CN107987868A - The method of grease substep deoxidation liquid fuel was prepared - Google Patents
The method of grease substep deoxidation liquid fuel was prepared Download PDFInfo
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- CN107987868A CN107987868A CN201610946837.4A CN201610946837A CN107987868A CN 107987868 A CN107987868 A CN 107987868A CN 201610946837 A CN201610946837 A CN 201610946837A CN 107987868 A CN107987868 A CN 107987868A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method of grease substep deoxidation liquid fuel was prepared, include the following steps：(1) grease esterification is converted into fatty acid methyl ester；(2) fatty acid methyl ester is converted into fatty alcohol with hydrogen under copper-based catalysts effect；And (3) fatty alcohol dehydration isomery under molecular sieve catalyst effect prepares alkene, isomerizing olefins content is more than 86% in the alkene, reaction temperature is 190 DEG C~240 DEG C, and the absolute pressure of reaction is 0.1MPa~0.5MPa, and the volume space velocity of fatty alcohol is 0.2h‑1~3h‑1, the molecular sieve catalyst is the one or more in ZSM 35, ZSM 5, ZSM 22, SAPO 31, SAPO 11, Y molecular sieve, beta-molecular sieve and modenite.The method of liquid fuel was prepared of the present invention, has the advantages that catalyst is cheap and easy to get, significantly reduces hydrogen consumption, volume increase glycerine.
Description
Technical field
The present invention relates to the method for grease deoxidation liquid fuel was prepared, belongs to biomass energy technology field.More specifically
It is to be related to grease through esterification, hydrogenation, dehydration/isomery substep deoxidation liquid fuel was prepared.
Background technology
Liquid fuel, such as gasoline, diesel oil, Aviation Fuel, are very important power fuel, are socio-economic development
Important substance basis.Long-term a large amount of liquid fuels prepared using fossil resource, produce the negative shadows such as greenhouse effects to environment
Ring.And the reserves of these non-renewable resources can be reduced year by year with continuous consumption.Reproducible animal and plant fat deoxidation
The liquid fuel of preparation, has calorific value high, has good burning performance, and excellent characteristics such as the similar, good compatibility of fossil fuel composition, by
Pay attention to extensive.Therefore, the research of countries in the world pay attention to day by day grease deoxidation liquid fuel was prepared technology.
Grease deoxidation liquid fuel was prepared, can be first by grease in vulcanization NiMo/ γ-Al2O3Or CoMo/ γ-Al2O3Urge
The lower hydrogenation deoxidation of agent effect is converted into alkane, and long chain alkane is again through having loaded the acidic molecular sieve of the noble metals such as Pt, Pd (such as
Pt/ZSM-22) catalytic isomerization liquid fuel was prepared.Change catalyst and isomerisation conditions, can selective main product gasoline, diesel oil
Or aviation fuel.For example, the oil hydrogenation of Canada's Canmet energy technologys center exploitation prepares the skill of high cetane number diesel oil
Art, and Neste Oil companies of Finland prepare diesel oil, and the life of UOP exploitations in the Porvoo grease catalytic hydrodeoxygenations established
Material aviation kerosine technology.
The hydrogenation catalyst of vulcanization can reduce catalytic activity because sulphur is lost in, and therefore produce sulphur pollution.Selection nickel,
The hydrogenation metal catalysts such as palladium, platinum, ruthenium, can be to avoid the relevant issues of sulphur.Recently, 102876350 A of CN disclose Ru systems and urge
Agent is catalyzed grease or aliphatic acid hydrogenation deoxidation prepares the technology of alkane class A fuel A.Or it will be directly hydrogenated with bifunctional catalyst
Deoxidation and cracking/isomery are coupling in single hop and complete, for example, Herskowitz etc. with Pt/SAPO-11 catalysis greases 300~
450 DEG C, 1~6MPa, 0.5~5.0h-1Under conditions of single step reaction obtain condensation point and the relatively low diesel component of cold filter plugging point.But
The noble metal catalysts such as Pt, Pd are selected to significantly improve the cost of catalyst.
