-40 DEG C, is mainly made up of isoparaffin.
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| CN114540077A (en) * | 2020-11-25 | 2022-05-27 | 中国石油天然气股份有限公司 | Preparation method of biological aviation kerosene |
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