Moreover, grease direct hydrogenation deoxidation, oxygen element removes in the form of complete hydrogenation is converted into water, this not only needs to disappear
Substantial amounts of hydrogen is consumed, and glycerine (hydrogenation produces propane) can be lost, for example, every mole of hard fatty acids glycerine ester through hydrogenation is completely de-
Oxygen theory hydrogen-consuming volume is not less than 12 moles.
Grease is first hydrolyzed (or esterification), be then catalyzed aliphatic acid (or fatty acid methyl ester) hydrogenation deoxidation and prepare liquid combustion
Material, can effectively discharge glycerine.For example, the method that fatty acid methyl ester disclosed in CN103725305A prepares liquid hydrocarbon fuel,
Fatty acid methyl ester hydrogenation deoxidation and is mainly cracked into/isomery under the effect of Ni/H β bifunctional catalysts, obtains liquid fuel.
Selective decarboxylation/the carbonyl of aliphatic acid (or fatty acid methyl ester) is catalyzed, makes oxygen element with CO2The form removing of/CO, can substantially reduce
Hydrogen consumption.Murzin etc. reports supporting Pt, the Al of Pd noble metals2O3Or SiO2Catalyst energy high selectivity is catalyzed aliphatic acid
Decarboxylation.Under conditions of 250~350 DEG C, 0.1~2MPa, stearic acid conversion ratio is more than 80%, and n-heptadecane selectivity is about
93%.Compared with hydrogenation deoxidation reacts, hydrogen gas consumption is remarkably decreased.The catalyst of fatty acid ester selectivity decarboxylation/carbonyl is also
Through report, for example, Pt/Al2O3It is catalyzed the non-hydrogenation deoxidation of methyl stearate.These pass through the non-hydrogenation deoxidation reaction pressure of decarboxylation/carbonyl
Power is usually less than 2MPa, can significantly reduce hydrogen consumption.These advantages cause the great interest of researcher.
Grease direct hydrogenation deoxidation, or obtain alkane through aliphatic acid or its methyl ester hydrogenation deoxidation or selective decarboxylation/decarbonylation
Hydrocarbon, is required for by isomerization to improve the cryogenic properties of fuel (cold filter plugging point, freezing point).Paraffin hydro isomery, not only because of cracking
Gaseous component is produced, reduces liquid fuel yield, and is required for using noble metals such as Pt, Pd, this can significantly improve catalyst
Cost.For this reason, the method that CN101331210A provides preposition isomery, it is different to carry out skeleton by unrighted acid or its ester
Structure, then carries out hydrogenation deoxidation again, to obtain the excellent liquid fuel of cryogenic properties.
CN101484552A discloses a kind of method for manufacturing base oil, and aliphatic acid and higher alcohols mainly are generated ester,
Then hydrogenate again as alcohol, alcohol dehydration under aluminium oxide or the aluminium oxide catalyst effect for having loaded zirconium oxide be alpha-olefin, then general
Alpha-olefin is oligomeric, base oil is made in hydrogenation.The patent mainly by aluminium oxide or loaded zirconium oxide aluminium oxide catalyst will
Fatty alcohol is converted into alpha-olefin, alpha-olefin be it is oligomeric prepare the suitable feedstock of lubricating oil, but straight-chain hydrocarbons is still, as fuel
Its cryogenic properties is to be improved.
The content of the invention
It is existing to overcome it is a primary object of the present invention to provide a kind of method of grease substep deoxidation liquid fuel was prepared
The problem of noble metal catalyst used is of high cost in liquid fuel was prepared method, severe reaction conditions.
A kind of method of grease substep deoxidation liquid fuel was prepared provided by the invention, includes the following steps：
(1) grease esterification is converted into fatty acid methyl ester；
(2) fatty acid methyl ester is converted into fatty alcohol with hydrogen under copper-based catalysts effect；And
(3) fatty alcohol dehydration isomery under molecular sieve catalyst effect prepares alkene, isomeric olefine content in the alkene
More than 86%.
To improve liquid fuel property, isomeric olefine can be further hydrogenated with or rectifying separation.
The method of grease substep deoxidation liquid fuel was prepared of the present invention, wherein, the grease is animal and plant fat,
The total content of fatty glyceride and free fatty is more than 90% in the animal and plant fat, fat in the fatty glyceride
Fat carbon chain lengths are C12~C24Content be more than 80%.
The method of grease substep deoxidation liquid fuel was prepared of the present invention, wherein, sulphur, phosphorus, nitrogen, chlorine in the grease
100ppm, 200ppm, 300ppm, 400ppm and 800ppm are respectively smaller than with the content of metal impurities.
The method of grease substep deoxidation liquid fuel was prepared of the present invention, wherein, the grease methyl esters turns to grease
Fatty acid methyl ester is converted into methanol reaction.The grease methyl esters turns to homogeneous acid catalytic reaction, heterogeneous acid catalysts react,
Phase base catalyzed reactions, heterogeneous base catalyzed reactions or supercritical reaction.
The method of grease substep deoxidation liquid fuel was prepared of the present invention, wherein, the reaction condition of the step (2)
For：Use the hydrogenation catalyst using copper as metal active centres, 180 DEG C~280 DEG C of reaction temperature；The absolute pressure 2MPa of reaction
~6MPa；The molar ratio 5 of hydrogen and fatty acid methyl ester:1~20:1；The volume space velocity 0.4h of fatty acid methyl ester-1~2h-1.It is described
Hydrogenation catalyst using copper as metal active centres, can participate in the metals such as zinc, iron, chromium, barium, manganese, and be dispersed in Al2O3、SiO2
Deng on high specific surface carrier to improve catalyst activity.
The method of grease substep deoxidation liquid fuel was prepared of the present invention, wherein, the fatty dehydration of alcohols of the step (3)
The reaction temperature of isomery is 190 DEG C~240 DEG C, is preferably 190 DEG C~200 DEG C；The absolute pressure of reaction for 0.1MPa~
0.5MPa, is preferably 0.1MPa~0.3MPa；The volume space velocity of fatty alcohol is 0.2h-1~3h-1。
The method of grease substep deoxidation liquid fuel was prepared of the present invention, wherein, molecular sieve is urged in the step (3)
Agent be ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, beta-molecular sieve and modenite in one kind or
It is several.
Beneficial effects of the present invention：
1st, in the technology of existing oil and fat preparation liquid fuel, the improvement of catalyst is mainly directed to, to enable grease to
Alkane is hydrogenated to, then carrying out isomerization reaction in the case where the bifunctional catalyst for having loaded noble metal acts on obtains liquid fuel；
And the present invention mainly employs multistep and gently reacts, alkene is converted into using acidic molecular sieve catalysis dehydration of alcohols, and it is synchronous and heterogeneous
Change obtains isomeric olefine, and used catalyst is commercial molecular sieve catalyst cheap and easy to get, and present invention preparation is highly different
The liquid fuel of structure；
2nd, the present invention uses ester hydrogenation to significantly reduce hydrogen compared to ester direct hydrogenation deoxidation for alcohol and then the mode being dehydrated
Consumption, reduces material consumption, and increases production the higher glycerol product of added value.
Embodiment
The method of the present invention is further illustrated below by embodiment, the experimental method used in following embodiments
Unless otherwise specified, it is conventional method.
Grease of the present invention can be butter, lard, chicken fat, rapeseed oil, soybean oil, cottonseed oil, palm oil, corn
Oil, rubber seed oil, waste oil from restaurant, gutter oil, acidification oil, the oil that becomes sour etc..
In order to improve the quality of liquid fuel, simplify follow-up refinery practice, and extend the service life of catalyst, it should appropriate drop
Sulphur in Low grease, phosphorus, nitrogen, the content of chlorine and metal impurities, grease is after refined, sulphur, phosphorus, nitrogen, chlorine and metal impurities
Content should be respectively smaller than 100ppm, 200ppm, 300ppm, 400ppm and 800ppm.
Fatty acid methyl ester and hydrogen are reacted to the hydrogenation catalyst that copper is metal active centres, can participate in zinc, iron,
The metals such as chromium, barium, manganese, and it is dispersed in Al2O3、SiO2Deng on high specific surface carrier to improve catalyst activity.
The reactor of fatty acid methyl ester and hydrogen catalytic hydrogenation, can be that reaction kettle, moving-burden bed reactor and fixed bed are anti-
Answer device etc., preferably fixed-bed tube reactor.
Heterogeneous acid catalyst, refers to that solubility is less than 0.1%, and NH in the reaction system3Desorption temperature after absorption
Spend the acidic catalyst for 150 DEG C -600 DEG C.It is preferred that ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, β
Molecular sieve and modenite.
The reactor of fatty dehydration of alcohols isomery, can be reaction kettle, tower reactor and fixed bed reactors, preferably tower
Reactor or fixed bed reactors.
The liquid fuel component that above method step (3) obtains is mainly C6–C18Alkene, can be directly added into liquid combustion
Used in material, can continue to carry out hydrogenation step is then branched alkane adds liquid fuel；Wherein isomeric olefine or branch
Change the content of alkane more than 86%, the presence of isomeric olefine or branched alkane can improve the octane number of liquid fuel.
The materials, reagents and the like used in the following examples, unless otherwise specified, commercially buys.
Embodiment 1
Sodium methoxide (dosage is the 0.5% of oil quality) catalysis purified soyabean oil and methanol (molar ratio of methanol to oil 6：1) exist
60 DEG C of reaction 2h, by grease esterification.After separation, the content of fatty acid methyl ester is 97%.
Fatty acid methyl ester passes through the tubular reactor catalytic hydrogenation reaction for having loaded commercial copper zinc-aluminium hydrogenation catalyst, technique
Condition is：180 DEG C, 6MPa, the molar ratio of hydrogen and fatty acid methyl ester be 20:1st, volume space velocity 0.4h-1.Fatty acid methyl ester is urged
Change the fatty alcohol content that hydrogenation reaction obtains and reach 98%.
In the tubular reactor for having loaded ZSM-35 molecular sieve catalyst, the process conditions of fatty dehydration of alcohols isomerization reaction
For 240 DEG C, 0.1MPa, fatty alcohol volume space velocity be 0.3h-1.Reaction obtains C6-C18Isomeric olefine content reach 96%
Liquid fuel.
Embodiment 2
The rubber seed oil that acid number is 30mgKOH/g reacts 1h with methanol at 240 DEG C, by grease esterification.Separate and recover first
After alcohol, the content of fatty acid methyl ester is 90%.
Fatty acid methyl ester passes through the tubular reactor catalytic hydrogenation reaction for having loaded commercial Cu-Cr catalyst, process conditions
For：280 DEG C, 2MPa, the molar ratio of hydrogen and fatty acid methyl ester be 5:1st, volume space velocity 2h-1.Fatty acid methyl ester catalytic hydrogenation
React obtained fatty alcohol content and reach 92%.
In the tower reactor for having loaded ZSM-5 molecular sieve catalyst, the process conditions of fatty dehydration of alcohols/isomerization reaction
For 190 DEG C, 0.2MPa, fatty alcohol volume space velocity be 1.6h-1.Reaction obtains C6-C18Isomeric olefine content reach 90%
Liquid fuel.
Embodiment 3
The waste oil from restaurant that the catalysis of ZSM-5 acidic molecular sieves is become sour reacts 2h with methanol at 160 DEG C, by grease esterification.
After separation, the content of fatty acid methyl ester is 92%.
Fatty acid methyl ester passes through the tubular reactor catalytic hydrogenation reaction for having loaded commercial CuZnAl catalyst, process conditions
For：210 DEG C, 4MPa, the molar ratio of hydrogen and fatty acid methyl ester be 8:1st, volume space velocity 1h-1.Fatty acid methyl ester catalytic hydrogenation
React obtained fatty alcohol content and reach 95%.
In the tubular reactor for having loaded ZSM-22 molecular sieve catalysts, the technique bar of fatty dehydration of alcohols/isomerization reaction
Part is 200 DEG C, 0.3MPa, the volume space velocity of fatty alcohol are 0.8h-1.Reaction obtains C6-C18Isomeric olefine content reach 86%
Liquid fuel.
Embodiment 4
Butter react 2h with methanol in 260 DEG C, 6MPa, by grease esterification.After separating and recovering methanol, fatty acid methyl
The content of ester is 96%.
The tubular reactor catalytic hydrogenation reaction that fatty acid methyl ester has had the CuZnAl catalyst of iron 1% by having loaded ginseng,
Process conditions are：240 DEG C, 4MPa, the molar ratio of hydrogen and fatty acid methyl ester be 5:1st, volume space velocity 1.5h-1.Fatty acid methyl
The fatty alcohol content that ester catalysis hydrogenation reaction obtains reaches 94%.
In the tubular reactor for having loaded SAPO-31 molecular sieve catalysts, the technique bar of fatty dehydration of alcohols/isomerization reaction
Part is 220 DEG C, 0.5MPa, the volume space velocity of fatty alcohol are 1.6h-1.Reaction obtains C6-C18Isomeric olefine content reach 94%
Liquid fuel.
Embodiment 5
Cottonseed oil reacts 1.5h with methanol at 210 DEG C, by grease esterification.After separating and recovering methanol, fatty acid methyl
The content of ester is 94%.
Fatty acid methyl ester passes through the tubular reactor catalytic hydrogenation reaction for having loaded commercial CuZnAl catalyst, process conditions
For：250 DEG C, 5MPa, the molar ratio of hydrogen and fatty acid methyl ester be 7:1st, volume space velocity 0.6h-1.Fatty acid methyl ester catalysis adds
The fatty alcohol content that hydrogen reacts reaches 97%.
Loading ZSM-5 and ZSM-22 (1：1 mixing) molecular sieve catalyst tubular reactor in, fatty dehydration of alcohols/
The process conditions of isomerization reaction are 200 DEG C, 0.1MPa, the volume space velocity of fatty alcohol are 2.5h-1.Reaction obtains C6-C18Isomery
Olefin(e) centent reaches 98% liquid fuel.
Beneficial effects of the present invention：
1st, in the technology of existing oil and fat preparation liquid fuel, the improvement of catalyst is mainly directed to, to enable grease to
Alkane is hydrogenated to, then carrying out isomerization reaction in the case where the bifunctional catalyst for having loaded noble metal acts on obtains liquid fuel；
And the present invention mainly employs multistep and gently reacts, alkene is converted into using acidic molecular sieve catalysis dehydration of alcohols, and it is synchronous and heterogeneous
Change obtains isomeric olefine, and used catalyst is commercial molecular sieve catalyst cheap and easy to get, and present invention preparation is highly different
(reaction obtains C to the liquid fuel of structure6-C18Isomeric olefine content more than 86%)；
2nd, the present invention uses ester hydrogenation to significantly reduce hydrogen compared to ester direct hydrogenation deoxidation for alcohol and then the mode being dehydrated
Consumption, reduces material consumption, and increases production the higher glycerol product of added value.
Certainly, the present invention can also have other various embodiments, ripe in the case of without departing substantially from spirit of the invention and its essence
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
- A kind of 1. method of grease substep deoxidation liquid fuel was prepared, it is characterised in that this method comprises the following steps：(1) grease esterification is converted into fatty acid methyl ester；(2) fatty acid methyl ester is converted into fatty alcohol with hydrogen under copper-based catalysts effect；And(3) fatty alcohol dehydration isomery under molecular sieve catalyst effect prepares alkene, and isomeric olefine content exceedes in the alkene 86%.
- 2. the method for grease substep deoxidation liquid fuel was prepared according to claim 1, it is characterised in that the grease is Animal and plant fat, the total content of fatty glyceride and free fatty is more than 90% in the animal and plant fat, the fat Fatty carbon chain length is C in acid glyceride12~C24Content be more than 80%.
- 3. the method for grease substep deoxidation liquid fuel was prepared according to claim 2, it is characterised in that in the grease Sulphur, phosphorus, nitrogen, the content of chlorine and metal impurities are respectively smaller than 100ppm, 200ppm, 300ppm, 400ppm and 800ppm.
- 4. the method for grease substep deoxidation liquid fuel was prepared according to claim 1, it is characterised in that the grease first It is esterified and is converted into fatty acid methyl ester for grease and methanol reaction.
- 5. the method for grease substep deoxidation liquid fuel was prepared according to claim 4, it is characterised in that the grease first It is esterified as homogeneous acid catalyzed reaction, heterogeneous acid catalysts reaction, homogeneous base catalyzed reactions, heterogeneous base catalyzed reactions or overcritical Reaction.
- 6. the method for grease substep deoxidation liquid fuel was prepared according to claim 1, it is characterised in that the step (2) reaction condition is：Use the hydrogenation catalyst using copper as metal active centres, 180 DEG C~280 DEG C of reaction temperature, reaction Absolute pressure 2MPa~6MPa, the molar ratio 5 of hydrogen and fatty acid methyl ester:1~20:1, the volume space velocity of fatty acid methyl ester 0.4h-1~2h-1。
- 7. the method for grease substep deoxidation liquid fuel was prepared according to claim 1, it is characterised in that the step (3) molecular sieve catalyst is ZSM-35, ZSM-5, ZSM-22, SAPO-31, SAPO-11, Y molecular sieve, beta-molecular sieve and mercerising in One or more in zeolite.
- 8. the method for grease substep deoxidation liquid fuel was prepared according to any one of claims 1 to 7, it is characterised in that The reaction temperature of the fatty dehydration of alcohols isomery of the step (3) is 190 DEG C~240 DEG C, the absolute pressure of reaction for 0.1MPa~ 0.5MPa, the volume space velocity of fatty alcohol is 0.2h-1~3h-1。
- 9. the method for grease substep deoxidation liquid fuel was prepared according to claim 8, it is characterised in that the step (3) reaction temperature of fatty dehydration of alcohols isomery is 190 DEG C~220 DEG C, and the absolute pressure of reaction is 0.1MPa~0.3MPa, fat The volume space velocity of alcohol is 0.2h-1~3h-1。
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Cited By (5)
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| CN113004953A (en) * | 2021-03-16 | 2021-06-22 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN114480024A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel from grease |
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| CN116333782A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by grease selective hydrodeoxygenation |
| WO2023116168A1 (en) * | 2021-12-23 | 2023-06-29 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by means of selective catalytic deoxidation of grease, and liquid fuel |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114480024A (en) * | 2020-10-27 | 2022-05-13 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel from grease |
| CN113004953A (en) * | 2021-03-16 | 2021-06-22 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN113004953B (en) * | 2021-03-16 | 2022-05-20 | 中国人民解放军空军勤务学院 | Method for preparing biological aviation fuel by using coconut oil |
| CN116333782A (en) * | 2021-12-23 | 2023-06-27 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by grease selective hydrodeoxygenation |
| WO2023116169A1 (en) * | 2021-12-23 | 2023-06-29 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by means of selective catalytic deoxidation of grease, and liquid fuel |
| WO2023116168A1 (en) * | 2021-12-23 | 2023-06-29 | 中国石油天然气股份有限公司 | Method for preparing liquid fuel by means of selective catalytic deoxidation of grease, and liquid fuel |
| CN114574233A (en) * | 2022-03-11 | 2022-06-03 | 福州大学化肥催化剂国家工程研究中心 | Method for preparing second-generation biodiesel from acidified oil |
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